WO2015008709A1 - 光硬化性組成物 - Google Patents
光硬化性組成物 Download PDFInfo
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- WO2015008709A1 WO2015008709A1 PCT/JP2014/068615 JP2014068615W WO2015008709A1 WO 2015008709 A1 WO2015008709 A1 WO 2015008709A1 JP 2014068615 W JP2014068615 W JP 2014068615W WO 2015008709 A1 WO2015008709 A1 WO 2015008709A1
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C08L33/04—Homopolymers or copolymers of esters
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
Definitions
- the present invention relates to a photocurable composition, and in particular, to a photocurable composition that is fast-curing even with a low integrated light quantity and can be cured in a short time.
- An organic polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a silicon-containing group that can be crosslinked by forming a siloxane bond (hereinafter also referred to as “crosslinkable silicon group”) is obtained at room temperature. It is also known that the rubber has a property that it can be cross-linked by formation of a siloxane bond accompanied by hydrolysis reaction of a cross-linkable silicon group due to moisture or the like to obtain a rubber-like cured product.
- organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a (meth) acrylate polymer are used for sealing materials, adhesives, paints, etc. Widely used.
- the curable composition used for sealing materials, adhesives, paints, etc. and the rubber-like cured product obtained by curing have various properties such as curability, adhesiveness, storage stability, mechanical properties such as modulus, strength, and elongation. Properties are required, and many studies have been made on organic polymers containing crosslinkable silicon groups. In recent years, rapid curing is required in various fields such as an electronic component / electronic device assembling field, but in the case of a moisture-curing adhesive, there is a problem that a bonding time after application is shortened.
- Patent Document 1 discloses a polymer having two or more hydrolyzable silyl groups in one molecule, and the polymer by light irradiation.
- a photocrosslinkable composition comprising a compound that crosslinks a compound, and a compound containing a compound that generates an acid or a base upon irradiation with light as a compound that crosslinks a polymer by light irradiation.
- the crosslinkable composition is exemplified (Patent Document 1, Claims 1 to 3).
- An object of the present invention is to provide a fast-curing type photocurable composition that exhibits excellent adhesive performance even with a low integrated light quantity and can be cured in a short time, and has excellent workability.
- the photocurable composition of the present invention comprises (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, and (C1) silicon having a Si—F bond.
- the (B) photobase generator is preferably a photolatent tertiary amine.
- a substance that generates an amine compound by the action of active energy rays is referred to as a photolatent amine compound.
- a substance that generates an amine compound having a primary amino group is a photolatent primary amine
- a substance that generates an amine compound having a secondary amino group is a photolatent group.
- Substances that generate secondary amines and amine compounds having tertiary amino groups are referred to as photolatent tertiary amines, respectively.
- the curable composition of the present invention preferably further contains (D) a silane coupling agent.
- the (A) crosslinkable silicon group-containing organic polymer is a polyoxyalkylene polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule, and on the average in the molecule is 0.8. It consists of a saturated hydrocarbon polymer containing 8 or more crosslinkable silicon groups and a (meth) acrylic acid ester polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule. It is preferable that it is 1 or more types selected from the group.
- cured material of this invention forms a hardened
- the cured product of the present invention is a cured product formed by the method for producing a cured product of the present invention.
- the product manufacturing method of the present invention is characterized by manufacturing a product using the photocurable composition of the present invention.
- the first aspect of the product of the present invention is a product manufactured by the product manufacturing method of the present invention.
- the 2nd aspect of the product of this invention is a product manufactured using the manufacturing method of the hardened
- a third aspect of the product of the present invention is a product using the photocurable composition of the present invention as an adhesive.
- a fourth aspect of the product of the present invention is a product using the photocurable composition of the present invention as a coating agent.
- the present invention is a photocurable composition that does not cure when irradiated with active energy rays, but cures when irradiated with active energy rays.
- the photocurable composition of the present invention is not cured immediately after irradiation with active energy rays depending on the irradiation conditions of active energy rays, and can be cured after a lapse of a certain period of time.
- the photocurable composition of the present invention is used as an adhesive, it can be adhered after being applied for a certain period of time after the adhesive is applied.
- the photocurable composition of the present invention comprises (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, (C1) a compound having a Si—F bond, and / or (C2) three.
- One or more fluorine-type compounds selected from the group consisting of boron fluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyvalent fluoro compound.
- 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.
- 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 Copolymers of acrylonitrile and styrene, etc., hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; dibasic acids such as adipic acid and glycols A polyester polymer obtained by condensation of lactones or ring-opening polymerization of lactones; a (meth) acrylic acid ester polymer obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid ester monomer, vinyl polymer obtained by
- 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.
- a group represented by the following general formula (1) is preferable.
- 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 a halogen atom; , —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 Represents 20 hydrocarbon groups, and when two or more R 1 are present They may be the same or different.
- X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different.
- a represents 0, 1, 2, or 3
- b represents 0, 1, or 2, respectively.
- p in the following general formula (2) need not be the same. p represents an integer of 0 to 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.
- a + (sum of b) is preferably in the range of 1 to 5.
- 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.
- crosslinkable silicon group a crosslinkable silicon group represented by the following general formula (3) is preferable because it is easily available.
- R 1 and X are the same as described above, and a is an integer of 1, 2 or 3.
- a in the formula (3) is preferably 2 or more, and more preferably 3.
- R 1 examples include alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, and R 1 3 SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.
- the hydrolyzable group represented by X is not particularly limited as long as it is other than an F atom, and may be any conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.
- 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.
- 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.
- a methoxy group or an ethoxy group is usually used.
- crosslinkable silicon group examples include trialkoxysilyl groups [—Si (OR) 3 ] such as trimethoxysilyl group and triethoxysilyl group, dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group.
- examples thereof include a silyl group [—SiR 1 (OR) 2 ]. Due to high reactivity, a trialkoxysilyl group [—Si (OR) 3 ] is preferable, and a trimethoxysilyl group is more preferable.
- R is an alkyl group such as a methyl group or an ethyl group.
- 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. Particularly preferred is 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.
- 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.
- the crosslinkable silicon group is only at the end of the main chain of the molecular chain, so that 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)
- 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. .
- repeating unit represented by the general formula (4) examples 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.
- a method for synthesizing a polyoxyalkylene polymer for example, a polymerization method 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
- KOH alkali catalyst
- organic aluminum 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 for example, a polymerization method using a double metal cyanide complex catalyst shown in JP-B-46-27250 and JP-B-59-15336
- a polyoxyalkylene system having a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less and a narrow molecular weight distribution 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.
- a urethane bond component examples 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.
- lifted The thing obtained from reaction with coalescence can be mention
- 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).
- 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
- 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.
- polymer reaction method examples 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.
- an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.
- polyoxyalkylene polymer having a crosslinkable silicon group examples include JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767.
- No. 57-164123 Japanese Patent Publication No. 3-2450, Japanese Patent Application Laid-Open No. 2005-213446, No. 2005-306891, International Publication No. WO 2007-040143, 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.
- Diene compounds such as butadiene and isoprene are homopolymerized or copolymerized with the above olefin compounds. After that, it can be obtained by a method such as hydrogenation.
- 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.
- 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.
- Examples of the method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-62-254149, JP-A-62-2904, 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.
- (meth) acrylic-ester type monomer which comprises the principal chain of the said (meth) acrylic-ester type polymer
- (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, de
- 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, phenylthioethyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as 3-methoxybutyl, 2-hydroxyethyl (meth
- the following vinyl monomers can be copolymerized together with the (meth) acrylic acid ester monomer.
- the vinyl monomers include styrene monomers such as styrene, vinyl toluene, ⁇ -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 prop
- 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.
- (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
- 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). Synthesis method described in JP-A-2003-313397), radical polymerization method using radical polymerization reaction is preferable.
- 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.
- 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 free radical polymerization method and living radical polymerization method using a chain transfer agent having a specific functional group, such as an addition-cleavage transfer reaction (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 above (meth) acrylic acid ester-based polymer having a crosslinkable silicon group may be used alone or in combination of two or more.
- 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.
- Japanese Laid-Open Patent Publication No. 63-112642 Japanese Laid-Open Patent Publication No. 6-172631, and Japanese Laid-Open Patent Publication No. 11-116763
- the invention is not particularly limited thereto.
- Preferable specific examples include a crosslinkable silicon group and a molecular chain substantially having the following general formula (5): —CH 2 —C (R 3 ) (COOR 4 ) — (5) (Wherein R 3 represents a hydrogen atom or a methyl group, R 4 represents an alkyl group having 1 to 5 carbon atoms) and a 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 consisting of a (meth) acrylate 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 carbon atoms, more preferably 1 to 4 carbon atoms. 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 or the like having 6 or more carbon atoms, usually 7 to 30, preferably 8 to 20 Long chain alkyl groups.
- 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 by mass ratio.
- Examples of monomer units other than the formulas (5) and (6) that may be contained in the copolymer include ⁇ such as acrylic acid and methacrylic acid. , ⁇ -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, ⁇ -methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.
- 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 )
- the acrylate polymer for example, it has a crosslinkable silicon group described in JP-A No.
- 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 (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 with respect to 100 parts by mass in total of the polymer and the polyoxyalkylene polymer. It is within the range of 50 parts by mass, and more preferably within the range of 25 to 45 parts by mass. If the amount of the (meth) acrylic acid ester polymer is more than 60 parts by mass, the viscosity becomes high and workability deteriorates, which is not preferable.
- 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.
- 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 is preferably used in an amount of 10 to 200 parts by weight, more preferably 20 to 80 parts by weight.
- the photobase generator (B) acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer when irradiated with light.
- the photobase generator (B) is not particularly limited as long as it is a substance that generates a base by the action of active energy rays such as ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays.
- Ultraviolet rays / 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.
- the base generated from the photobase generator (B) is not particularly limited, but is preferably an organic base such as an amine compound.
- a first base 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 Amines having a group; tertiary alkylamines such as trimethylamine, triethylamine, tributylamine, 1,8-diazabicyclo [2.2.2] octane (DABCO); tertiary heterocyclic such as 4-isopropylmorpholine Amine; 4-dimethylaminopyridine, N, N-dimethyl (3-phenoxy- Tertiary aromatic amines such as 2-hydroxypropyl) amine; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 Amidines such as (DBN); phosphazene derivatives such as tris (dimethylamino) (
- Examples of the acyclic amidines include guanidine compounds and biguanide compounds.
- Examples of the guanidine compound include guanidine, 1,1,3,3-tetramethylguanidine, 1-butylguanidine, 1-phenylguanidine, 1-o-tolylguanidine, 1,3-diphenylguanidine and the like.
- Examples of biguanide compounds include butyl biguanide, 1-o-tolyl biguanide and 1-phenyl biguanide.
- 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,
- 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
- cyclic amidines examples 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 [4.4.0] dec-5-ene, 7-isopropyl-1, 5,7-triaza-bicyclo [4.4.0] dec-5-ene and the like.
- imidazoline compounds examples include 1-methylimidazoline, 1,2-dimethylimidazoline, 1-methyl-2-ethylimidazoline, 1-methyl-2-octylimidazoline, and the like.
- imidazole compound examples include imidazole and 2-ethyl-4-methylimidazole.
- tetrahydropyrimidine compounds include 1-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-methyl-2-ethyl- 1,4,5,6-tetrahydropyrimidine, 1-methyl-2-butyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-octyl-1,4,5,6-tetrahydropyrimidine, etc. Can be mentioned.
- triazabicycloalkene compound examples 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.
- diazabicycloalkene compounds examples 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.
- DBU undecene-7
- DBN 1,5-diazabicyclo [4.3.0] nonene-5
- the photobase generator (B) used in the present invention a known photobase generator can be used, but 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.
- photolatent primary amine and photolatent secondary amine examples 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-ni Rophenyl) ethylcyclohexyl
- photolatent tertiary amine examples include ⁇ -forms such as dimethyl benzyl ammonium salt of phenylglyoxylic acid and tri-n-butyl ammonium salt of phenylglyoxylic acid described in JP-A-55-22669.
- Ketocarboxylic acid ammonium salt trimethylbenzhydrylammonium iodide, 1- (9H-fluoren-9-yl) -1-azabicyclo [2,2,2] octanium bromide described in JP-A-2007-119766, 1- (2-acetyl-9H-fluoren-9-yl) -1-azabicyclo [2,2,2] octanium bromide, 1- (2-methoxy-9H-fluoren-9-yl) -1-azabicyclo [2, 2,2] octanium bromide, 1- (2-phenacyl-9H-fluoren-9-yl) -1 Benzhydrylammonium salt derivatives such as azabicyclo [2,2,2] octonium bromide; ⁇ -onium acetophenone derivatives; [(2-hydroxy-3-phenoxypropyl) dimethylaminio] described in WO2002 / 051905 (4 -Nitrobenzoyl)
- ⁇ -aminoketone derivatives phenacyltriethylammonium tetraphenylborate, (4-methoxyphenacyl) triethylammonium tetraphenylborate, 1-phenacyl- (1-azonia-) described in JP-T-2001-513765 and WO2005 / 014696 4-azabicyclo [2,2,2] -octane) tetraphenylborate, (1,4-phenacyl-1,4-diazoniabicyclo [2.2.2] octane) bis (tetraphenylborate), 1-naphtho Ilmethyl- (1-azonia-4-azabicyclo [2,2,2] -octane ) Tetraphenylborate, 1- (4′-phenyl) phenacyl- (1-azonia-4-azabicyclo [2.2.2] octane) tetraphenylborate, 5- (4′-pheny
- carboxylate represented by the following formula (I) (for example, JP 2009-280785 A and JP 2011-80032 A); 2- (carboxymethylthio) thioxanthone described in JP 2007-262276 A Carboxylic acid ammonium salts such as 3-quinuclidinol salts and 3-quinuclidinol salts of 2- (carboxymethoxy) thioxanthone; trans-o-coumaric acid derivatives described in JP 2010-254982 A and JP 2011-213783 A; N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -N-methylacetamide, N- (N ′-( 4,5-dimethoxy-2-nitrobenzyloxycarbonyl) amino Propyl) diamine derivative such as 6-heptane lactam; may be used photolatent amine compounds such as.
- photolatent amine compounds such as.
- the Ar group is an aromatic ring, and the aromatic ring may contain a benzoyl group, a nitro group, an alkoxy group, or an alkyl group as a substituent, and the substituent of the aromatic ring has a ring structure.
- R ′ and R ′′ are each a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group.
- M is an alkali metal, an alkaline earth metal, or an imidazole represented by the following formula (II), It is a base consisting of either an amidine represented by the following formula (III), a guanidine represented by the following formula (IV), or a phosphazene derivative represented by the following formula (V), where n is 1 or An integer of 2 is shown.
- each R independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (which may contain a hetero atom such as S), or a phenyl group.
- m represents an integer of 1 to 3.
- R 21 to R 25 each independently represent a hydrogen atom, an alkyl group or an aryl group, and the alkyl group may have a cyclic structure.
- R 31 to R 37 each independently represent a hydrogen atom, an alkyl group or an aryl group, and the alkyl group may have a cyclic structure.
- ⁇ -aminoketone compounds represented by the following formulas (VII) to (X) are preferable examples.
- 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, 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,
- R 52 and R 53 independently of one another are hydrogen, C 1 -C 18 alkyl, C 3 -C 18 alkenyl, C 3 -C 18 alkynyl or phenyl, and if R 52 is hydrogen or C 1 -C If it is 18 alkyl, 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 a carbonyl group and R 53 are attached form a benzo cyclopentanone group; R 54 and R 56, taken together, C 3 alkylene bridge to form; and R 55 R 57 together is propylene or pentylene.
- R 75 each independently represents an aromatic or heteroaromatic group, and examples thereof include those similar to R 51 in the above formula (VII).
- R 71 and R 72 are the same as R 52 and R 53 in the formula (VII), and when a plurality of R 71 and R 72 are present, they may be the same or different.
- R 73 is an alkyl group having 1 to 12 carbon atoms; —OH, —alkoxy having 1 to 4 carbon atoms, —CN, or —COO (alkyl having 1 to 4 carbon atoms) substituted with 2 to 2 carbon atoms.
- R 73 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 74 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).
- R 74 is an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl-alkyl group having 1 to 3 carbon atoms, or unsubstituted Or a phenyl group substituted by an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or —COO (alkyl having 1 to 4 carbon atoms), or R 74 is alkylene group having 1 to 7 carbon atoms together with R 73, phenyl - alkylene group having a carbon number of 1 to 4, o-xylylene group, a 2-butenylene group, or Okisaarukire carbon atoms 2 or 3 Or a group, or R 73 and R 74 together -O -, - or an alkylene group having 4 to 7 carbon atoms which may be interrupted S- or by -CO-
- Y 1 represents a divalent group represented by the following formula (XI), a divalent group represented by —N (R 81 ) — or —N (R 81 ) —R 82 —N (R 81 ) —, R 81 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 82 represents an unbranched or branched alkylene group having 2 to 16 carbon atoms which can be interrupted by one or more —O— or —S—.
- Y 2 represents an alkylene group having 1 to 6 carbon atoms, a cyclohexylene group or a direct bond.
- examples of the photobase generator (B) include ⁇ -ammonium ketone compounds represented by the following formula (XII).
- 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 anions, toluic acid) Anions, phenylglyoxylate anions, etc.).
- 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
- 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.
- tetraphenylborate anion and phenylglyoxylate anion are particularly preferable.
- R 91 is the same as R 51 in the formula (VII).
- R 92 , R 93 and R 94 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 92 and R 93 and / or Or R 94 and R 93 independently of one another form a C 2 to C 12 alkylene bridge; or R 92 , R 93 , R 94 together with the nitrogen atom to which they are attached, P 1 , P 2 , P ⁇ T / 4> type phosphazene base or a group of the following structural formula (a), (b), (c), (d), (e), (f) or (g) is formed .
- R 95 is hydrogen or C 1 -C 18 alkyl; or R 95 and R 91 together with the carbon atoms to which they are attached form a benzocyclopentanone group.
- R 91 and R 95 are the same as in the formula (XII), and l and q are each independently a number of 2 to 12.
- examples of the photobase generator (B) include a benzylamine compound represented by the following formula (XIII).
- R 101 is the same as R 51 in the formula (VII).
- R 102 and R 103 are independently of one another hydrogen or C 1 -C 18 alkyl.
- R 104 and R 106 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 105 and R 107 taken together, independently of R 104 and R 106 are C 2 -C 4 which are unsubstituted or substituted by one or more C 1 -C 4 alkyl groups. 12 forms an alkylene bridge.
- examples of the photobase generator (B) include benzylammonium salts represented by the following formula (XIV).
- V - and V in the formula (XII) - are the same as.
- R 111 is the same as R 51 in the formula (VII).
- R 112 to R 114 are each independently the same as R 92 , R 93 and R 94 in the formula (XII).
- R 115 and R 116 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, 1 to 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 115 and R 116 may be bonded to each other to form a ring structure.
- 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.
- benzylammonium salt derivatives, benzyl-substituted amine derivatives, ⁇ -aminoketone derivatives, ⁇ -ammoniumketone derivatives are preferable.
- no base is generated when not exposed to light, and base is generated efficiently when exposed to light. Therefore, benzylammonium salt derivatives and benzyl-substituted amine derivatives are more preferable.
- photobase generators (B) may be used alone or in combination of two or more.
- the mixing ratio of the photobase generator (B) is not particularly limited, but is preferably 0.01 to 50 parts by weight, preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the (A) crosslinkable silicon group-containing organic polymer. More preferred is 40 parts by mass, and even more preferred is 0.5 to 30 parts by mass.
- the (C1) silicon compound having a Si—F bond acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer.
- a known compound containing a silicon group having Si—F bond hereinafter sometimes referred to as a fluorosilyl group
- 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.
- the low molecular organosilicon compound which has a fluoro silyl group from the point from which a compound becomes low viscosity is preferable.
- silicon compound having (C1) Si—F bond examples include compounds having a fluorosilyl group represented by the following formula (8) such as fluorosilanes represented by the following formula (7)
- the organic polymer having a fluorosilyl group also referred to as a fluorinated polymer in the present specification
- the like are preferable examples.
- R 11 4-d SiF d (7)
- R 11 is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 12 SiO— (R 12 is each independently having 1 to 20 carbon atoms) 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 when there are a plurality of R 12 s , they may be the same or different.
- R 11 and d are the same as those in the formula (7), Z is each independently a hydroxyl group or a hydrolyzable group other than fluorine, and e is any of 0-2. , F is 0 to 2, and d + e + f is 3.
- R 11 , R 12 and Z are present, they may be the same or different.
- fluorosilanes represented by the formula (7) include known fluorosilanes represented by the formula (7), and are not particularly limited.
- fluorodimethylvinylsilane fluorodimethylphenylsilane, fluorodimethylbenzylsilane, vinyltrifluorosilane, vinyldifluoromethylsilane, and ⁇ -methacryloxypropyl because raw materials are easily available and synthesis is easy.
- 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 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.
- 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
- 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.
- inorganic compounds such as tetrafluorosilane and octafluorotrisilane can be used.
- Silicon compound represented by the above formula (7), fluorotrimethoxysilane, difluorodimethoxysilane, trifluoromethoxysilane, fluorotriethoxysilane, difluorodiethoxysilane, trifluoroethoxysilane, methylfluorodimethoxysilane, methyl Difluoromethoxysilane, methyltrifluorosilane, methylfluorodiethoxysilane, methyldifluoroethoxysilane, vinylfluorodimethoxysilane, vinyldifluoromethoxysilane, vinyltrifluorosilane, vinyl Low molecular weight organosilicon compounds such as orodiethoxysilane, vinyldifluoroethoxysilane, phenylfluorodimethoxysilane, phenyldifluoromethoxysilane, phenyltrifluorosilane, phenylfluorodieth
- 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)
- hydrolyzable silicon group represented by the above formula (9) examples include alkoxysilyl groups, siloxane bonds, halosilyl groups such as chlorosilyl groups, hydrosilyl groups, and the like.
- fluorinating agent used for fluorination of the alkoxysilyl group are not particularly limited.
- fluorinating agent used for fluorination of the halosilyl group are not particularly limited.
- 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 BF3 or the like to obtain a fluorosilyl group.
- 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.
- 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. 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).
- a polymer having a fluorosilyl group represented by the above formula (8) is preferable.
- the fluorosilyl group 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,
- 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.
- the fluorinated polymer can be suitably used as a resin component of a curable composition exhibiting fast curing properties.
- 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.
- 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.
- 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.
- 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.
- each silicon group may be the same or different.
- 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.
- 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.
- 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.
- the method (i) include the following methods.
- 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.
- 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.
- the above-mentioned crosslinkable silicon group-containing organic polymer (A) is used.
- the above-mentioned crosslinkable silicon group-containing organic polymer (A) is used.
- 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.
- the hydrolyzable silicon group is converted to a fluorosilyl group with a fluorinating agent.
- 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.
- 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 fluorination may take time. If the temperature is 150 ° C or higher, the fluorinated polymer may be decomposed.
- 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.
- 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.
- fluorination hardly progresses after the dehydration operation, and the reactivity tends to be improved by adding a small amount of water. Is preferably added.
- 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.
- 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.
- 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.
- 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).
- 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 hydrolyzable groups in the reactive silicon group.
- 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 above method (i) can also be synthesized from a general-purpose reactive silicon group-containing low molecular compound using the above fluorination method.
- 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.
- 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 less, more preferably 0 ° C. or less, and particularly preferably ⁇ 20 ° C. or less.
- 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 (C1) 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 (C1), (A) cross-linking Is preferably 0.2 to 80 parts by mass, more preferably 0.3 to 30 parts by mass, and still more preferably 0.5 to 20 parts by mass 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 (C1) for example, a low molecular organic silicon having a fluorosilane group represented by the formula (7) or a fluorosilyl group represented by the formula (8)
- (A) 0.01 to 10 parts by mass is preferable with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer. Part by mass is more preferable.
- the blending ratio of the photobase generator (B) used as a curing catalyst and the silicon compound (C1) having a Si—F bond is such that (B) :( C1) is a mass ratio. Is preferably 1: 0.008 to 1: 300, more preferably 1: 0.016 to 1:40.
- (C2) one or more fluorine compounds selected from the group consisting of boron trifluoride, boron trifluoride complexes, fluorinating agents and alkali metal salts of polyvalent fluoro compounds are crosslinkable silicon groups. It acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer.
- boron trifluoride complex examples include boron trifluoride amine complex, alcohol complex, ether complex, thiol complex, sulfide complex, carboxylic acid complex, and water complex.
- boron trifluoride complexes an amine complex having both stability and catalytic activity is particularly preferable.
- Examples of the amine compound used for the boron trifluoride amine complex include ammonia, monoethylamine, triethylamine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, guanidine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, N-methyl-3,3'-iminobis (propylamine), ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, 1,9-diaminononane, ATU (3,9-bis (3-aminopropyl) -2 , 4 8,10-tetraoxaspiro [5.5] undecane), CTU
- a compound having a plurality of primary amino groups such as amine, piperazine, cis-2,6-dimethylpiperazine, cis-2,5-dimethylpiperazine, 2-methylpiperazine, N, N'-di-t-butylethylenediamine 2-aminomethylpiperidine, 4-aminomethylpiperidine, 1,3-di- (4-piperidyl) -propane, 4-aminopropylaniline, homopiperazine, N, N'-diphenylthiourea, N, N'- Compounds having a plurality of secondary amino groups such as diethylthiourea and N-methyl-1,3-propanediamine, and methylaminopropylamine, ethylaminopropylamine, ethylaminoethylamine, laurylaminopropylamine, 2-hydroxy Ethylaminopropylamine, 1- (2-aminoethyl) piperazine, N
- ⁇ -aminopropyltriethoxysilane ⁇ -aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltriethoxysilane, N- ⁇ (Aminoethyl) - ⁇ -aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltriethoxysilane, (aminoethylaminomethyl) phenethyltriethoxysilane, N- (6-aminohexyl) ) Aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltriethoxysilane, N- (2-aminoethyl) L) Aminosilane compounds such as 11-aminoundecyltrieth
- the fluorinating agent includes a nucleophilic fluorinating agent having a fluorine anion as an active species and an electrophilic fluorinating agent having an electron deficient fluorine atom as an active species.
- nucleophilic fluorinating agent examples include 1,1,2,3,3,3-hexafluoro-1-such as 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane.
- examples thereof include dialkylaminopropane compounds, trialkylamine trishydrofluoride compounds such as triethylamine trishydrofluoride, and dialkylaminosulfur trifluoride compounds such as diethylaminosulfur trifluoride.
- electrophilic fluorinating agent examples include N-fluoro such as bis (tetrafluoroboric acid) N, N′-difluoro-2,2′-bipyridinium salt compound and trifluoromethanesulfonic acid N-fluoropyridinium salt compound.
- N-fluoro such as bis (tetrafluoroboric acid) N, N′-difluoro-2,2′-bipyridinium salt compound and trifluoromethanesulfonic acid N-fluoropyridinium salt compound.
- 4-fluoro-1,4-diazoniabicyclo [2.2.pyridinium salt compounds such as bis (tetrafluoroboric acid) 4-fluoro-1,4-diazoniabicyclo [2.2.2] octane salts.
- N-fluorobis (sulfonyl) amine compounds such as octane compounds and N-fluorobis (phenylsulfonyl) amines.
- 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane compounds are particularly preferable because they are liquid compounds and are easily available.
- alkali metal salt of the polyvalent fluoro compound examples include sodium hexafluoroantimonate, potassium hexafluoroantimonate, sodium hexafluoroarsenate, potassium hexafluoroarsenate, lithium hexafluorophosphate, sodium hexafluorophosphate, Potassium hexafluorophosphate, sodium pentafluorohydroxoantimonate, potassium pentafluorohydroxoantimonate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, sodium tetrakis (trifluoromethylphenyl) borate, tri Sodium fluoro (pentafluorophenyl) borate, potassium trifluoro (pentafluorophenyl) borate, difluorobis (pentafluorophenyl) Sulfonyl) sodium borate, difluoro (pentafluor
- tetrafluoroboric acid or hexafluorophosphoric acid is preferable as the polyvalent fluoro compound component in the alkali metal salt of the polyvalent fluoro compound.
- the alkali metal in the alkali metal salt of the polyvalent fluoro compound is preferably at least one alkali metal selected from the group consisting of lithium, sodium and potassium.
- the blending ratio of the (C2) fluorine-based compound is not particularly limited, but is preferably 0.001 to 10 parts by weight, and 0.001 to 5 parts per 100 parts by weight of the (A) crosslinkable silicon group-containing organic polymer. Mass parts are more preferred, and 0.001 to 2 parts by mass are even more preferred. These fluorine compounds may be used alone or in combination of two or more.
- the photocurable composition of the present invention preferably further contains (D) a silane coupling agent.
- (D) a silane coupling agent By blending the (D) silane coupling agent, adhesion to general adherends such as metals, plastics, and glass can be improved.
- silane coupling agent (D) examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyl.
- Amino such as trimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane Group-containing silanes; N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl)- Ketimine type silanes such as 1-propanamine; ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - Epoxy group-containing silanes such as glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ - (3,4-epoxy
- 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 (D) is not particularly limited, but is preferably 0.2 to 20 parts by weight, preferably 0.3 to 200 parts by weight with respect to 100 parts by weight of the (A) crosslinkable silicon group-containing organic polymer. 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable. These silane coupling agents may be used alone or in combination of two or more.
- a photosensitizer In the photocurable composition of the present invention, a photosensitizer, a bulking agent, a plasticizer, a moisture absorbent, a curing catalyst, a physical property modifier that improves tensile properties, a reinforcing agent, a colorant, if necessary, Various additives such as flame retardants, anti-sagging agents, antioxidants, anti-aging agents, ultraviolet absorbers, solvents, fragrances, pigments and dyes may be added.
- a carbonyl compound having a triplet energy of 225 to 310 kJ / mol is preferable.
- the photosensitizer is more preferably an energy ray-cleaving radical generator that is a type of photoradical generator that generates radicals by cleavage of the compound by irradiation with energy rays such as light.
- the energy ray-cleaving radical generator is used, the curing rate is much faster than when using photosensitizers such as benzophenones and thioxanthones known as sensitizers for photobase initiators.
- the photocurable composition of the present invention can be cured immediately after energy beam irradiation.
- 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.
- cleavage-type radical generators include, for example, 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, ( ⁇ 6 -isopropyl Benzene)-( ⁇ 5 -cyclopentadienyl) -iron (II) X
- the blending ratio of the photosensitizer is not particularly limited, but is preferably 0.01 to 5% by mass, 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.
- extender examples 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.
- plasticizer examples 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.
- 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.
- 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.
- 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.
- the toxicity of the resulting photocurable composition may increase depending on the amount of the organic tin compound added.
- the method for producing the photocurable composition of the present invention is not particularly limited.
- the components (A), (B), and (C1) and / or (C2) are blended in a predetermined amount, and if necessary. It can be manufactured by mixing other compounding substances and degassing and stirring. There is no particular limitation on the order of blending each component and other compounding substances, and it may be determined as appropriate.
- the photocurable composition of the present invention can be made into a one-component type or a two-component type as required, and 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.
- cured material of this invention forms a hardened
- the cured product of the present invention is a cured product formed by this method.
- the manufacturing method of the product of this invention is manufactured using the photocurable composition of this invention, It is characterized by the above-mentioned.
- the product of the present invention is a product produced by using this method, and can be suitably used for electronic circuits, electronic parts, building materials, automobiles and the like.
- the light curable composition of the present invention is not particularly limited as a condition for irradiating light, but when irradiating active energy rays during curing, the active energy rays include rays such as ultraviolet rays, visible rays, infrared rays, In addition to electromagnetic waves such as X-rays and ⁇ -rays, electron beams, proton beams, neutron beams, etc. can be used, but curing speed, availability and price of irradiation equipment, easy handling under sunlight and general lighting In view of the properties, curing by ultraviolet ray or electron beam 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. It is done.
- the irradiation energy of ultraviolet rays for example, preferably 10 ⁇ 20,000mJ / cm 2, more preferably 50 ⁇ 10,000mJ / cm 2. If it is less than 10 mJ / cm 2 , the curability may be insufficient. If it is greater than 20,000 mJ / cm 2 , it will not only waste time and cost, but also damage the substrate. May end up.
- the method for applying the photocurable composition of the present invention to an adherend is not particularly limited, but screen printing, stencil printing, roll printing, spin coating, and the like are preferably used.
- the product is bonded to the adherend.
- the product may be produced by applying a photocurable composition to an adherend and irradiating light to cure the composition.
- the photocurable composition of the present invention is a fast-curing type photocurable composition excellent in workability, and is particularly useful as an adhesive / adhesive composition, and includes an adhesive, a sealing material, an adhesive, and a coating. It can be suitably used as a material, potting material, paint, putty material, primer and the like.
- the photocurable composition of the present invention includes, for example, a coating agent used for moisture-proofing and insulation of a mounted circuit board and the like, a coating for solar power generation panels and the outer peripheral portion of the panel, and the like; , Architectural and industrial sealing agents, such as sealing agents for vehicles; electrical and electronic component materials such as solar cell back surface sealing agents; electrical insulating materials such as insulation coating materials for electric wires and cables; adhesives; adhesives; elasticity Adhesives; can be suitably used for applications such as contact adhesives.
- a coating agent used for moisture-proofing and insulation of a mounted circuit board and the like a coating for solar power generation panels and the outer peripheral portion of the panel, and the like
- Architectural and industrial sealing agents such as sealing agents for vehicles; electrical and electronic component materials such as solar cell back surface sealing agents; electrical insulating materials such as insulation coating materials for electric wires and cables; adhesives; adhesives; elasticity Adhesives; can be suitably used for applications such as contact adhesives.
- a methanol solution of sodium methoxide is added to the obtained polyoxypropylene diol, methanol is distilled off under heating and reduced pressure, and the terminal hydroxyl group of the polyoxypropylene diol is converted to sodium alkoxide to obtain a polyoxyalkylene polymer M1. It was.
- the polyoxyalkylene polymer M1 is reacted with allyl chloride at the blending ratio shown in Table 1 to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. Coalescence was obtained.
- This polyoxyalkylene polymer having an allyl group at the end is reacted with trimethoxysilane, which is a silicon hydride compound, by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and trimethoxysilyl at the end.
- a polyoxyalkylene polymer A1 having a group was obtained.
- the peak top molecular weight was 12,000 and the molecular weight distribution was 1.3.
- the number of terminal trimethoxysilyl groups was 1.7 per molecule.
- the polyoxyalkylene polymer M1 is the polyoxyalkylene polymer M1 obtained in Synthesis Example 1
- the polyoxyalkylene polymer M5 is the polyoxyalkylene polymer M5 obtained in Synthesis Example 6.
- a polyoxyalkylene system having a trimethoxysilyl group at the terminal obtained in Synthesis Example 1 was added to a new flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser at the blending ratio shown in Table 2.
- Polymer A1 and toluene were added. 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. 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.
- fluorinated polymer C1-1 a polyoxyalkylene polymer C1-1 having a trifluorosilyl group at the terminal (hereinafter referred to as fluorinated polymer C1-1).
- 1H-NMR spectrum of the obtained fluorinated polymer C1-1 was measured, and the silylmethylene (—CH2-Si) of the polymer A1 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-).
- the polyoxyalkylene polymer A1 is the polyoxyalkylene polymer A1 obtained in Synthesis Example 1
- the polyoxyalkylene polymer A5 is the polyoxyalkylene polymer A5 obtained in Synthesis Example 6.
- Acrylic polymer A2 having a trimethoxysilyl group having a polystyrene-equivalent weight average molecular weight of about 6000, Mw / Mn of 1.6, and Tg of 61.2 ° C. Obtained.
- the copper catalyst was removed and purified through an activated alumina column to obtain poly (n-butyl acrylate) having a Br group at the end.
- the number average molecular weight of the obtained polymer was 10700, and the molecular weight distribution was 1.15.
- (N-butyl acrylate) A4 (hereinafter referred to as acrylic polymer A4) was obtained.
- the viscosity of the obtained polymer was 44 Pa ⁇ s, the number average molecular weight was 11900, and the molecular weight distribution was 1.12. Further, according to 1H-NMR analysis, the number of methyldimethoxysilyl groups per molecule of the polymer was 1.46.
- 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 M5. It was.
- the polyoxyalkylene polymer M5 is reacted with allyl chloride at the blending ratio shown in Table 1 to remove unreacted allyl chloride, and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. Coalescence was obtained.
- 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 A5 having a group was obtained.
- the peak top molecular weight was 15000 and the molecular weight distribution was 1.3.
- the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.
- fluorinated polymer C3 A polyoxyalkylene polymer C3 having a fluorosilyl group at the terminal (hereinafter referred to as fluorinated polymer C3) was obtained.
- Example 1 In a mixing ratio shown in Table 3, the polyoxyalkylene polymer A3 obtained in Synthesis Example 4 was added to a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser, It dehydrated by heating (100 degreeC), deaeration, and stirring for 2 hours. After cooling, fluorinated polymer C1-1 obtained in Synthesis Example 1, photobase generator B1, and KBM-1003 [manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane] as a water absorbent were added, respectively. A photocurable composition was prepared by mixing and stirring.
- the compounding amount of each compounding substance is indicated by g, the numerical value in parentheses is the solid content, and the polyoxyalkylene polymer A3 is the polyoxyalkylene polymer A3 obtained in Synthesis Example 4,
- the acrylic polymer A4 is the acrylic polymer A4 obtained in Synthesis Example 5
- the acrylic polymer A2 is the acrylic polymer A2 obtained in Synthesis Example 2
- the fluorinated polymer C1-1 is Synthesis Example 1.
- the fluorinated polymer C1-1 obtained in the above, the fluorinated compound C1-2 is the fluorinated compound C1-2 obtained in Synthesis Example 3, and details of other compounding substances are as follows.
- Photobase generator B1; PBG-SA1 [trade name of San Apro Co., Ltd., photolatent tertiary amine that generates DBU by light, 8- (9-oxo-9H-thioxanthen-2-yl) methyl -1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate] 20% by mass and propylene carbonate 80% by mass.
- Photobase generator B2 WPBG-082 [trade name, manufactured by Wako Pure Chemical Industries, Ltd., photolatent amine that generates guanidine by light, guanidine 2- (3-benzoylphenyl) propionate] 30% by mass and N-methyl Mixture with 70% by weight of pyrrolidone.
- KBM-1003 trade name, vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
- the resulting photocurable composition was subjected to a curability test and an adhesion test by the following methods. The results are shown in Tables 4 and 5.
- 1) Curability test A photocurable composition was applied to a metal plate to a thickness of about 50 ⁇ m, and after UV irradiation [irradiation conditions: metal halide lamp (illuminance 50 mW / cm 2 ), integrated light quantity: 2000 mJ / cm 2 ] or UV irradiation.
- ⁇ Gelation (intermediate between liquid and solid)
- Adhesion test A photocurable composition is applied to a stainless steel plate (25 mm ⁇ 100 mm ⁇ 1.5 mm) to a thickness of about 50 ⁇ m, and UV irradiation [irradiation conditions: metal halide lamp (illuminance: 50 mW / cm 2 ), integrated light intensity] : 200 mJ / cm 2 ]. Immediately after UV irradiation, it was overlapped with the central part of the same size stainless steel plate and bonded to form a cross. It was determined whether or not it would not move by hand after being left for 24 hours at 23 ° C. and 50% RH. The case where it did not move was evaluated as ⁇ , and the case where it moved was evaluated as x.
- Examples 2 to 5 A photocurable composition was prepared in the same manner as in Example 1 except that the compounding materials were changed as shown in Table 3. The photocurable composition was subjected to a curable test and an adhesive test in the same manner as in Example 1. The results are shown in Tables 4 and 5.
- Example 1 A photocurable composition was prepared in the same manner as in Example 1 except that the compounding materials were changed as shown in Table 3. The photocurable composition was subjected to a curable test and an adhesive test in the same manner as in Example 1. The results are shown in Tables 4 and 5.
- Example 6 A photocurable composition was prepared in the same manner as in Example 1 except that the compounding materials were changed as shown in Table 6.
- the surface curability test of the photocurable composition was performed by the following method, and the results are shown in Table 6.
- a photocurable composition is poured into a round container having a diameter of 20 mm so as to have a thickness of 7 mm, UV non-irradiation and UV irradiation [irradiation conditions: metal halide lamp (illuminance: 330 mW / cm 2 ), integration. [Light quantity: 3000 mJ / cm 2 ] Under a dark room at 23 ° C. and RH 50%, the time until the surface became non-sticky by touch with a finger every 30 seconds (tack-free time) was measured.
- the compounding amount of each compounding substance is indicated by g, the numerical value in parentheses is the solid content, and the polyoxyalkylene polymer A3 is the polyoxyalkylene polymer A3 obtained in Synthesis Example 4,
- the fluorinated polymer C1-3 is the fluorinated polymer C1-3 obtained in Synthesis Example 7, and details of other compounding substances are as follows.
- Photobase generator B3 a propylene carbonate solution containing 50% by mass of Irgacure (registered trademark) 907 (manufactured by BASF, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one).
- Photobase generator B4 DMSO solution containing 50% by mass of Irgacure (registered trademark) 369 (manufactured by BASF, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1).
- Photobase generator B5 Irgacure (registered trademark) 379EG [trade name, manufactured by BASF, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl ] -1-Butanone] A mixture of 50% by mass and 50% by mass of propylene carbonate.
- Darocur 1173 trade name, cleavage type photo radical generator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, manufactured by BASF.
- the compounding amount of each compounding substance is indicated by g, the numerical value in parentheses is the solid content, and the polyoxyalkylene polymer A3 is the polyoxyalkylene polymer A3 obtained in Synthesis Example 4.
- the fluorinated polymer C1-3 is the fluorinated polymer C1-3 obtained in Synthesis Example 7, and details of other compounding substances are as follows.
- Photobase generator B1 PBG-SA1 [trade name, manufactured by San Apro Co., Ltd., a photolatent tertiary amine that generates DBU by light, 8- (9-oxo-9H-thioxanthen-2-yl) methyl -1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate] 20% by mass and propylene carbonate 80% by mass.
- Photobase generator B5 Irgacure (registered trademark) 379EG [trade name, manufactured by BASF, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl ] -1-Butanone] A mixture of 50% by mass and 50% by mass of propylene carbonate.
- Fluorine compound C2 A mixture of 10% by mass of boron trifluoride monoethylamine and 90% by mass of propylene carbonate.
- KBM-1003 Trade name, vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
- Darocur 1173 trade name, cleavage type photo radical generator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, manufactured by BASF.
- a surface curability test (a) was performed on the obtained photocurable compositions of Examples 12 and 13 and Comparative Example 2 by the following method. The results are shown in Table 9.
- (A) A photocurable composition is poured into a cylindrical container having a diameter of 20 mm and a height of 7 mm so as to have a thickness of 7 mm, UV non-irradiation and UV irradiation [irradiation conditions: metal halide lamp (illuminance: 330 mW / cm 2 ), Accumulated light quantity: 3000 mJ / cm 2 ]
- the surface of the photocurable composition after standing for a certain period of time shown in Table 10 in an environment of 23 ° C. and RH 50% in a dark room is checked with a finger to confirm the degree of curing.
- the photocurable composition of the present invention is a photocurable composition that does not cure when not irradiated with active energy rays but is cured by irradiation with active energy rays and has excellent workability. In addition, it can be cured in a short time even with a low integrated light amount. Furthermore, the photocurable composition of the present invention exhibited excellent adhesion performance even with a low integrated light amount. Moreover, it did not harden
Abstract
Description
本発明の硬化物は、本発明の硬化物の製造方法により形成されてなる硬化物である。
-R2-O-・・・(4)
前記一般式(4)中、R2は炭素数1~14の直鎖状もしくは分岐アルキレン基であり、炭素数1~14の、さらには2~4の、直鎖状もしくは分岐アルキレン基が好ましい。
-CH2O-、-CH2CH2O-、-CH2CH(CH3)O-、-CH2CH(C2H5)O-、-CH2C(CH3)2O-、-CH2CH2CH2CH2O-
等が挙げられる。ポリオキシアルキレン系重合体の主鎖骨格は、1種類だけの繰り返し単位からなってもよいし、2種類以上の繰り返し単位からなってもよい。
o-フェニルフェノール(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、フェノキシジエチレングリコール(メタ)アクリレート、フェノキシポリエチレングリコール(メタ)アクリレート、フェニルチオエチル(メタ)アクリレート等の芳香族(メタ)アクリル酸エステル系モノマー;(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸3-メトキシブチル、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸グリシジル、(メタ)アクリル酸2-アミノエチル等の(メタ)アクリル酸エステル系モノマー;γ-(メタクリロイルオキシプロピル)トリメトキシシラン、γ-(メタクリロイルオキシプロピル)ジメトキシメチルシラン、メタクリロイルオキシメチルトリメトキシシラン、メタクリロイルオキシメチルトリエトキシシラン、メタクリロイルオキシメチルジメトキシメチルシラン、メタクリロイルオキシメチルジエトキシメチルシラン等のシリル基含有(メタ)アクリル酸エステル系モノマー;(メタ)アクリル酸のエチレンオキサイド付加物等の(メタ)アクリル酸の誘導体;(メタ)アクリル酸トリフルオロメチルメチル、(メタ)アクリル酸2-トリフルオロメチルエチル、(メタ)アクリル酸2-パーフルオロエチルエチル、(メタ)アクリル酸2-パーフルオロエチル-2-パーフルオロブチルエチル、(メタ)アクリル酸パーフルオロエチル、(メタ)アクリル酸トリフルオロメチル、(メタ)アクリル酸ビス(トリフルオロメチル)メチル、(メタ)アクリル酸2-トリフルオロメチル-2-パーフルオロエチルエチル、(メタ)アクリル酸2-パーフルオロヘキシルエチル、(メタ)アクリル酸2-パーフルオロデシルエチル、(メタ)アクリル酸2-パーフルオロヘキサデシルエチル等のフッ素含有(メタ)アクリル酸エステル系モノマー等が挙げられる。
-CH2-C(R3)(COOR4)- ・・・(5)
(式中、R3は水素原子またはメチル基、R4は炭素数1~5のアルキル基を示す)で表される(メタ)アクリル酸エステル単量体単位と、下記一般式(6):
-CH2-C(R3)(COOR5)- ・・・(6)
(式中、R3は前記に同じ、R5は炭素数6以上のアルキル基を示す)で表される(メタ)アクリル酸エステル単量体単位からなる共重合体に、架橋性珪素基を有するポリオキシアルキレン系重合体をブレンドして製造する方法である。
これら塩基は単独で用いてもよく、2種以上組み合わせて用いてもよい。
グアニジン系化合物としては、グアニジン、1,1,3,3-テトラメチルグアニジン、1-ブチルグアニジン、1-フェニルグアニジン、1-o-トリルグアニジン、1,3-ジフェニルグアニジンなどを挙げることができる。
ビグアニド系化合物としては、ブチルビグアニド、1-o-トリルビグアニドや1-フェニルビグアニドを挙げることができる。
R52及びR53は、互いに独立して、水素、C1-C18アルキル、C3-C18アルケニル、C3-C18アルキニル又はフェニルであり、そしてもしR52が水素又はC1-C18アルキルであれば、R53は、更に、基-CO-R64(式中、R64は、C1-C18アルキル又はフェニルである)であるか;或いは、R51とR53は、カルボニル基及びR53が結合しているC原子と一緒になって、ベンゾシクロペンタノン基を形成し;R54とR56が、一緒になって、C3アルキレン橋を形成し;R55とR57が、一緒になって、プロピレン又はペンチレンである。
R73は炭素原子数1~12のアルキル基;-OH、-炭素原子数1~4のアルコキシ、-CNもしくは-COO(炭素原子数1~4のアルキル)で置換された炭素原子数2~4のアルキル基を表すか、または、R73は炭素原子数3~5のアルケニル基、炭素原子数5~12のシクロアルキル基またはフェニル-炭素原子数1~3のアルキル基を表す。R74は炭素原子数1~12のアルキル基;または-OH、-炭素原子数1~4のアルコキシ基、-CNもしくは-COO(炭素原子数1~4のアルキル)で置換された炭素原子数2~4のアルキル基を表すかまたはR74は炭素原子数3~5のアルケニル基、炭素原子数5~12のシクロアルキル基、フェニル-炭素原子数1~3のアルキル基、または、未置換であるかまたは炭素原子数1~12のアルキル基、炭素原子数1~4のアルコキシ基もしくは-COO(炭素原子数1~4のアルキル)によって置換されたフェニル基を表すか、あるいはR74はR73と一緒になって炭素原子数1~7のアルキレン基、フェニル-炭素原子数1~4のアルキレン基、o-キシリレン基、2-ブテニレン基または炭素原子数2もしくは3のオキサアルキレン基を表すか、あるいはR73およびR74は一緒になって-O-、-S-もしくは-CO-で中断され得る炭素原子数4~7のアルキレン基を表すか、またはR73及びR74は一緒になってOH、炭素原子数1~4のアルコキシ基もしくは-COO(炭素原子数1~4のアルキル)で置換され得る炭素原子数3~7のアルキレン基を表す。R73及びR74が複数存在する場合それらは同じであっても異なっていてもよい。
Y1は下記式(XI)で示される2価の基、-N(R81)-又は-N(R81)-R82-N(R81)-で示される2価の基を表し、R81は炭素原子数1~8のアルキル基、炭素原子数3~5のアルケニル基、フェニル-炭素原子数1~3のアルキル基、炭素原子数1~4のヒドロキシアルキル基もしくはフェニル基を表し、R82は1もしくはそれ以上の-O-または-S-により中断され得る枝分かれしていないまたは枝分かれした炭素原子数2~16のアルキレン基を表す。
Y2は炭素原子数1~6のアルキレン基、シクロヘキシレン基もしくは直接結合を表す。
R92、R93およびR94は、それぞれ互いに独立に、水素、C1~C18アルキル、C3~C18アルケニル、C3~C18アルキニルもしくはフェニルであり;またはR92とR93および/もしくはR94とR93が、互いに独立にC2~C12アルキレン架橋を形成しているか;あるいはR92、R93、R94が、結合している窒素原子とともに、P1、P2、P<t/4>型のホスファゼン塩基を、または、下記構造式(a)、(b)、(c)、(d)、(e)、(f)もしくは(g)の基を形成している。
R95は、水素またはC1~C18アルキルであり;あるいはR95およびR91は、結合している炭素原子とともに、ベンゾシクロペンタノン基を形成している。
前記光塩基発生剤(B)の配合割合は特に制限はないが、(A)架橋性珪素基含有有機重合体100質量部に対して、0.01~50質量部が好ましく、0.1~40質量部がより好ましく、0.5~30質量部がさらに好ましい。
(式(7)において、R11はそれぞれ独立して、置換あるいは非置換の炭素原子数1~20の炭化水素基、またはR12SiO-(R12はそれぞれ独立に、炭素原子数1~20の置換あるいは非置換の炭化水素基、又はフッ素原子である)で示されるオルガノシロキシ基のいずれかを示す。dは1~3のいずれかであり、dが3であることが好ましい。R11及びR12が複数存在する場合、それらは同じであっても異なっていてもよい。)
(式(8)中、R11及びdはそれぞれ式(7)と同じであり、Zはそれぞれ独立して水酸基又はフッ素以外の加水分解性基であり、eは0~2のいずれかであり、fは0~2のいずれかであり、d+e+fは3である。R11、R12及びZが複数存在する場合、それらは同じであっても異なっていてもよい。)
また、合成の容易さからフルオロジメチルシリル基、ジフルオロメチルシリル基、トリフルオロシリル基、フルオロメトキシメチルシリル基、フルオロエトキシメチルシリル基、フルオロメトキシエチルシリル基、フルオロジメトキシシリル基、フルオロジエトキシシリル基、ジフルオロメトキシシリル基、ジフルオロエトキシシリル基がより好ましく、安定性の観点からフルオロジメチルシリル基、ジフルオロメチルシリル基、トリフルオロシリル基などのフッ素以外に加水分解性基を持たないケイ素基がさらに好ましく、硬化性の高さからは、ジフルオロメチルシリル基、ジフルオロメトキシシリル基、ジフルオロエトキシシリル基、トリフルオロシリル基など、ケイ素基上に2個ないし3個のフッ素が置換したケイ素基が好ましく、トリフルオロシリル基が最も好ましい。
-SiR11 3-pZp ・・・(9)
(式(9)中、R11及びZはそれぞれ式(8)と同じであり、pは1~3のいずれかである。)
ハロシリル基のフッ素化に使用されるフッ素化剤の具体例としては、特に限定されず、例えば、AgBF4、SbF3、ZnF2、NaF、KF、CsF、NH4F、CuF2、NaSiF6、NaPF6、NaSbF6、NaBF4、Me3SnF、KF(HF)1.5~5などが挙げられる。
ヒドロシリル基のフッ素化に使用されるフッ素化剤の具体例としては、特に限定されず、例えば、AgF、PF5、Ph3CBF4、SbF3、NOBF4、NO2BF4などが挙げられる。
シロキサン結合を有する化合物はBF3などにより開裂し、フルオロシリル基が得られる。
有機重合体中のSiF結合の位置も特に制限はなく、重合体分子内のいずれの部位にあっても効果を発揮し、主鎖または側鎖の末端であれば-SiR’2F、重合体の主鎖に組み込まれていれば、-SiR’F-または≡SiF(R’はそれぞれ独立に、任意の基)の形で表される。
主鎖又は側鎖の末端にSi-F結合を有する有機重合体としては、前述した式(8)で示されるフルオロシリル基を有する重合体が好適である。フルオロシリル基が重合体の主鎖中に組み込まれたものの例としては、-Si(CH3)F-、-Si(C6H5)F-、-SiF2-、≡SiFなどが挙げられる。
(イ)分子中に水酸基、エポキシ基やイソシアネート基等の官能基を有する重合体に、この官能基に対して反応性を示す官能基およびフルオロシリル基を有する化合物を反応させる方法。たとえば、末端に水酸基を有する重合体とイソシアネートプロピルジフルオロメチルシランを反応させる方法や、末端にSiOH基を有する重合体とジフルオロジエトキシシランを反応させる方法が挙げられる。
(ロ)分子中に不飽和基を含有する重合体に、フルオロシリル基を有するヒドロシランを作用させてヒドロシリル化する方法。たとえば、末端にアリル基を有する重合体に、ジフルオロメチルヒドロシランを反応させる方法が挙げられる。
(ハ)不飽和基を含有する重合体に、メルカプト基およびフルオロシリル基を有する化合物を反応させる方法。たとえば、末端にアリル基を有する重合体に、メルカプトプロピルジフルオロメチルシランを反応させる方法が挙げられる。
フッ素化剤としては、例えば、前述したフッ素化剤が挙げられ、中でも、BF3エーテル錯体、BF3アルコール錯体、BF3二水和物は活性が高く、効率よくフッ素化が進行し、さらに副生成物に塩等が生じず、後処理が容易であるためにより好ましく、BF3エーテル錯体が特に好ましい。
さらに、BF3エーテル錯体によるフッ素化は、加熱しなくても反応が進行するが、より効率よくフッ素化を行なうためには、加熱することが好ましい。加熱温度としては50℃以上150℃以下が好ましく、60℃以上130℃がより好ましい。50℃以下であると反応が効率よく進行せず、フッ素化に時間がかかる場合がある。150℃以上であるとフッ素化ポリマーが分解する虞がある。BF3錯体によるフッ素化において、用いる重合体(X)の種類によっては着色が起こる場合があるが、着色の抑制の点から、BF3アルコール錯体、BF3二水和物を用いることが好ましい。
前記三フッ化ホウ素のアミン錯体の市販品としては、例えば、エアプロダクツジャパン株式会社製のアンカー1040、アンカー1115、アンカー1170、アンカー1222、BAK1171等が挙げられる。
これらの中でも、多価フルオロ化合物のアルカリ金属塩における多価フルオロ化合物成分としては、テトラフルオロホウ酸又はヘキサフルオロリン酸が好ましい。また、多価フルオロ化合物のアルカリ金属塩におけるアルカリ金属としては、リチウム、ナトリウム及びカリウムからなる群から選ばれる一種以上のアルカリ金属であることが好ましい。
また、本発明の製品の製造方法は、本発明の光硬化性組成物を用いて製造することを特徴とする。本発明の製品は、該方法を用いて製造されてなる製品であり、電子回路、電子部品、建材、自動車等に好適に利用可能である。
フルオロシリル基を有するポリオキシアルキレン系重合体C1-1(フッ素化ポリマーC1-1)の合成
攪拌装置、窒素ガス導入管、温度計および環流冷却器を備えたフラスコに、エチレングリコールを開始剤とし、亜鉛ヘキサシアノコバルテート-グライム錯体触媒の存在下、プロピレンオキシドを反応させて得られた水酸基価換算重量平均分子量11000、かつ分子量分布1.3のポリオキシプロピレンジオールを得た。得られたポリオキシプロピレンジオールにナトリウムメトキシドのメタノール溶液を添加し、加熱減圧下メタノールを留去してポリオキシプロピレンジオールの末端水酸基をナトリウムアルコキシドに変換し、ポリオキシアルキレン系重合体M1を得た。
得られた末端にトリメトキシシリル基を有するポリオキシアルキレン系重合体A1の分子量をGPCにより測定した結果、ピークトップ分子量は12000、分子量分布1.3であった。1H-NMR測定により末端のトリメトキシシリル基は1分子あたり1.7個であった。
表2に示す配合割合にて、撹拌装置、窒素ガス導入管、温度計および還流冷却管を備えた新たなフラスコに、合成例1で得られた末端にトリメトキシシリル基を有するポリオキシアルキレン系重合体A1、及びトルエンを入れた。23℃にて30分間撹拌後、110℃に加温し減圧撹拌を2時間行い、トルエンを除去した。この容器に先ほど得られた混合物を窒素気流下にてゆっくりと滴下し、滴下終了後、反応温度を120℃に昇温し、30分間反応させた。反応終了後、減圧脱気を行い未反応物の除去を行い、末端にトリフルオロシリル基を有するポリオキシアルキレン系重合体C1-1(以下、フッ素化ポリマーC1-1と称する)を得た。
得られたフッ素化ポリマーC1-1の1H-NMRスペクトル(Shimadzu社製のNMR400を用いて、CDCl3溶媒中で測定)を測定したところ、原料である重合体A1のシリルメチレン(-CH2-Si)に対応するピーク(m,0.63ppm)が消失し、低磁場側(0.7ppm~)にブロードピークが現れた。
フラスコに溶剤である酢酸エチル40質量部、メチルメタクリレート59質量部、2-エチルヘキシルメタクリレート25質量部、γ-メタクリロキシプロピルトリメトキシシラン22質量部、及び金属触媒としてルテノセンジクロライド0.1質量部を仕込み窒素ガスを導入しながら80℃に加熱した。ついで、3-メルカプトプロピルトリメトキシシラン8質量部をフラスコ内に添加し80℃で6時間反応を行った。室温に冷却後、ベンゾキノン溶液(95%THF溶液)を20質量部添加して重合を停止した。溶剤および未反応物を留去し、ポリスチレン換算の質量平均分子量が約6000、Mw/Mnが1.6であり、Tgが61.2℃であるトリメトキシシリル基を有するアクリル系重合体A2を得た。
撹拌装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、窒素気流下にてBF3ジエチルエーテル錯体(東京化成工業(株)製)0.1g、及びビニルトリメトキシシラン(商品名:KBM-1003、信越化学工業(株)製)0.10gを入れた。23℃にて30分間撹拌後、窒素パージし、50℃にて24時間放置し、γ-グリシドキシプロピルトリメトキシシランを含む反応物(以下、フッ素化化合物C1-2と称する)を得た。
ポリオキシプロピレンジオールにナトリウムメトキシド(NaOMe)のメタノール溶液を添加してメタノールを留去し、更に塩化アリルを添加して末端の水酸基をアリル基に変換した。未反応の塩化アリルを減圧脱揮により除去し、さらに生成した金属塩を水により抽出除去して、末端にアリル基を有するポリオキシプロピレンを得た。得られたアリル基末端ポリオキシプロピレンに対し、白金ビニルシロキサン錯体のイソプロパノール溶液を添加し、トリメトキシシランを反応させ、PPG換算の数平均分子量が約15000、1分子当たり1.5個の末端トリメトキシシリル基を有するポリアルキレン系重合体A3を得た。
末端にハロゲンを有するポリ(アクリル酸n-ブチル)の合成(原子移動ラジカル重合法)
50mlフラスコに臭化第一銅0.63g(4.4mmol)、ペンタメチルジエチレントリアミン0.76g(4.4mmol)、アセトニトリル5ml、2,5-ジブロモアジピン酸ジエチル1.6g(4.4mmol)、アクリル酸n-ブチル44.7g(349mmol)を仕込み、凍結脱気をおこなった後、窒素雰囲気下で70℃7時間反応させた。活性アルミナのカラムを通して銅触媒を除去精製することにより末端にBr基を有するポリ(アクリル酸n-ブチル)を得た。得られた重合体の数平均分子量は10700、分子量分布1.15であった。
窒素雰囲気下、200mlフラスコに上記で得た末端にBr基を有するポリ(アクリル酸n-ブチル)35g、ペンテン酸カリウム2.2g(16.1mmol)、DMAc35mLを仕込み、70℃で4時間反応させた。反応混合液中の未反応のペンテン酸カリウムおよび生成した臭化カリウムを水抽出精製により除去し、末端にアルケニル基を有するポリ(アクリル酸n-ブチル)を得た。得られた重合体の数平均分子量は11300、分子量分布1.12であった。また1H-NMR分析より求めた重合体1分子あたりのアルケニル基の個数は1.82個であった。
200mL耐圧反応管に上記で得た末端にアルケニル基を有するポリ(アクリル酸n-ブチル)15g、メチルジメトキシシラン1.8mL(14.5mmol)、オルトギ酸メチル0.26mL(2.4mmol)、白金ビス(ジビニルテトラメチルジシロキサン)10-4mmolを仕込み、100℃で4時間反応させ、末端にメチルジメトキシシリル基を有するポリ(アクリル酸n-ブチル)A4(以下、アクリル系重合体A4と称する)を得た。得られた重合体の粘度は44Pa・sであり、数平均分子量は11900、分子量分布1.12であった。また1H-NMR分析により重合体1分子あたりのメチルジメトキシシリル基の個数は1.46個であった。
攪拌装置、窒素ガス導入管、温度計および環流冷却器を備えた新しいフラスコに、分子量約2,000のポリオキシプロピレンジオールを開始剤とし、亜鉛ヘキサシアノコバルテート-グライム錯体触媒の存在下、プロピレンオキシドを反応させて得られた水酸基価換算分子量14500、かつ分子量分布1.3のポリオキシプロピレンジオールを得た。得られたポリオキシプロピレンジオールにナトリウムメトキシドのメタノール溶液を添加し、加熱減圧下メタノールを留去してポリオキシプロピレンジオールの末端水酸基をナトリウムアルコキシドに変換し、ポリオキシアルキレン系重合体M5を得た。
得られた末端にメチルジメトキシシリル基を有するポリオキシアルキレン系重合体A5の分子量をGPCにより測定した結果、ピークトップ分子量は15000、分子量分布1.3であった。H1-NMR測定により末端のメチルジメトキシシリル基は1分子あたり1.7個であった。
表2に示すように、攪拌装置、窒素ガス導入管、温度計および環流冷却器を備えたフラスコに、減圧脱気後、窒素ガス置換して、窒素気流下にてBF3ジエチルエーテル錯体2.4g入れ、50℃に加温した。続いて脱水メタノール1.6gの混合物をゆっくりと滴下し混合させた。撹拌装置、窒素ガス導入管、温度計および還流冷却管を備えた新たなフラスコに、合成例6で得られた重合体A5を100g、トルエン5g入れた。23℃にて30分間撹拌後、110℃に加温し減圧撹拌を2時間行い、トルエンを除去した。この容器に先ほど得られた混合物を窒素気流下にて4.0gゆっくりと滴下し、滴下終了後、反応温度を120℃に昇温し、30分間反応させた。反応終了後、減圧脱気を行い未反応物の除去を行った。末端にフルオロシリル基を有するポリオキシアルキレン系重合体C3(以下、フッ素化ポリマーC3と称する)を得た。得られたフッ素化ポリマーC3の1HNMRスペクトル(Shimazu社製のNMR400を用いて、CDCl3溶媒中で測定)を測定したところ、原料である重合体A5のシリルメチレン(-CH2-Si)に対応するピーク(m,0.63ppm)が消失し、低磁場側(0.7ppm~)にブロードピークが現れた。
表3に示す配合割合にて、攪拌機、温度計、窒素導入口、モノマー装入管および水冷コンデンサーを装着した300mLのフラスコに、合成例4で得たポリオキシアルキレン系重合体A3を添加し、加熱(100℃)、脱気、撹拌を2時間することによって脱水をした。冷却後、合成例1で得たフッ素化ポリマーC1-1、光塩基発生剤B1、及び水分吸収剤としてKBM-1003[信越化学工業(株)製、ビニルトリメトキシシラン]、をそれぞれ添加し、混合撹拌することにより光硬化性組成物を調製した。
光塩基発生剤B1;PBG-SA1[サンアプロ(株)製の商品名、光によりDBUを発生する光潜在性第3級アミン、8-(9-オキソ-9H-チオキサンテン-2-イル)メチル-1,8-ジアザビシクロ[5.4.0]-7-ウンデセニウムテトラフェニルボレート]20質量%とプロピレンカーボネート80質量%との混合物。
光塩基発生剤B2;WPBG-082[和光純薬(株)製の商品名、光によりグアニジンを発生する光潜在性アミン、グアニジン2-(3-ベンゾイルフェニル)プロピオネート]30質量%とN-メチルピロリドン70質量%との混合物。
KBM-1003;信越化学工業(株)製の商品名、ビニルトリメトキシシラン。
1)硬化性試験
金属板上に光硬化性組成物を約50μm厚に塗布し、UV照射後[照射条件:メタルハライドランプ(照度50mW/cm2)、積算光量:2000mJ/cm2]又はUV照射を行わずに、照度550ルクス(蛍光灯)、23℃50%RHの条件で表2に示す一定時間放置後の光硬化性組成物表面を指触にて硬化具合を確認する。
○:硬化、△:ゲル化(液状と固体の中間)、×:未硬化。
ステンレス板(25mm×100mm×1.5mm)上に光硬化性組成物を約50μm厚に塗布し、UV照射[照射条件:メタルハライドランプ(照度:50mW/cm2)、積算光量:200mJ/cm2]する。
UV照射後直ちに、同じ大きさのステンレス板の中央部と重ねて、十字になるように貼り合せた。23℃50%RHの条件で24時間放置後、手で動かないかどうかを判定した。動かない場合を〇、動く場合を×と評価した。
表3に示した如く配合物質を変更した以外は実施例1と同様の方法により光硬化性組成物を調製した。該光硬化性組成物の硬化性試験及び接着性試験を実施例1と同様の方法により行い、その結果を表4及び5に示した。
表3に示した如く配合物質を変更した以外は実施例1と同様の方法により光硬化性組成物を調製した。該光硬化性組成物の硬化性試験及び接着性試験を実施例1と同様の方法により行い、その結果を表4及び5に示した。
表6に示した如く配合物質を変更した以外は実施例1と同様の方法により光硬化性組成物を調製した。該光硬化性組成物の表面硬化性試験を下記方法により行い、その結果を表6に示した。
直径20mmの大きさの丸い容器に厚みが7mmになるように光硬化性組成物を注ぎ、UV未照射及びUV照射[照射条件:メタルハライドランプ(照度:330mW/cm2)、積算光量:3000mJ/cm2]後の暗室下23℃RH50%の環境下において、30秒ごとに指触にて表面がべたつかなくなるまでの時間(タックフリータイム)を測定した。
光塩基発生剤B3:Irgacure(登録商標)907(BASF社製、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン)を50質量%含むプロピレンカーボネート溶液。
光塩基発生剤B4:Irgacure(登録商標)369(BASF社製、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1)を50質量%含むDMSO溶液。
光塩基発生剤B5:Irgacure(登録商標)379EG〔BASF社製の商品名、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン〕50質量%とプロピレンカーボネート50質量%との混合物。
ダロキュア1173:BASF社製の商品名、開裂型光ラジカル発生剤、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン。
攪拌機、温度計、窒素導入口、モノマー装入管および水冷コンデンサーを装着した300mLのフラスコに、表7及び8に示す配合割合にて各配合物質をそれぞれ添加し、混合撹拌することにより光硬化性組成物を調製した。
光塩基発生剤B1:PBG-SA1[サンアプロ(株)製の商品名、光によりDBUを発生する光潜在性第3級アミン、8-(9-オキソ-9H-チオキサンテン-2-イル)メチル-1,8-ジアザビシクロ[5.4.0]-7-ウンデセニウムテトラフェニルボレート]20質量%とプロピレンカーボネート80質量%との混合物。
光塩基発生剤B5:Irgacure(登録商標)379EG〔BASF社製の商品名、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン〕50質量%とプロピレンカーボネート50質量%との混合物。
フッ素系化合物C2:三フッ化ホウ素モノエチルアミン10質量%とプロピレンカーボネート90質量%との混合物。
KBM-1003:信越化学工業(株)製の商品名、ビニルトリメトキシシラン。
ダロキュア1173:BASF社製の商品名、開裂型光ラジカル発生剤、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン。
(a)直径20mm、高さ7mmの円筒形容器に厚みが7mmになるように光硬化性組成物を注ぎ、UV未照射及びUV照射[照射条件:メタルハライドランプ(照度:330mW/cm2)、積算光量:3000mJ/cm2]後直ちに、暗室下23℃RH50%の環境下で表10に示す一定時間放置後の光硬化性組成物表面を指触にて硬化具合を確認する。
○:硬化、△:ゲル化(液状と固体の中間)、×:未硬化。
(b)直径20mm、高さ7mmの円筒形容器に厚みが7mmになるように光硬化性組成物を注ぎ、UV未照射及びUV照射[照射条件:メタルハライドランプ(照度:1500mW/cm2)、積算光量:3000mJ/cm2]後直ちに、暗室下23℃RH50%の環境下において、10分までは1分ごとに、10分から120分までは10分ごとに、120分から8時間までは1時間ごとに指触にて表面がべたつかなくなるまでの時間(タックフリータイム)を測定した。また、UV照射後のタックフリータイムが1時間未満のものを○、2時間以上3時間未満のものを△、3時間以上のものを×、UV未照射時のタックフリータイムが8時間以上のものを○、4時間以上8時間未満のものを△、4時間未満のものを×と評価した。
Claims (11)
- (A)架橋性珪素基含有有機重合体と、
(B)光塩基発生剤と、
(C1)Si-F結合を有するケイ素化合物、及び/又は(C2)三フッ化ホウ素、三フッ化ホウ素の錯体、フッ素化剤及び多価フルオロ化合物のアルカリ金属塩からなる群から選択される1種以上のフッ素系化合物と、
を含有することを特徴とする光硬化性組成物。 - 前記(B)光塩基発生剤が、光潜在性第3級アミンであることを特徴とする請求項1記載の光硬化性組成物。
- (D)シランカップリング剤をさらに含有することを特徴とする請求項1又は2記載の光硬化性組成物。
- 前記(A)架橋性珪素基含有有機重合体が、1分子中に平均して0.8個以上の架橋性珪素基を含有するポリオキシアルキレン系重合体、1分子中に平均して0.8個以上の架橋性珪素基を含有する飽和炭化水素系重合体、及び1分子中に平均して0.8個以上の架橋性珪素基を含有する(メタ)アクリル酸エステル系重合体からなる群から選択される1種以上であることを特徴とする請求項1~3のいずれか1項記載の光硬化性組成物。
- 請求項1~4のいずれか1項記載の光硬化性組成物に対し、光を照射することにより硬化物を形成することを特徴とする硬化物の製造方法。
- 請求項5記載の方法により形成されてなる硬化物。
- 請求項1~4のいずれか1項記載の光硬化性組成物を用いて製造することを特徴とする製品の製造方法。
- 請求項7記載の方法により製造されてなる製品。
- 請求項5記載の方法を用いて製造されてなる製品。
- 請求項1~4のいずれか1項記載の光硬化性組成物を接着剤として用いてなる製品。
- 請求項1~4のいずれか1項記載の光硬化性組成物をコーティング剤として用いてなる製品。
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JP5927750B2 (ja) | 2016-06-01 |
KR20160055779A (ko) | 2016-05-18 |
JPWO2015008709A1 (ja) | 2017-03-02 |
CN105392845A (zh) | 2016-03-09 |
KR102305831B1 (ko) | 2021-09-27 |
EP3023462A4 (en) | 2017-04-12 |
EP3023462A1 (en) | 2016-05-25 |
CN105392845B (zh) | 2020-10-20 |
US20160152783A1 (en) | 2016-06-02 |
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