JP6562378B2 - Liquid gasket for electronic equipment - Google Patents

Description

  The present invention relates to an in-situ molded liquid gasket for electronic equipment containing an oxyalkylene polymer having a hydrolyzable group bonded to a silicon atom and having a silicon-containing group that can be crosslinked by forming a siloxane bond. Hereinafter, a silicon-containing group that has a hydrolyzable group bonded to a silicon atom and can be cross-linked by forming a siloxane bond is also referred to as a cross-linkable silicon group.

  Electronic devices such as mobile phones, smartphones, tablets, mobile PCs, MP3 players, digital video recorders, digital cameras, and hard disk drives protect internal electronic circuits, memory, CPU, and battery parts from external dust and moisture. For this purpose, these parts are usually contained in two housing members such as a main body and a lid, and the two housing members are sealed by a sealing means such as an O-ring provided around the housing member. In addition, the liquid crystal display member, the operation member such as a button, the battery, and the like may be individually sealed by a sealing means provided around the component. As the sealing means, a solid gasket, a liquid gasket, or the like is used.

  In the electronic device manufacturing process, when a defective product is generated, the defective portion is replaced and repaired. Such reworking is called reworking, and if reworking is necessary after sealing the housing member described above, the sealing must be removed.

  A solid gasket such as an O-ring is an elastic sealing material molded in advance, and is tightened and sealed with a screw or the like. In this case, the gasket can be easily removed by removing a screw or the like. Therefore, rework work is easy when a solid gasket is used. However, solid gaskets are expensive because they are manufactured using a mold, and there is a problem that it is difficult to cope with diversification of gasket shapes.

  Liquid gaskets (on-site molded gaskets) are those that apply uncured liquid material to the area to be sealed and harden it into a gasket, called FIPG (Formed In Place Gasket) and CIPG (Cured In Place Gasket) ) Is called. In these gaskets, no mold is required.

  FIPG is a method in which an uncured liquid material is applied to a portion to be sealed, a housing member is sandwiched, and then cured. The sealing performance is excellent because it is a seal by adhesion, but usually the cured product is strongly adhered to the substrate, and the removal of the gasket is not easy. For this reason, FIPG is not a suitable method for rework work. In addition, since the liquid material is sandwiched between the housing members, there is a case in which a portion of the housing member that protrudes is not desired when the housing member is sandwiched.

  CIPG is a method in which an uncured liquid material is applied to a portion to be sealed and cured before sandwiching the housing member. Patent Document 1 discloses a photocurable sealing material composition that can be used as CIPG. Since the sealing agent disclosed in Patent Document 1 sandwiches the housing member after the sealing agent is cured, the reworking work is easy, the shape retention is excellent due to photocuring, and a seal is not desired when the housing member is sandwiched. It is thought that it does not protrude into the part. However, generally, CIPG cannot obtain a sufficient sealing performance unless it is subjected to processes such as screw tightening and pressure tightening.

  Among these gaskets, FIPG has the best sealing performance but is not suitable for rework. However, if there is a FIPG that is excellent in reworkability, it is considered very useful. That is, the housing member can be removed with a small force, and the gasket does not break at the time of removal and remains on one housing member. After reworking, the gasket can be used as it is to reconnect the housing member. The FIPG is capable of maintaining sealing performance such as waterproof performance.

  Patent Document 2 discloses a waterproof sealing method for small portable electronic devices using a curable liquid composition containing an oxyalkylene polymer having a crosslinkable silicon group (Patent Document 2, Example 1). The oxyalkylene polymer having a crosslinkable silicon group is liquid at room temperature, and crosslinks at room temperature by the action of moisture such as moisture in the air to produce a cured product such as rubber. For this reason, Patent Document 2 discloses that a curable liquid composition containing an oxyalkylene polymer having a crosslinkable silicon group can be suitably used as a FIPG used in a small portable electronic device. Further, Example 1 of Patent Document 2 discloses that the peeling mode between the cured gasket and the housing member is interface peeling. This is because it is possible to remove the housing member with a small force, and it is considered that it is excellent in reworkability because it remains in one housing member without rupturing at the time of removal. However, it is difficult to maintain the sealing performance such as the initial waterproof performance even after recombination. This is because the cured gasket does not have adhesiveness to a base material such as a housing member so that the peeled cured adhesive does not have adhesiveness.

JP 2009-96839 A JP 2011-086817 A

  The problem to be solved by the present invention is FIPG for electronic equipment using a curable liquid composition containing a crosslinkable silicon group-containing organic polymer, which is exposed to air before irradiation with active energy rays. Therefore, it is intended to provide a liquid gasket for electronic equipment that can take a sufficient working time since it does not cure, and that can be cured in a short time while having a sufficient bonding time after irradiation with active energy rays.

  In addition, in a housing member joined using a liquid gasket, when the housing member is sandwiched after irradiation with active energy rays, the housing member does not protrude to an undesired portion and can be removed with a small force. It is possible to provide a liquid gasket which can be re-joined by using the gasket as it is after reworking, and can maintain the sealing performance such as the initial waterproof performance even after re-joining.

  In order to solve the above problems, a liquid gasket for electronic equipment according to the present invention relates to the following invention.

(1) (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, (C) a silicon compound having a Si-F bond, (D) a compound having a photoradically polymerizable vinyl group A liquid gasket for electronic equipment.
(2) The liquid gasket for electronic equipment according to (1), further comprising (E) a tackifier resin.
(3) The (A) crosslinkable silicon group-containing organic polymer is one selected from the group consisting of a crosslinkable silicon group-containing polyoxyalkylene polymer and a crosslinkable silicon group-containing (meth) acrylic polymer. It is the above, The liquid gasket for electronic devices as described in any one of (1)-(2) characterized by the above-mentioned.
(4) The liquid gasket for electronic equipment according to any one of (1) to (3), wherein the photobase generator (B) is a photolatent tertiary amine.
(5) A product manufactured using the liquid gasket for electronic equipment according to any one of (1) to (4).
(6) A reworking method for an electronic device, wherein (A) the on-site molding liquid gasket for the electronic device is (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, (C) Si A step of preparing an in-situ molded liquid gasket containing a silicon compound having a -F bond, (D) a compound having a radical photopolymerizable vinyl group, and (b) one of electronic devices in an uncured state of the liquid gasket. Applying to the part of the housing member to be sealed, irradiating the active energy ray and sandwiching the other housing member, (c) Removing the housing member of the electronic device that requires rework after curing, and replacing the internal parts And (d) using the cured liquid gasket as a gasket as it is and resealing the housing member. Work method.

  The liquid gasket for electronic equipment of the present invention does not cure even when exposed to air before irradiation with active energy rays, so that sufficient work time can be taken, and sufficient time for bonding after irradiation with active energy rays is sufficient. In the housing member joined using this FIPG, when the housing member is sandwiched after irradiation with active energy rays, the housing member does not protrude to an undesired portion. The housing member can be removed with a small force, and after reworking, the gasket can be used as it is to reconnect the housing member, and the sealing performance such as the initial waterproof performance can be maintained even after the reconnection.

  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 liquid gasket for electronic equipment of the present invention includes (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, (C) a silicon compound having a Si-F bond, and (D) a photoradical. And a compound having a polymerizable vinyl group.

  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 hydrocarbons Are shown, when the R ¹ there are two or more, they may be the same or may be different. X represents a hydroxyl group or a hydrolyzable group, and when two or more 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 an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ¹ ₃ SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.

  The hydrolyzable group represented by X is not particularly limited as long as it is other than the F atom, and may be any conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxyl group, an amide group, and an aminooxy group are more preferable. An alkoxyl group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among alkoxyl groups, those having fewer carbon atoms have higher reactivity, and the reactivity decreases 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. A silyl group [—SiR ¹ (OR) ₂ ] may be mentioned, and due to its high reactivity, a trialkoxysilyl group [—Si (OR) ₃ ] is preferable, and a 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.

  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, and polyoxyalkylene heavy compounds having a hydroxyl group. 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, the following vinyl monomer 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 (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferably, it is a (meth) acrylic acid ester-based polymer using one or two or more (meth) acrylic acid alkyl ester monomers and optionally using other (meth) acrylic acid monomers, 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 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 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.

  Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group, and an addition-fragmentation chain transfer (RAFT) polymerization method, Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferable. 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 (Japanese Patent Laid-Open No. 2001-40037) are also suitable.

  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, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms), and a (meth) acrylate monomer unit represented by the following general formula (6):
—CH ₂ —C (R ³ ) (COOR ⁵ ) — (6)
(Wherein R ³ is the same as described above, and R ⁵ represents an alkyl group having 6 or more carbon atoms). A copolymer comprising 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, etc., having 1 to 5 carbon atoms, preferably 1 to 4, 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.

R ^{5 in the} general formula (6) is, for example, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group and the like having 6 or more carbon atoms, usually 7 to 30, preferably 8 to 20 Long chain alkyl groups. 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 the acrylate polymer, for example, it has a crosslinkable silicon group described in JP-A-63-112642, and the molecular chain has substantially (1) 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 (2) 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 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.

  In the present invention, the (B) photobase generator acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer when irradiated with light. 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. Organic acid and base salts that decompose by decarboxylation by irradiation with active energy rays such as light and infrared, (2) Compounds that decompose by intranuclear nucleophilic substitution reaction or rearrangement reaction and release amines, or ( 3) Known photobase generators such as those that cause some chemical reaction upon release of energy rays such as ultraviolet rays, visible light, and infrared rays to release bases can be used.

(B) Although it does not specifically limit as a base generate | occur | produced from a photobase generator, Organic bases, such as an amine compound, are preferable, for example, 1st, such as ethylamine, propylamine, octylamine, cyclohexylamine, 1, 5- diaminopentane etc. Primary 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 groups Amines having a group; tertiary alkylamines such as trimethylamine, triethylamine, tributylamine, 1,8-diazabicyclo [2.2.2] octane (DABCO); tertiary heterocyclic groups 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); and phosphazene derivatives such as tris (dimethylamino) (methylimino) phosphorane described in JP 2011-80032 A, and amine compounds having a tertiary amino group are preferred and strong bases Amidines and phosphazene derivatives are more preferred. As the amidines, both acyclic amidines and cyclic amidines can be used, and cyclic amidines are more preferable.
These bases may be used alone or in combination of two or more.

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

  Among the non-cyclic amidine compounds, when a photobase generator that generates an aryl-substituted guanidine compound or an aryl-substituted biguanide compound such as phenylguanidine, 1-o-tolylbiguanide or 1-phenylbiguanide is used, When used as a catalyst for the coalesced (A), it is preferable because it shows a tendency that the curability of the surface is good and a tendency that the adhesiveness of the resulting cured product becomes good.

  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 compound include 1,5,7-triaza-bicyclo [4.4.0] dec-5-ene, 7-methyl-1,5, described in JP2011-80032A. 7-triaza-bicyclo [4.4.0] dec-5-ene, 7-ethyl-1,5,7-triaza-bicyclo [44.0] dec-5-ene, 7-isopropyl-1, 5,7-triaza-bicyclo [4.4.0] dec-5-ene and the like.

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

  Examples of the imidazole compound 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 and the like Can be mentioned.

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

  Examples of the 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, 5-diazabicyclo [4.4.0] decene- 4-phenyl-1,5-diazabicyclo [4.4.0] decene-5, 1,8-diazabicyclo [5.3.0] decene-7, 1,8-diazabicyclo [7.4.0] tridecene -8,1,8-diazabicyclo [5.4.0] undecene-7,6-methylbutylamino-1,8-diazabicyclo [5.4.0] undecene-7,6-methyloctylamino-1,8 -Diazabicyclo [5.4.0] undecene-7,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7,6-butylbenzylamino-1,8-diazabicyclo [5.4. 0] undecene-7,6-dihexylamino-1,8-diazabicyclo [5.4.0] undecene-7,9-methyl-1,8-diazabicyclo [5.4.0] undecene-7,9-me 1,8-diazabicyclo [5.3.0] decene-7, 1,6-diazabicyclo [5.5.0] dodecene-6, 1,7-diazabicyclo [6.5.0] tridecene-7, 1,8-diazabicyclo [7.5.0] tetradecene-8, 1,10-diazabicyclo [7.3.0] dodecene-9, 1,10-diazabicyclo [7.4.0] tridecene-9, 1, 14-diazabicyclo [11.3.0] hexadecene-13, 1,14-diazabicyclo [11.4.0] heptadecene-13, and the like.

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

  As the (B) photobase generator used in the present invention, a known photobase generator can be used, and a photolatent amine compound that generates an amine compound by the action of active energy rays is preferable. The photolatent amine compound includes a photolatent primary amine that generates an amine compound having a primary amino group by the action of active energy rays, and an amine compound having a secondary amino group by the action of active energy rays. Either a photolatent secondary amine that generates a photolatent or a photolatent tertiary amine that generates an amine compound having a tertiary amino group by the action of active energy rays can be used, but the generated base is high. A photolatent tertiary amine is more preferred from the viewpoint of exhibiting catalytic activity.

Examples of the photolatent primary amine and 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) hexyldiamine, o- Nitrobenzyl N-carbamate cyclohexyl, 2-nitrobenzylcyclohexyl carbamate, 1- (2-nitro Phenyl) ethylcyclohexyl carbamate, 2,6-dinitrobenzylcyclohexyl carbamate, 1- (2,6-dinitrophenyl) ethylcyclohexyl carbamate, 1- (3,5-dimethoxyphenyl) -1-methylethylcyclohexyl carbamate, bis [[ (2-Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, ortho-nitrobenzyl urethane compounds such as N- (2-nitrobenzyloxycarbonyl) pyrrolidine; α, α-dimethyl-3,5-dimethoxybenzylcyclohexyl Dimethoxybenzyl urethane compounds such as carbamate and 3,5-dimethoxybenzylcyclohexylcarbamate; 1- (3,5-dimethoxybenzoyl) -1- (3,5-dimethoxyphenyl) methylcyclohexyl Carbamate, 2-hydroxy-2-phenylacetophenone cyclohexyl carbamate, dibenzoin isophorone dicarbamate, 1-benzoyl-1-phenylmethylcyclohexyl carbamate, 2-benzoyl-2-hydroxy-2-phenylethylcyclohexyl carbamate, etc. O-acyloximes such as o-benzylcarbonyl-N- (1-phenylethylidene) hydroxylamine; [(pentane-1,5-diyl) biscarbamoyl] bis (diphenylmethylidenehydroxylamine), α- (cyclohexyl) O-carbamoyloximes such as carbamoyloxyimino) -α- (4-methoxyphenyl) acetonitrile; N- (octylcarbamoyloxy) phthalimide, N- (cyclohe N-hydroxyimidocarbamates such as xylcarbamoyloxy) succinimide; formanilide derivatives such as 4,4′-methylenebis (formalinide); N-cyclohexyl-2-naphthalenesulfonamide, N-cyclohexyl-p-toluenesulfonamide, etc. And aromatic amines such as cobalt amine complexes such as Co (NH ₂ C ₃ H ₇ ) Br + ClO ₄ ^— .

  Examples of the photolatent 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 light. Examples thereof include benzyloxycarbonylamine derivatives that generate amidine, and salts of carboxylic acid and tertiary amine.

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

In the formula (I), R ⁵¹ is an aromatic or heteroaromatic group, and R ⁵¹ is an aromatic group (which is unsubstituted or C ₁ -C ₁₈ alkyl, 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, wherein R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ and R ⁶² are hydrogen or C ₁ -C ₁₈ alkyl), preferably phenyl, Naphthyl, phenanthryl, anthracyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2, 3-b] thienyl, thiatrenyl, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolidinyl, isoquinolyl, quinolyl Phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, terphenyl, stilbenyl 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 18} alkyl, then R ⁵³ is further a group —CO—R ^{64 where} R ⁶⁴ is C ₁ -C ₁₈ alkyl or phenyl; or R ⁵¹ and R ⁵³ are Together with the C atom to which the carbonyl group and R ⁵³ are bonded, a benzocyclopentanone group is formed.
R ⁵⁴ and R ⁵⁶ together form a C ₂ -C ₁₂ alkylene bridge that is unsubstituted or substituted by one or more C ₁ -C ₄ alkyl groups. R ⁵⁵ and ^{R 57,} taken ^together, independently of ^{R 54} and ^{R 56,} _C 2 -C which is unsubstituted or substituted by one or more _C 1 -C ₄ alkyl group _{A 12} alkylene bridge is formed. R ⁵⁴ and R ⁵⁶ are preferably taken together to form a C ₃ alkylene bridge, and R ⁵⁵ and R ⁵⁷ are preferably taken together are propylene or pentylene.

In the formula ^{(II) ~ (IV),} R 51 ~R 53 is the same as ^R 51 ^{to R 53} of each of the formula (I).
R ⁶⁶ is an alkyl group having 1 to 12 carbon atoms; —OH, —alkoxy having 1 to 4 carbon atoms, —CN, or —COO (alkyl having 1 to 4 carbon atoms); 4 represents an alkyl group, or R ⁶⁶ represents an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a phenyl-alkyl group having 1 to 3 carbon atoms. R ⁶⁷ is an alkyl group having 1 to 12 carbon atoms; or —OH, —an alkoxy group having 1 to 4 carbon atoms, —CN or —COO (alkyl having 1 to 4 carbon atoms). Represents an alkyl group having 2 to 4 or R ⁶⁷ is an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl-alkyl group having 1 to 3 carbon atoms, or unsubstituted Or a phenyl group substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or —COO (alkyl having 1 to 4 carbon atoms), or R ⁶⁷ is In combination with RR ⁶⁶ , an alkylene group having 1 to 7 carbon atoms, a phenyl-alkylene group having 1 to 4 carbon atoms, an o-xylylene group, a 2-butenylene group, or an oxygen group having 2 or 3 carbon atoms. Represents a oxaalkylene group, or R ⁶⁶ and R ⁶⁷ together represent a C 4-7 alkylene group which may be interrupted by —O—, —S— or —CO—, or R ⁶⁶ and R ⁶⁷ together represents OH, an alkoxy group having 1 to 4 carbon atoms, or an alkylene group having 3 to 7 carbon atoms that can be substituted with —COO (alkyl having 1 to 4 carbon atoms). When a plurality of R ⁶⁶ and R ⁶⁷ are present, they may be the same or different.
Y ¹ represents a divalent group represented by the following formula (V), a divalent group represented by —N (R ⁶⁸ ) — or —N (R ⁶⁸ ) —R ⁶⁹ —N (R ⁶⁸ ) —, R ⁶⁸ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, a phenyl-alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or a phenyl group. , R ⁶⁹ represents an unbranched or branched alkylene group of 2 to 16 carbon atoms which can be interrupted by one or more —O— or —S—.
Y ² represents an alkylene group having 1 to 6 carbon atoms, a cyclohexylene group or a direct bond.

  Examples of the α-aminoketone compound represented by the formula (I) include 5- (4′-phenyl) phenacyl-1,5-diazabicyclo [4.3.0] nonane described in JP-A No. 2001-512421. 5-phenacyl-1,5-diazabicyclo [4.3.0] nonane, 5-naphthoylmethyl-1,5-diazabicyclo [4.3.0] nonane, 5- (1′-pyrenylcarbonylmethyl)- 1,5-diazabicyclo [4.3.0] nonane, 5- (4′-nitro) phenacyl-1,5-diazabicyclo [4.3.0] nonane, 5- (2 ′, 4′-dimethoxy) phenacyl -1,5-diazabicyclo [4.3.0] nonane, 5- (9′-anthroylmethyl) -1,5-diazabicyclo [4.3.0] nonane, 8- (4′-phenyl) phenacyl- (1 8- diazabicyclo [5.4.0] -7-undecene), and the like.

  Examples of the α-aminoketone compound represented by the formula (II) include 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane (Irgacure 907), 2-benzyl- described in JP-A-11-71450. 2-dimethylamino-1- (4-morpholinophenyl) -butanone (Irgacure 369), 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone (Irgacure 379), etc. Can be mentioned.

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

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

In the formula ^{(VI), R} 51 ~R ⁵³ is the same as ^R 51 ^{to R 53} of each of the formula (I).
R ^{70 to} R ⁷² are each independently of one another hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₃ -C ₁₈ alkynyl or phenyl; or R ⁷⁰ and R ⁷¹ and / or R ⁷² And R ⁷¹ independently of one another form a C _{2 to} C ₁₂ alkylene bridge; or R ^{70 to} R ⁷² together with the nitrogen atom to which they are 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} of said formula (I), l and q is a number from 2 to 12 each, independently of one another.

  Specific examples of the α-ammonium ketone derivatives include, for example, phenacyltriethylammonium tetraphenylborate, (4-methoxyphenacyl) triethylammonium tetraphenylborate described in JP-T-2001-513765 and WO2005 / 014696. -Phenacyl- (1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate, (1,4-phenacyl-1,4-diazoniabicyclo [2.2.2] octane) bis ( Tetraphenylborate), 1-naphthoylmethyl- (1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate, 1- (4′-phenyl) phenacyl- (1-azonia-4- Azabicyclo [2.2.2] octane) tetraphenylbo 5- (4′-phenyl) phenacyl- (5-azonia-1-azabicyclo [4.3.0] -5-nonene) tetraphenylborate, 5- (4′-methoxy) phenacyl- (5- Azonia-1-azabicyclo [4.3.0] -5-nonene) tetraphenylborate, 5- (4′-nitro) phenacyl- (5-azonia-1-azabicyclo [4.3.0] -5-nonene ) Tetraphenylborate, 5- (4′-phenyl) phenacyl- (8-azonia-1-azabicyclo [5.4.0] -7-undecene) tetraphenylborate and the like.

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

In the formula ^{(VII), R 51, R} 54 ~R 57 is the same as ^{R 51, R} 54 ^{~R 57} of each of the formula (I).
R ⁷³ and R ⁷⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, 20 alkylthio groups, C1-C20 alkylsilyl groups, C1-C20 acyl groups, amino groups, cyano groups, C1-C20 alkyl groups, phenyl groups, naphthyl groups, phenoxy groups, and phenoxy groups. It represents a phenyl group which may be substituted with a group selected from the group of ruthio 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, for example, 5-benzyl-1,5-diazabicyclo [4.3.0] nonane and 5- (anthracen-9-yl-methyl)-described in JP-T-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-diazabicik [4.3.0] nonane, 5- (naphth-2-yl-methyl) -1,5-diazabicyclo [4.3.0] nonane, 1,4-bis (1,5-diazabicyclo [4.3 Benzylamine derivatives such as .0] nonanylmethyl) benzene and 8- (2 ′, 6′-dichlorobenzyl) -1,8-diazabicyclo [5.4.0] undecane.

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

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

  Specific examples of benzylammonium salt derivatives include photobase generators described in WO2010 / 095390 and WO2009 / 122664, such as (9-anthryl) methyltriethylammonium tetraphenylborate, (9-oxo-9H). -Thioxanthen-2-yl) methyltriethylammonium tetraphenylborate, (9-anthryl) methyl 1-azabicyclo [2.2.2] octanium tetraphenylborate, (9-oxo-9H-thioxanthen-2-yl) ) Methyl 1-azabicyclo [2.2.2] octanium tetraphenylborate, 9-anthrylmethyl-1-azabicyclo [2.2.2] octanium tetraphenylborate, 5- (9-anthrylmethyl)- 1,5-diazabicyclo 4.3.0] -5-nonenium tetraphenylborate, 8- (9-anthrylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium phenylglyoxylate, N- (9-anthrylmethyl) -N, N, N-trioctylammonium tetraphenylborate, 8- (9-oxo-9H-thioxanthen-2-yl) methyl-1,5-diazabicyclo [4.3.0 ] -5-Nonenium tetraphenylborate, 8- (4-benzoylphenyl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate, {8- (t-butyl- 2-Naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate, 8- (9-oxo-9H-thioxan) 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-T-2001-515500, 5- (2 ′-(2 ″ -naphthyl) allyl) -1,5-diazabicyclo [4.3.0] nonane, 5- (2 ′-(4 ″ -diethylaminophenyl) allyl) -1,5-diazabicyclo [4 .3.0] nonane, 5- (1′-methyl, 2 ′-(4 ″ -biphenyl) allyl) -1,5-diazabicyclo [4.3.0] nonane, 5- (1′-methyl, 2 '-(2 "-thioxanthyl) allyl) -1,5-diazabicyclo [4.3.0] nonane, 5- (1'-methyl, 2'-(2" -fluorenyl) allyl) -1,5-diazabicyclo [4.3.0] Nonane, 8- (2′- 4 "- biphenyl) allyl) - (1,8-diazabicyclo [5.4.0] -7-undecene), and the like.

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

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

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

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

  Examples of benzyloxycarbonylguanidines include benzyloxycarbonyltetramethylguanidine described in WO97 / 31033.

  Examples of the diamine derivative include N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -N-methylacetamide described in JP2011-116869A. N- (N ′-(4,5-dimethoxy-2-nitrobenzyloxycarbonyl) aminopropyl) -6-heptane lactam and the like.

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

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

  Examples of the carboxylic acid ammonium salt include diazabicycloundecene (DBU) ketoprofen salt described in JP2009-280785A, 2-methylimidazole ketoprofen salt, and diazabicyclo described in JP2011-80032A. Xanthone acetate of undecene (DBU), thioxanthone acetate of diazabicycloundecene (DBU), 3-quinuclidinol salt of 2- (carboxymethylthio) thioxanthone described in JP-A-2007-262276, 2- (carboxymethoxy) ) 3-quinuclidinol salt of thioxanthone, and 3-quinuclidinol salt of trans-o-coumaric acid described in JP 2010-254982 A and JP 2011-213783 A.

  Among the photobase generators (B) described above, a photolatent tertiary amine is preferable from the viewpoint that the generated base exhibits high catalytic activity, and the base generation efficiency is good and the storage stability as a composition is good. From the above, benzylammonium salt derivatives, benzyl-substituted amine derivatives, α-aminoketone derivatives, α-ammoniumketone derivatives are preferable, and in particular, since base generation efficiency is better, α-aminoketone derivatives and α-ammoniumketone derivatives are more preferable. Preferably, α-aminoketone derivatives are more preferable than the solubility in the blend. Among the α-aminoketone derivatives, the α-aminoketone compound represented by the above formula (I) is preferable from the basic strength of the generated base, and the α-aminoketone compound represented by the above formula (II) is preferable from the viewpoint of availability.

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

  In the present invention, (C) the silicon compound having a Si—F bond acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer. As the (C) silicon compound having a Si—F bond, known compounds containing a silicon group having a Si—F bond (hereinafter sometimes referred to as a fluorosilyl group) can be widely used. Both low molecular weight compounds and high molecular weight compounds can be used, but organosilicon compounds having a fluorosilyl group are preferred, and organic polymers having a fluorosilyl group are more suitable because of their high safety. Moreover, the low molecular organosilicon compound which has a fluoro silyl group from the point from which a compound becomes low viscosity is preferable.

  Specific examples of the (C) silicon compound having a Si-F bond include compounds having a fluorosilyl group represented by the following formula (8) such as fluorosilanes represented by the following formula (7) (this specification) The organic polymer having a fluorosilyl group (also referred to herein as a fluorinated polymer) and the like are preferred examples.

R ¹¹ _4-d SiF _d (7)
(In Formula (7), each R ¹¹ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ¹² SiO— (R ¹² is independently each having 1 to 20 carbon atoms. Or a substituted or unsubstituted hydrocarbon group, or a fluorine atom), d is any one of 1 to 3, and d is preferably 3. R ¹¹ And when there are a plurality of R ^{12 s} , they may be the same or different.)

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

  Examples of the fluorosilanes represented by the formula (7) include known fluorosilanes represented by the formula (7), and 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, fluorotri Phenylsilane, difluorodimethylsilane, difluorodiethylsilane, difluorodibutylsilane, difluoromethylphenylsilane, difluorodiphenylsilane, trifluoroethylsilane, trifluoro Propylsilane, trifluorobutylsilane, trifluorophenylsilane, γ-glycidoxypropyl trifluorosilane, γ-glycidoxypropyldifluoromethylsilane, vinyltrifluorosilane, vinyldifluoromethylsilane, γ-methacryloxypropylfluorodimethyl Silane, γ-methacryloxypropyl difluoromethylsilane, γ-methacryloxypropyl trifluorosilane, 3-mercaptopropyl trifluorosilane, octadecylfluorodimethylsilane, octadecyldifluoromethylsilane, octadecyltrifluorosilane, 1,3-difluoro-1 , 1,3,3-tetramethyldisiloxane, 1,3,5,7-tetrafluoro-1,3,5,7-tetrasilatricyclo [3.3.1.1 (3,7)] Kang, 1,1-difluoro-1-silacycle 3-pentene, etc. fluoro tris (trimethylsiloxy) silane.

  Of these, fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, vinyltrifluorosilane, vinyldifluoromethylsilane, and γ-methacryloxypropyl because of the availability of raw materials and the ease of synthesis. Fluorodimethylsilane, γ-methacryloxypropyl difluoromethylsilane, γ-methacryloxypropyl trifluorosilane, 3-mercaptopropyl trifluorosilane, octadecylfluorodimethylsilane, octadecyldifluoromethylsilane, octadecyltrifluorosilane, 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), examples of the hydrolyzable group represented by Z in the formula (8) include the same groups as the hydrolyzable group represented by X in the formula (1). Specific examples include hydrogen atoms, halogen atoms other than fluorine, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Etc. 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. Particularly preferred.

R ¹¹ in the 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, R Examples thereof include a triorganosiloxy group represented by R ¹² SiO— in which ¹² is a methyl group, a phenyl group or the like. Of these, a methyl group is particularly preferred.

Specific examples of the fluorosilyl group represented by the formula (8) include silicon groups having no hydrolyzable groups other than fluorine, such as fluorodimethylsilyl group, fluorodiethylsilyl group, fluorodipropylsilyl group, fluoro A silicon group in which one fluorine is substituted on a silicon group such as a diphenylsilyl group or a fluorodibenzylsilyl group; on a silicon group such as a difluoromethylsilyl group, a difluoroethylsilyl group, a difluorophenylsilyl group or a difluorobenzylsilyl group A silicon group having two fluorines; a silicon group having three fluorines on a silicon group which is a trifluorosilyl group; Methoxymethylsilyl group, fluoroethoxymethylsilyl group, fluoromethoxy group Rusilyl group, fluoromethoxyphenylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group, fluorodipropoxysilyl group, fluorodiphenoxysilyl group, fluorobis (2-propenoxy) silyl group, difluoromethoxysilyl group, difluoroethoxysilyl Group, difluorophenoxysilyl group, fluorodichlorosilyl group, difluorochlorosilyl group, and the like, a silicon group having no hydrolyzable group other than fluorine, and a fluorosilyl group in which R11 is a methyl group are preferable, and a trifluorosilyl group Is more preferable.
In addition, because of ease of synthesis, fluorodimethylsilyl group, difluoromethylsilyl group, trifluorosilyl group, fluoromethoxymethylsilyl group, fluoroethoxymethylsilyl group, fluoromethoxyethylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group , A difluoromethoxysilyl group and a difluoroethoxysilyl group are more preferable, and a silicon group having no hydrolyzable group other than fluorine such as a fluorodimethylsilyl group, a difluoromethylsilyl group and a trifluorosilyl group is more preferable from the viewpoint of stability. From the viewpoint of high curability, a silicon group in which 2 to 3 fluorine atoms are substituted on a silicon group, such as a difluoromethylsilyl group, a difluoromethoxysilyl group, a difluoroethoxysilyl group, or a trifluorosilyl group, is preferable. Fluoro silyl group is most preferred.

  The compound having a fluorosilyl group represented by the formula (8) is not particularly limited, and any of monomolecular compounds and polymer compounds can be used. For example, inorganic compounds such as tetrafluorosilane and octafluorotrisilane can be used. Silicon compound; fluorosilanes represented by the above formula (7), fluorotrimethoxysilane, difluorodimethoxysilane, trifluoromethoxysilane, fluorotriethoxysilane, difluorodiethoxysilane, trifluoroethoxysilane, methylfluorodimethoxysilane, methyl Difluoromethoxysilane, methyltrifluorosilane, methylfluorodiethoxysilane, methyldifluoroethoxysilane, vinylfluorodimethoxysilane, vinyldifluoromethoxysilane, vinyltrifluorosilane, vinylfull Low molecular organosilicon compounds such as lodiethoxysilane, vinyldifluoroethoxysilane, phenylfluorodimethoxysilane, phenyldifluoromethoxysilane, phenyltrifluorosilane, phenylfluorodiethoxysilane, phenyldifluoroethoxysilane, fluorotrimethylsilane; And polymer compounds such as fluorinated polysiloxanes having a fluorosilyl group represented by 8), such as fluorosilanes represented by the above formula (7), or the end of the main chain or side chain represented by the formula (8). A polymer having a fluorosilyl group is preferred.

The fluorosilanes represented by the formula (7) and the compound having a fluorosilyl group represented by the formula (8) may be commercially available reagents or synthesized from raw material compounds. The synthesis method is not particularly limited, but a compound having a hydrolyzable silicon group represented by the following formula (9) and a fluorinating agent are known methods (for example, Organometallics 1996, 15, 2478 (Ishikawa et al. ) Etc.) is preferably used.
-SiR ¹¹ _3-p Z _p (9)
(In Formula (9), R ¹¹ and Z are the same as in Formula (8), respectively, and p is any one of 1 to 3).

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

Specific examples of the fluorinating agent used for fluorination of the alkoxysilyl group are 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 the fluorinating agent used for fluorination of the halosilyl group are not particularly limited. For example, AgBF ₄ , SbF ₃ , ZnF ₂ , NaF, KF, CsF, NH ₄ F, CuF ₂ , NaSiF ₆ , _{NaPF 6, NaSbF 6, NaBF 4} , Me 3 SnF, KF (HF) , and the like _1.5-5.
Specific examples of the fluorinating agent used for fluorination of the hydrosilyl group are not particularly limited, and examples thereof include AgF, PF ₅ , Ph ₃ CBF ₄ , SbF ₃ , NOBF ₄ , and NO ₂ BF ₄ .
A compound having a siloxane bond is cleaved with BF ₃ or the like to obtain a fluorosilyl group.

Among synthetic methods fluoro silyl group using these fluorinating agents, that the reaction is simple, the high reaction efficiency, etc. It is highly safe, fluorination method of the alkoxysilane with BF ₃ A chlorosilane fluorination method using CuF ₂ or ZnF ₂ is preferred.

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 Complex, BF ₃ phenol complex, etc. can be used, but because of easy handling, BF ₃ ether complex, BF ₃ thioether complex, BF ₃ amine complex, BF ₃ alcohol complex, BF ₃ carboxylic acid complex, BF ₃ hydration Things are preferred. Among them, BF ₃ ether complex, BF ₃ alcohol complex, and BF ₃ hydrate are preferable because of high reactivity, and 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 a known organic polymer having a Si—F bond. Polymers can be widely used.
The position of the SiF bond in the organic polymer is not particularly limited, and is effective at any site in the polymer molecule. If it is at the end of the main chain or side chain, -SiR ' ₂ F, polymer Is incorporated in the main chain, it is represented in the form of —SiR′F— or ≡SiF (R ′ is independently an arbitrary group).
As the organic polymer having a Si—F bond at the end of the main chain or side chain, a polymer having a fluorosilyl group represented by the above formula (8) is preferable. Examples of those in which a fluorosilyl group is incorporated in the main chain of the polymer include —Si (CH ₃ ) F—, —Si (C ₆ H ₅ ) F—, —SiF ₂ —, ≡SiF, and the like. .

  The fluorinated polymer is a single polymer having the same fluorosilyl group and main chain skeleton, that is, the number of fluorosilyl groups per molecule, the bonding position thereof, and the number of Fs that the fluorosilyl group has, In addition, the polymer may be a single polymer having the same main chain skeleton, or may be a mixture of a plurality of polymers, any or all of which are different. In both cases 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 properties. In order to obtain a rubber-like 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 the polymer. One, preferably 1.1 to 5, more preferably 1.2 to 3 may be present. When the number of fluorosilyl groups contained in one molecule is less than 1 on average, curability becomes insufficient, and it may be difficult to develop good rubber elastic behavior. Further, when the average number of fluorosilyl groups contained in one molecule is more than 5, the elongation of the rubber-like cured product may be small. As described above, the fluorosilyl group may be present at the end of the main chain or the side chain of the polymer molecular chain, or may be incorporated in the main chain. When present at the end of the polymer, the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that a rubber-like cured product having high strength, high elongation, and low elastic modulus is obtained. It becomes easy to be done. When two or more fluorosilyl groups are present in one molecule, each silicon group may be the same or different.

  Further, the fluorinated polymer contains a substituent other than a fluorosilyl group such as a silicon group having only a hydrolyzable group other than fluorine as a hydrolyzable group (for example, a methyldimethoxysilyl group) as well as a fluorosilyl group. 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 hydrolyzable group. Can be mentioned.

  In the fluorinated polymer, any method may be used for introducing the fluorosilyl group, but the introduction method (method (i)) by the reaction of a low molecular silicon compound having a fluorosilyl group with a polymer, and other than fluorine. A method (method (ii)) of modifying a silicon group of a polymer containing a reactive silicon group having a hydrolyzable group (hereinafter sometimes referred to as “polymer (X)”) to a fluorosilyl group. Can be mentioned.

Specific examples of the method (i) include the following methods.
(A) A method in which a polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in a molecule is reacted with a compound having a functional group and a fluorosilyl group that are reactive with the functional group. For example, a method of reacting a polymer having a hydroxyl group at the terminal with isocyanate propyldifluoromethylsilane, or a method of reacting a polymer having a SiOH group at the terminal with difluorodiethoxysilane.
(B) A method of hydrosilylating a polymer containing an unsaturated group in the molecule with a hydrosilane having a fluorosilyl group. For example, a method in which a polymer having an allyl group at a terminal is reacted with difluoromethylhydrosilane can be mentioned.
(C) A method of reacting a polymer containing an unsaturated group with a compound having a mercapto group and a fluorosilyl group. For example, a method in which a polymer having an allyl group at the terminal is reacted with mercaptopropyldifluoromethylsilane can be mentioned.

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

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

The fluorinating agent used in the production of the fluorinated polymer may also act as a curing catalyst for the fluorinated polymer, and when water is present when producing the fluorinated polymer using the method (ii) above. The silanol condensation reaction proceeds and the viscosity of the resulting fluorinated polymer may increase. For this reason, it is desirable that the production of the fluorinated polymer be performed in an environment free from water as much as possible. Before the fluorination, the polymer (X) to be fluorinated is subjected to azeotropic dehydration using toluene, hexane or the like. It is preferable to perform a dehydration operation such as providing. However, when a BF ₃ amine complex is used, fluorination hardly progresses after the dehydration operation, and the reactivity tends to be improved by adding a small amount of water. Is preferably added. In view of the stability of the fluorinated polymer, it is preferable to remove the fluorinating agent and by-product fluorinating agent-derived components after fluorination by filtration, decantation, liquid separation, vacuum devolatilization, or the like. When producing a fluorinated polymer with a fluorinating agent of BF ₃ systems described above, BF ₃ from components produced by BF ₃ and reaction remaining fluorinated polymers produced is, 500 ppm than in B quantity It is preferable that it is less than 100 ppm, and it is especially preferable that it is less than 50 ppm. By removing BF ₃ and the component derived from BF _3, it is possible to suppress an increase in viscosity of the obtained fluorinated polymer itself and a mixture of the fluorinated polymer and the polymer (X). Considering this point, a fluorination method using a BF ₃ ether complex or a BF ₃ alcohol complex is preferable because the boron component can be removed relatively easily by vacuum devolatilization, and a method using a 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 the amount of the fluorinating agent is reduced. May be partially fluorinated by adjusting the fluorination conditions. For example, in the above method (ii), when the fluorinated polymer is produced using the polymer (X), the amount of the fluorinating agent is not particularly limited, and the moles of fluorine atoms in the fluorinating agent are not limited. The amount may be an amount that is at least equimolar with respect to the molar amount of the polymer (X). When all the hydrolyzable groups contained in the polymer (X) are to be fluorinated by the method (ii), the molar amount of fluorine atoms in the fluorinating agent is contained in the polymer (X). It is preferable to use the fluorinating agent in such an amount that it is equimolar or more with respect to the total molar amount of the hydrolyzable group in the reactive silicon group. Here, the “fluorine atom in the fluorinating agent” means a fluorine atom effective for fluorination in the fluorinating agent, specifically, a hydrolyzable group in the reactive silicon group of the polymer (X). A fluorine atom that can be substituted.

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

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

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

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

  The blending ratio of the silicon compound (C) having the Si-F bond is not particularly limited, but when a polymer compound having a number average molecular weight of 3000 or more such as a fluorinated polymer is used as the component (C), (A) crosslinking 0.01 to 80 parts by mass is preferable, 0.01 to 30 parts by mass is more preferable, and 0.05 to 20 parts by mass is further preferable with respect to 100 parts by mass of the functional silicon group-containing organic polymer. A low molecular compound having a fluorosilyl group having a number average molecular weight of less than 3000 as the component (C) (for example, a low molecular organic silicon having a fluorosilane represented by the formula (7) or a fluorosilyl group represented by the formula (8) In the case of using a compound, an inorganic silicon compound having a fluorosilyl group, etc., 0.01 to 10 parts by mass is preferable with respect to 100 parts by mass of (A) the crosslinkable silicon group-containing organic polymer, and 0.05 to 5 Part by mass is more preferable.

  As the compound (D) having a radical photopolymerizable vinyl group, a known radical photopolymerizable compound having a vinyl group can be used, and there is no particular limitation. For example, a (meth) acryloyl group may be used. And N-vinyl compounds in which a vinyl group is directly bonded to a nitrogen atom.

  Examples of the compound having a (meth) acryloyl group include a compound having a (meth) acryloyloxy group and a compound having a (meth) acrylamide group, and a compound having a (meth) acryloyloxy group from the viewpoint of storage stability. preferable. Moreover, the compound which has a (meth) acrylamide group from a reactive point is preferable.

  As the compound having the (meth) acryloyloxy group, either a monomer or an oligomer can be used, and a monomer having a (meth) acryloyloxy group is preferable from the viewpoint of viscosity. Moreover, the oligomer which has a (meth) acryloyloxy group from the point of the physical property of hardened | cured material is suitable.

  The monomer having the (meth) acryloyloxy group is not particularly limited as long as it is a compound having at least one (meth) acryloyloxy group, and examples thereof include monofunctional (meth) acrylates and polyfunctional (meth). Examples include acrylates.

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

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

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

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

  Examples of the acrylic oligomer include poly-n-butyl acrylate having an acryloyl group at both ends described in Production Example 1 of WO2012 / 008127 and one end described in Production Example 2 of the same publication. Poly (n-butyl acrylate) having an acryloyl group, poly (acrylic acid n-butyl / ethyl acrylate / 2-methoxyethyl acrylate) having acryloyl groups at both ends described in Production Example 1 of WO 2005/000927 Poly (n-butyl acrylate / 2-ethylhexyl acrylate) having acryloyl groups at both ends described in Production Example 2 of WO 2006/112420, both ends described in Production Example 3 of the same publication Use poly (2-ethylhexyl acrylate) with acryloyl group for the Can.

  As a skeleton component of the acrylic oligomer, poly (methyl methacrylate) (MMA), polystyrene (St), poly (acrylonitrile (AN) / St), poly (2-hydroxyethyl methacrylate (HEMA) / MMA), poly (HEMA) Many oligomers such as / butyl methacrylate (BMA)) are commercially available.

  Examples of commercially available acrylic oligomers include macromonomer AA-6, AA-714, AB-6, AJ-7, AN-6, AS-6, AW-6, and AZ manufactured by Toa Gosei Co., Ltd. -8, HA-6, HN-6, HS-6, RC-300, RC-100, RC-200 manufactured by Kaneka Corporation.

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

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

  As the carboxylic acid or anhydride thereof, dibasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid, or anhydrides thereof Thing etc. are mentioned.

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

  Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether; di- or polyglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or an alkylene oxide adduct thereof; phenol novolac type epoxy resin and cresol novolac type Novolak type epoxy resins such as epoxy resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like. In addition to these, the document “Epoxy Resin—Recent Advances” (Shisodo, published in 1990), Chapter 2 and the document “Polymer Processing”, Vol. 9, Volume 22 No. Epoxy Resin [Polymer Publications, Compounds published on pages 4 to 6 and pages 9 to 16 of 1973.

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

  In addition to these, the compounds described on pages 3 to 6 of the above-mentioned document “Polymer Processing”, separate volume epoxy resin, can be mentioned. In addition to these aromatic epoxy resins and aliphatic epoxy resins, epoxy compounds having a triazine nucleus in the skeleton, such as TEPIC (Nissan Chemical Co., Ltd.), Denacol EX-310 (Nagase Kasei Co., Ltd.), etc. can be mentioned. , Compounds described on pages 289 to 296 of the above-mentioned document “Polymer Processing”, separate volume epoxy resin, and the like. In the above, the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide or propylene oxide.

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

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

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

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

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

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

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

  Examples of the N-vinyl compound include N-vinyl pyrrolidone and N-vinyl caprolactam. In the present invention, the N-vinyl compound is preferable from the viewpoint of reactivity and the difficulty of oxygen inhibition.

  The blending ratio of the compound (D) having a radical photopolymerizable vinyl group is not particularly limited, but is preferably 10 to 700 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. 20-600 mass parts is more preferable, and 30-500 mass parts is still more preferable. These compounds having a photopolymerizable vinyl group may be used alone or in combination of two or more.

The liquid gasket of the present invention preferably further contains a tackifying resin as the component (E). By adding a tackifying resin, the liquid gasket of the present invention has tackiness after curing, and even when it is reattached, strong adhesiveness to a substrate such as a housing member can be obtained due to tackiness.

  Examples of tackifying resins include: styrene-based (co) polymers; coumarone-indene resins, coumarone resins such as coumarone resins mixed with naphthene resins, phenol resins, rosins, etc .; pt-butylphenol-acetylene resins; Phenolic resins such as phenol formaldehyde resins, xylene-phenol resins, xylene resins having a low degree of polymerization and a low softening point of about 60 to 100 ° C. Terpene resins; synthetic polyterpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, hydrogenated hydrocarbon resins and other petroleum hydrocarbon resins; rosin and rosin pentaerythritol Esters, rosin glycerol esters, hydrogenated rosin, highly water Added wood resin, methyl ester of hydrogenated rosin, triethylene glycol ester of hydrogenated rosin, pentaerythritol ester of hydrogenated rosin, polymerized rosin, glycerol ester of polymerized rosin, resin acid zinc, hardened rosin and other rosin derivatives Low molecular weight polystyrene, other special preparations and the like, but are not limited thereto. When a tackifying resin is contained, it is preferable in that it can provide adhesion to a hardly adhesive material. These tackifier resins may be used alone or in combination of two or more.

  The blending ratio of the (F) tackifying resin is not particularly limited, but the total amount of (A) a crosslinkable silicon group-containing organic polymer and (D) a compound having a photoradically polymerizable vinyl group is 100 parts by mass. On the other hand, 0.1-300 mass parts is preferable, 1-250 mass parts is more preferable, 5-200 mass parts is further more preferable. These tackifier resins may be used alone or in combination of two or more.

  The liquid gasket of the present invention has a crosslinking property that generates one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by light in addition to the (B) photobase generator. It is preferable to further contain a silicon group-containing compound. 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 can improve adhesion performance.

  Examples of 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 include a primary amino group and Any compound that generates an aminosilane compound having at least one amino group selected from the group consisting of secondary amino groups and a crosslinkable silicon group can be used. In the present specification, a crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by 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 hydrolyzable group couple | bonded is preferable. Of these, alkoxy groups such as a methoxy group and an ethoxy group are preferable because they are mildly hydrolyzable and easy to handle. In the aminosilane compound, a hydrolyzable group and a hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, preferably 2 or more, particularly preferably 3.

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

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

  As the sag-preventing agent, known sag-preventing agents can be widely used and are not particularly limited. For example, polyamide waxes; hydrogenated castor oil derivatives; calcium stearate, aluminum stearate, barium stearate, etc. Examples include metal soaps, organic bentonite, colloidal silica, modified polyester polyols, inorganic thixotropic agents such as asbestos powder, and organic thixotropic agents such as fatty acid amide. Further, when rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained. These anti-sagging agents may be used alone or in combination of two or more. In the liquid gasket of the present invention, when the anti-sagging agent is contained, the amount is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A).

  In the liquid gasket of the present invention, if necessary, a silane coupling agent, a photosensitizer, an extender, a plasticizer, a moisture absorbent, a curing catalyst, a property modifier for improving tensile properties, a reinforcing agent, a coloring Various additives such as an agent, a flame retardant, an antioxidant, an antioxidant, an ultraviolet absorber, a solvent, a fragrance, a pigment, a dye, and a resin filler may be added.

  The liquid gasket of the present invention can improve adhesion to general adherends such as metals, plastics, and glass by blending a silane coupling agent. Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane. Amino group-containing silanes such as N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propane Ketimine type silanes such as amines; γ-glycidoxypropyltrimethoxysilane, γ-glycid Epoxy group-containing silanes such as xylpropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyl Mercapto group-containing silanes such as methyldimethoxysilane; Vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; γ-isocyanatopropyl Isocyanate-containing silanes such as triethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; alkyl silanes such as hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane; Silane, phenyltriethoxysilane, diphenyldimethoxysilane, but phenyl group-containing silanes such as diphenyl diethoxy silane, etc., but is not limited thereto. 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 silane coupling agent is not particularly limited, but is preferably 0.2 to 20 parts by weight, and 0.3 to 15 parts by weight with respect to 100 parts by weight of the (A) crosslinkable silicon group-containing organic polymer. Is more preferable, and 0.5 to 10 parts by mass is even more preferable. These silane coupling agents may be used alone or in combination of two or more.

  As the photosensitizer, a carbonyl compound having a triplet energy of 225 to 310 kJ / mol is preferable. For example, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 , 4-diisopropylthioxanthone, isopropylthioxanthone, phthalimide, anthraquinone, 9,10-dibutoxyanthracene, acetophenone, propiophenone, benzophenone, acylnaphthalene, 2 (acylmethylene) thiazoline, 3-acylcoumarin and 3,3'-carbonyl Biscumarin, perylene, coronene, tetracene, benzanthracene, phenothiazine, flavin, acridine, ketocoumarin, etc. 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 the photosensitizer, an active energy ray-cleaving radical generator that is cleaved by irradiation with active energy rays to generate radicals is more preferable. When the active energy ray-cleaving radical generator is used, curing is much faster than when using photosensitizers such as benzophenones and thioxanthones known as photobase initiator sensitizers. It shows the speed, and it becomes possible to cure the photocurable composition of the present invention in a shorter time after irradiation with energy rays.

Examples of the energy ray-cleaving radical generator include arylalkyl ketones such as benzoin ether derivatives and acetophenone derivatives, oxime ketones, acylphosphine oxides, thiobenzoic acid S-phenyls, titanocenes, and the like. Examples include derivatives having molecular weight. 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, benzyldimethyl ketal, bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyryl-phenyl) titanium, (η ⁶ -isopropyl benzene) - (eta ⁵ - cyclopentadienyl) - iron (II Hexafluorophosphate, trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2, Examples include 4-dipentoxyphenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide.

  The blending ratio of the photosensitizer is not particularly limited, but is preferably 0.01 to 5% by mass and more preferably 0.025 to 2% by mass in the composition. These photosensitizers may be used independently and may use 2 or more types together.

  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.

  As the curing catalyst, known curing catalysts can be widely used, and are not particularly limited. Examples thereof include organometallic compounds and amines, and it is particularly preferable to use a silanol condensation catalyst. Examples of the silanol condensation catalyst include stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate. Organotin compounds such as dioctyltin dilaurate, dioctyltin diversate, tin octylate and tin naphthenate; dialkyltin oxides such as dimethyltin oxide, dibutyltin oxide and dioctyltin oxide; reaction products of dibutyltin oxide and phthalate, etc. ; Titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum trisacetylacetonate, aluminum trisethylate 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 Organic acid bismuth such as bismuth neodecanoate and bismuth rosinate; other acidic catalysts and basic catalysts known as silanol condensation catalysts. However, the toxicity of the resulting photocurable composition may increase depending on the amount of the organic tin compound added.

  The method for producing the liquid gasket of the present invention is not particularly limited. For example, a predetermined amount of the components (A) to (E) is blended, and other blended substances are blended as necessary, followed by deaeration and stirring. Can be manufactured. There is no particular limitation on the order of blending each component and other compounding substances, and it may be determined as appropriate.

  The liquid gasket of the present invention can be a one-component type or a two-component type as required, but can be suitably used particularly as a one-component type. The photocurable composition 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.

  The cured product of the present invention is a gasket formed by irradiating the liquid gasket of the present invention with light. The product of the present invention is a product manufactured using the liquid gasket of the present invention, and can be suitably used for electronic circuits, electronic components, automobiles and the like.

  Although there is no restriction | limiting in particular as conditions which irradiate light with respect to the liquid gasket of this invention, When irradiating an active energy ray at the time of hardening, as an active energy ray, rays, ultraviolet rays, visible rays, infrared rays, X-rays, In addition to electromagnetic waves such as γ rays, electron beams, proton beams, neutron beams, etc. can be used. However, due to the curing speed, the availability and price of irradiation equipment, the ease of handling under sunlight and general lighting, etc. Curing by ultraviolet ray or electron beam irradiation is preferable, and curing by ultraviolet ray irradiation is more preferable. The ultraviolet rays include g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), and the like. The active energy ray source is not particularly limited, 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. A light emitting diode is preferred.

For The irradiation energy such as ultraviolet, preferably ^{10~20,000mJ / cm 2, 50~10,000mJ / cm} 2 is more preferable. If it is less than 10 mJ / cm ² , the curability may be insufficient, and if it is 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 applying the liquid gasket of the present invention to the adherend is not particularly limited, but application methods such as screen printing, stencil printing, roll printing, spin coating, and application using a dispenser are preferably used.

  Further, in the present invention, there is no limitation on the timing of application and light irradiation of the liquid gasket to the adherend, and after irradiating the liquid gasket with light, it may be joined to the adherend to produce a product, Moreover, a liquid gasket may be apply | coated to a to-be-adhered body, a liquid gasket may be hardened by irradiating light, and a product may be manufactured.

  The electronic device in which the liquid gasket of the present invention is used is not particularly limited. For example, portable communication devices (for example, mobile phones, PDA terminals, smartphones, tablets, etc.), portable personal computers, digital watches, portable radios, portable televisions, digital cameras, portable digital video recorders, portable CD players, MD players And portable recording / recording / reproducing devices such as DVD players, MP3 players, and digital recorders. The liquid gasket of the present invention can also be used to individually protect the internal electronic circuit, memory, CPU or battery part.

  The liquid gasket of the present invention is applied to one or both of a plurality of housing members such as a main body and a lid, to be sealed, irradiated with active energy rays, and then combined with the housing member. Since the crosslinkable silicon group-containing organic polymer is cured by moisture in the air after irradiation with active energy rays, curing proceeds if the housing members are left after being combined. If it is desired to increase the curing rate, heating is also possible.

  The housing member can be provided with a groove at a position to be applied and the liquid gasket can be fixed, but the groove is not essential. Housing materials include polyamide resins (nylon, etc.), polycarbonate resins, ABS resins, PMMA resins, and other synthetic resins, synthetic resins made by adding glass fibers to these synthetic resins, SUS, mild steel and other metals, glass Ceramics such as can be used. Among these, synthetic resins, particularly synthetic resins reinforced with glass fibers, are preferable.

  The liquid gasket of the present invention is useful when reworking electronic equipment. When reworking, first separate the housing member such as the main body and the lid, but the liquid gasket of the present invention is not firmly bonded to the base material like a normal adhesive, so it is relatively easy to separate. Can do. At this time, the entire liquid gasket remains on one housing member, and part of the liquid gasket does not remain on the other housing member (no adhesive residue), and the interface peels cleanly.

  In the liquid gasket of the present invention, (D) a compound having a photopolymerizable vinyl group is cured by irradiation with active energy rays, so that the shape retention after irradiation with active energy rays is excellent and the housing member is made active energy rays. Immediately after irradiation, it becomes sticky and can be temporarily fixed immediately. Then, since the housing member can be recombined until (A) the crosslinkable silicon group-containing organic polymer is cured by moisture, the reworkability is excellent.

  If the material of the sealed housing member is different, the liquid gasket remains on the material with higher peel strength. When the material of the sealed housing member is the same, the liquid gasket remains on the housing member on the side where the liquid gasket is applied. When the gasket is mechanically fixed by a groove or the like provided in one housing member, the liquid gasket remains in the fixed housing member. Further, when the housing member is separated, if a part of the liquid gasket is forcibly peeled off, the liquid gasket is peeled off in the housing member on the peeled side. In any case, on the side where the liquid gasket is peeled off, it peels cleanly at the interface with the substrate, and there is no adhesive residue.

  After the housing member is separated and the defective portion is replaced, the liquid gasket remaining on one of the housing members can be sealed again without applying a new liquid gasket.

  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.

(Synthesis Example 1) Synthesis of polyoxyalkylene polymer A1 having a trimethoxysilyl group at its terminal A flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with ethylene glycol as an initiator, zinc Propylene oxide was reacted in the presence of a hexacyanocobaltate-glyme complex catalyst to obtain a polyoxypropylene triol. 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 by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt% to trimethoxysilane, which is a silicon hydride compound, 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. As a result of H1-NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis Example 2) Synthesis of polyoxyalkylene polymer A2 having a trimethoxysilyl group at the terminal A flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with ethylene glycol as an initiator, zinc Propylene oxide was reacted in the presence of a hexacyanocobaltate-glyme complex catalyst to obtain a polyoxypropylene triol. 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 by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt% to trimethoxysilane, which is a silicon hydride compound, 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. As a result of H1-NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis Example 3) Synthesis of (meth) acrylic polymer A3 having a trimethoxysilyl group 40.00 g of ethyl acetate, methyl methacrylate in a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser 70.00 g, 2-ethylhexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 30.00 g, 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 12.00 g, and metal catalyst 0.10 g of titanocene dicylide was charged and the contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the flask. 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 terminate the polymerization, and a trimethoxysilyl group (meta ) Acrylic 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 H1-NMR measurement was 2.00 per molecule.

(Synthesis Example 4) Synthesis of fluorinated polymer C 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 was used as an initiator, and zinc hexacyanocobalt A polyoxypropylene diol having a hydroxyl value-converted molecular weight of 14500 and a molecular weight distribution of 1.3 obtained by reacting propylene oxide in the presence of a tate-glyme complex catalyst was obtained. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene diol, methanol is distilled off under reduced pressure by heating, and the terminal hydroxyl group of the polyoxypropylene diol is converted to sodium alkoxide to obtain a polyoxyalkylene polymer M3. It was.

  Next, the polyoxyalkylene polymer M3 was reacted with allyl chloride to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. This polyoxyalkylene polymer having an allyl group at the terminal is reacted with methyldimethoxysilane, 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 methyldimethoxysilyl at the terminal. A polyoxyalkylene polymer A4 having a group was obtained. As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A4 having a methyldimethoxysilyl group by GPC, the peak top molecular weight was 15000 and the molecular weight distribution was 1.3. As a result of H1-NMR measurement, the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.

  A flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was degassed under reduced pressure, and then replaced with nitrogen gas, and 2.4 g of BF3 diethyl ether complex was placed under a nitrogen stream and heated to 50 ° C. did. Subsequently, a mixture of 1.6 g of dehydrated methanol was slowly added dropwise and mixed. In a new flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, and a reflux condenser, 100 g of the obtained polymer A4 and 5 g of toluene were placed. After stirring at 23 ° C. for 30 minutes, the mixture was heated to 110 ° C. and stirred under reduced pressure for 2 hours to remove toluene. 4.0 g of the mixture obtained previously was slowly dropped into this container under a nitrogen stream, and after completion of the dropping, the reaction temperature was raised to 120 ° C. and reacted for 30 minutes. After completion of the reaction, vacuum degassing was performed to remove unreacted substances. A polyoxyalkylene polymer C having a fluorosilyl group at the terminal (hereinafter referred to as fluorinated polymer C) was obtained. When the 1H NMR spectrum of the obtained fluorinated polymer C (measured in a CDCl3 solvent using NMR400 manufactured by Shimazu) was measured, a peak corresponding to silylmethylene (—CH 2 —Si) of polymer A4 as a raw material was measured. (M, 0.63 ppm) disappeared, and a broad peak appeared on the low magnetic field side (0.7 ppm-).

Example 1
Prepare the liquid gasket by adding each compounding substance to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, and mixing and stirring at the mixing ratio shown in Table 1. did.

In Table 1, the compounding amount of each compounding substance is shown in parts by mass, the polyoxyalkylene polymer A1 is the polyoxyalkylene polymer A1 obtained in Synthesis Example 1, and the polyoxyalkylene polymer A2 is synthesized. The polyoxyalkylene polymer A2 obtained in Example 2, the polyoxyalkylene polymer A3 is the polyoxyalkylene polymer A3 obtained in Synthesis Example 3, and the fluorinated polymer C was obtained in Synthesis Example 4. Fluorinated polymer C. Details of other compounding substances are as follows.
* 1 Irgacure (registered trademark) 379EG (manufactured by BASF, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), Dilute to 50% by mass with propylene carbonate solution. In Table 1, the mass part of solid content is described. )
* 2 Light acrylate DPM-A (Kyoeisha Chemical Co., Ltd., trade name, methoxydipropylene glycol acrylate)
* 3 UV3700B (made by Nippon Synthetic Chemical Industry Co., Ltd., urethane acrylate)
* 4 Pine Crystal KE-100 (Arakawa Chemical Industries, trade name, tackifying resin)
* 5 Irgacure (registered trademark) 1173 (manufactured by BASF, active energy ray-cleaving radical generator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one.)
* 6 AEROSIL (registered trademark) R972 (Nippon Aerosil Co., Ltd., hydrophobic silica)

  The obtained liquid gasket was tested by the following method. The results are shown in Table 1.

(Workability test without UV irradiation)
A composition prepared in Example 1 using a dispenser robot equipped with a needle having an inner diameter of 0.84 mm as a discharge needle under a fluorescent lamp having a film that cuts a wavelength of 500 nm or less attached under a condition of 23 ° C. and 50% RH. A workability test was conducted when UV was not irradiated. In an environment of 23 ° C. and 50% RH, continuous application to a PET film is performed, and the time during which dispensing can be applied by finger touch is measured.
A case where the work can be performed for 8 hours or more is marked as ◎, a case where the work can be performed for a period of 4 hours or more but less than 8 hours, a case where the nozzle tip is hardened in less than 4 hours and the work becomes impossible.

(Shape retention)
Using a dispenser robot equipped with a needle with an inner diameter of 0.84 mm as a dispensing needle, photocuring into a square of 75.00 mm in length, 25.00 mm in width, 2.00 mm in thickness, 65.00 mm in length and 18 mm in width The composition was applied, and UV irradiation [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm 2), integrated light quantity: 1000 mJ / cm 2] was performed. Immediately after irradiation, another glass plate of the same size was bonded. Then, in an environment of 23 ° C. and 50% RH, a 500 g weight was placed and cured for 15 minutes. After curing, compared to the width of the curable composition before pasting, the width is less than 2 times, the less than 3 times is Δ, and the width is 3 times or more.

(Initial waterproof)
Using a dispenser robot equipped with a needle with an inner diameter of 0.84 mm as a dispensing needle, photocuring into a square of 75.00 mm in length, 25.00 mm in width, 2.00 mm in thickness, 65.00 mm in length and 18 mm in width The composition was applied, and UV irradiation [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm 2), integrated light quantity: 1000 mJ / cm 2] was performed. Immediately after irradiation, another glass plate of the same size was bonded. Then, in an environment of 23 ° C. and 50% RH, a 500 g weight was placed and cured for 15 minutes. After curing, the laminated and bonded glass plate was immersed in a water tank having a depth of 1.0 m for 30 minutes, and the presence or absence of water intrusion into the gasket was visually determined. A sample without water intrusion was marked with ◯, and a sample with water intrusion was marked with ×.

(Water resistance of peeled liquid gasket)
Using a dispenser robot equipped with a needle with an inner diameter of 0.84 mm as a dispensing needle, photocuring into a square of 75.00 mm in length, 25.00 mm in width, 2.00 mm in thickness, 65.00 mm in length and 18 mm in width The composition was applied, and UV irradiation [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm 2), integrated light quantity: 1000 mJ / cm 2] was performed. Immediately after irradiation, another glass plate of the same size was bonded. Thereafter, the laminated and bonded glass plates were peeled off once and bonded again. After pasting again, in an environment of 23 ° C. and 50% RH, a 500 g weight was placed and cured for 15 minutes. After curing, the laminated and bonded glass plate was immersed in a water tank having a depth of 1.0 m for 30 minutes, and the presence or absence of water intrusion into the gasket was visually determined. A sample without water intrusion was marked with ◯, and a sample with water intrusion was marked with ×.

(Peelability)
Using a dispenser robot equipped with a needle with an inner diameter of 0.84 mm as a dispensing needle, photocuring into a square of 75.00 mm in length, 25.00 mm in width, 2.00 mm in thickness, 65.00 mm in length and 18 mm in width The composition was applied, and UV irradiation [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm 2), integrated light quantity: 1000 mJ / cm 2] was performed. Immediately after irradiation, another glass plate of the same size was bonded. Then, in an environment of 23 ° C. and 50% RH, a 500 g weight was placed and cured for 1 day. After curing, the laminated and laminated glass plates are peeled off and broken between the glass and the adhesive. The breaking at the interface of the glass plate was marked with ◯, and the cohesive failure of the adhesive was marked with ×.

(Examples 2-3, comparisons 1-4)
A photocurable composition and a curable composition were prepared in the same manner as in Example 1 except that the compounding materials were changed as shown in Table 1. A curable test and an adhesive test of the photocurable composition were performed in the same manner as in Example 1, and the results are shown in Table 1.

  The liquid gaskets of Comparative Examples 2 to 4 had poor shape retention, spread when the glass plates were bonded together, and could not be used as gaskets.

As shown in Table 1, the liquid gasket of the present invention does not harden when not irradiated with active energy rays, has excellent shape retention, and has sufficient time for bonding after irradiation with active energy rays. . In addition, in the housing member joined using the liquid gasket, the housing member can be removed with a small force without protruding to a portion where sealing is not desired. After reworking, the housing member can be re-used using the gasket as it is. It can be joined, and the sealing performance such as the initial waterproof performance is maintained even after recombination.

Claims (6)

(A) a crosslinkable silicon group-containing organic polymer;
(B) a photobase generator;
(C) a silicon compound having a Si-F bond;
(D) The liquid gasket for electronic devices characterized by containing the radically polymerizable vinyl group-containing compound.   (E) The liquid gasket for electronic devices of Claim 1 which further contains tackifying resin.   The (A) crosslinkable silicon group-containing organic polymer is at least one selected from the group consisting of a crosslinkable silicon group-containing polyoxyalkylene polymer and a crosslinkable silicon group-containing (meth) acrylic polymer. The liquid gasket for electronic devices according to claim 1, wherein the liquid gasket is used for electronic devices.   The liquid gasket for electronic equipment according to any one of claims 1 to 3, wherein the (B) photobase generator is a photolatent tertiary amine.   The product manufactured using the liquid gasket for electronic devices of any one of Claims 1-4. An electronic device assembly method that undergoes a rework process ,
(A) As the on-site liquid mold gasket for electronic equipment, (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, (C) a silicon compound having a Si-F bond, D) a step of preparing an in-situ molded liquid gasket containing a radically polymerizable vinyl group-containing compound;
(B) applying the liquid gasket to an area to be sealed of one housing member of an electronic device in an uncured state, irradiating with active energy rays, and sandwiching the other housing member;
(C) Each step of removing the housing member of the electronic device that requires rework after curing and replacing the internal components, and (d) Resealing the housing member using the cured liquid gasket as it is. A method for assembling an electronic device that undergoes a rework process, comprising :