WO2016104787A1 - 光硬化性組成物 - Google Patents

光硬化性組成物 Download PDF

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Publication number
WO2016104787A1
WO2016104787A1 PCT/JP2015/086413 JP2015086413W WO2016104787A1 WO 2016104787 A1 WO2016104787 A1 WO 2016104787A1 JP 2015086413 W JP2015086413 W JP 2015086413W WO 2016104787 A1 WO2016104787 A1 WO 2016104787A1
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group
compound
meth
polymer
crosslinkable silicon
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PCT/JP2015/086413
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English (en)
French (fr)
Japanese (ja)
Inventor
翔馬 河野
尚孝 河村
智洋 緑川
岡村　直実
宏士 山家
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セメダイン株式会社
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Priority to KR1020177010755A priority Critical patent/KR102494910B1/ko
Priority to CN201580057525.1A priority patent/CN107074999B/zh
Priority to JP2016566568A priority patent/JP6683133B2/ja
Publication of WO2016104787A1 publication Critical patent/WO2016104787A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences
    • C09J183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

Definitions

  • the present invention relates to a dual cure photocurable composition using moisture curing and active energy ray (light) curing.
  • the present invention relates to a dual cure photocurable composition that is excellent in temporary fixability of an adherend immediately after light irradiation and can be cured in a short time.
  • crosslinkable silicon group 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”) It can be made into a liquid that can be easily filled, and even at room temperature, it has the property that it can be cross-linked by the formation of siloxane bonds accompanied by hydrolysis reaction of cross-linkable silicon groups by the action of moisture in the air, etc. . For this reason, this polymer is widely used for sealing materials, adhesives, paints and the like.
  • the polymer having a crosslinkable silicon group include a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer.
  • Patent Document 1 discloses an adhesive composition containing a polymer having a hydrolyzable silyl group (corresponding to a crosslinkable silicon group) and a compound having a photopolymerizable polymerizable group.
  • the polymer having a hydrolyzable silyl group is a polymer that is cross-linked and cured by moisture in the air
  • the compound having a photopolymerizable polymerizable group is a compound that becomes a high molecular weight by light irradiation.
  • This adhesive composition is a liquid that can be applied before light irradiation, and when irradiated with light, a compound having a photopolymerizable polymerizable group becomes a polymer, and the adherend can be temporarily fixed and fixed. The adherend can be fixed without using a jig. If left as it is, the polymer having a hydrolyzable silyl group contained in the adhesive composition is cured, and finally an adhesive having a high strength can be obtained.
  • the curable composition using the compounds having different curing mechanisms is called a dual cure type of moisture curing and photocuring in the case of Patent Document 1, and even if there is no temporary fixing jig. Used for bonding that can be fixed.
  • a polymer having a crosslinkable silicon group is cured by moisture by the action of a curing catalyst.
  • a catalyst having a large catalytic action is used. Moisture permeates into the inside instantly, and when it is applied, curing proceeds and the bonding work cannot be performed.
  • a catalyst having a small catalytic action is used, curing does not easily proceed and it takes time for complete curing.
  • the adhesive is thinly applied, it is difficult to select an appropriate curing catalyst for the polymer having a crosslinkable silicon group.
  • Patent Document 2 discloses an adhesive composition using a photoacid generator as a curing catalyst for a polymer having a dual cure type and having a crosslinkable silicon group.
  • the generated acid acts as a curing catalyst.
  • curing of the polymer having a crosslinkable silicon group starts from the time of application to the adherend.
  • an acid which is a curing catalyst for a polymer having a crosslinkable silicon group is generated by light irradiation, curing of the polymer having a crosslinkable silicon group proceeds until light irradiation. do not do. For this reason, according to the adhesive composition described in Patent Document 2, it is possible to quickly make a B-stage after ultraviolet irradiation, and problems such as slumping can be avoided.
  • the photoacid generator is used in the adhesive composition described in Patent Document 2, for example, when an amine or an alkaline substance is mixed, an active acid catalyst generated from the photoacid generator reacts. , Photocationic polymerization is significantly inhibited. This is likely to occur when a basic substance is contained in the adherend as well as when a basic adhesion-imparting agent, a filler, or the like is blended in the composition. Therefore, the adhesive composition described in Patent Document 2, as described in the Examples of Patent Document 2, does not exhibit sufficient adhesive force immediately after UV irradiation and has poor adhesion, and the adherend is also not suitable. Limited. Moreover, there exists a problem of producing a rust and cannot apply to adhesion
  • an object of the present invention is a dual-cure photocurable composition using moisture curing and photocuring, and the curing does not proceed before light irradiation, so that sufficient work time can be taken.
  • a dual-cure type that produces a cured product with excellent temporary fixability immediately after irradiation, and after curing with light, ensures adequate bonding time and completes relatively quickly and does not generate corrosive acids.
  • the object is to provide a photocurable composition.
  • the present invention provides (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, (C1) a silicon compound having a Si—F bond, and (C2) three One or more fluorine compounds selected from the group consisting of boron fluoride, boron trifluoride complexes, fluorinating agents, and alkali metal salts of polyvalent fluoro compounds, and (D) one per molecule.
  • a photocurable composition containing a polyfunctional compound having more than (meth) acryloyl groups.
  • the photocurable composition comprises (E) a crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups by light. Furthermore, it is preferable to include.
  • the photocurable composition preferably further includes (F) a monofunctional compound having a photopolymerizable unsaturated group.
  • the photocurable composition further includes (G) a tackifier resin.
  • the (A) crosslinkable silicon group-containing organic polymer comprises a crosslinkable silicon group-containing polyoxyalkylene polymer and a crosslinkable silicon group-containing (meth) acrylic polymer. It is suitable that it is 1 or more types selected from a group.
  • the photobase generator (B) 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 organic polymer having a crosslinkable silicon group is (a-1) a polymer having a crosslinkable silicon group and a photoradically polymerizable vinyl group in the molecule ( However, it is preferably selected from the group consisting of organic polymers having a crosslinkable silicon group other than (a-2) and (a-1) except for those having a Si—F bond.
  • the present invention provides a cured product formed by irradiating the photocurable composition with light.
  • the present invention provides a product manufactured using the above photocurable composition. Furthermore, in order to achieve the above object, the present invention provides a product using the photocurable composition as an adhesive. Moreover, in order to achieve the said objective, this invention provides the electronic device product which uses the said photocurable composition.
  • the present invention provides a method for reworking an electronic device, wherein (A) an on-site liquid mold gasket for an electronic device is (A) a crosslinkable silicon group-containing organic polymer; In-situ molded liquid gasket containing a photobase generator, (C1) a silicon compound having a Si—F bond, and (D) a polyfunctional compound having more than one (meth) acryloyl group in one molecule.
  • a dual-cure photocurable composition using moisture curing and photocuring the curing does not proceed before light irradiation, and sufficient work time can be taken.
  • a cured product having excellent temporary fixability is produced, and after curing with light, a dual cure type that does not generate corrosive acid and complete curing relatively quickly while ensuring an appropriate bonding time.
  • a photocurable composition can be provided.
  • the photocurable composition according to the present embodiment includes (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, (C1) a silicon compound having a Si—F bond, and / or (C2) at least one fluorine-based compound selected from the group consisting of boron trifluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyvalent fluoro compound, and (D) in one molecule And a polyfunctional compound having more than one (meth) acryloyl group.
  • the photocurable composition according to the present embodiment may be referred to as “the composition according to the present embodiment”.
  • the crosslinkable silicon group-containing organic polymer is not particularly limited as long as it is an organic polymer having a crosslinkable silicon group.
  • the main chain is an organic polymer that is not polysiloxane, and organic polymers having various main chain skeletons excluding polysiloxane are easily available, and cause of contact failure in the field of electrical applications. This is preferable in that it does not contain or generate low molecular cyclic siloxane.
  • the crosslinkable silicon group-containing organic polymer may have a photoradically polymerizable vinyl group together with the crosslinkable silicon group.
  • the crosslinkable silicon group-containing organic polymer further has a photoradically polymerizable vinyl group in the molecule, the initial tackiness and / or flexibility of the photocurable composition according to the present embodiment can be improved. It can be made easier to hold, and heat resistance and the like due to post-curing can be further improved.
  • a polymer having a crosslinkable silicon group and a photoradically polymerizable vinyl group in the molecule except for those having a Si—F bond
  • component (a-2) The organic polymer having a crosslinkable silicon group other than (a-1) is referred to as component (a-2).
  • the crosslinkable silicon group-containing organic polymer (A) the component (a-1) and / or the component (a-2) can also be used.
  • (A) Specific examples of the main chain skeleton of the crosslinkable silicon group-containing organic polymer include polyoxyalkylene polymers such as polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-polyoxypropylene copolymers.
  • a hydrocarbon polymer such as an ethylene-propylene copolymer, polyisobutylene, polyisoprene, polybutadiene, hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; two bases such as adipic acid; Polyester polymer obtained by condensation of acid and glycol or ring-opening polymerization of lactones; (meth) acrylic acid ester obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate Polymer: (meth) acrylic acid ester monomer, vinyl acetate, acrylic Vinyl polymer obtained by radical polymerization of monomers such as nitrile and styrene; Graft polymer obtained by polymerizing vinyl monomer in organic polymer; Polysulfide polymer; Polyamide polymer; Polycarbonate polymer A diallyl phthalate polymer and the like. These skeletons may be contained alone in (A) the crosslinkable silicon group-containing organic
  • 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 they have high moisture permeability and are excellent in deep part curability when made into a one-component composition.
  • the crosslinkable silicon group of the crosslinkable silicon group-containing organic polymer 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 general formula (1) is suitable.
  • 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, or an aryl having 6 to 20 carbon atoms Group, an aralkyl group having 7 to 20 carbon atoms, a triorganosiloxy group represented by R 1 3 SiO— (R 1 is the same as above), or a —CH 2 OR 1 group (R 1 is the same as above) It is.
  • R 1 is a group in which at least one hydrogen atom on the 1st to 3rd carbon atoms is halogen, —OR 41 , —NR 42 R 43 , —N ⁇ R 44 , —SR 45 (R 41 , R 42 , R 43 and R 45 are each a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms or having no substituent, and R 44 is a divalent substitution having 1 to 20 carbon atoms.
  • R 1 is preferably a methyl group.
  • the plurality of R 1 may be the same or different.
  • X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, the plurality of X may be the same or different.
  • a is an integer of 0, 1, 2, or 3.
  • a is preferably 2 or more, more preferably 3.
  • Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.
  • the number of silicon atoms forming the crosslinkable silicon group may be one or two or more. In the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.
  • the hydrolyzable group represented by X is not particularly limited as long as it is other than F atom.
  • Examples thereof include an alkoxy group, an acyloxy group, an amino group, an amide group, an aminooxy group, and an alkenyloxy group.
  • an alkoxy group is preferable from a viewpoint that hydrolysis property is moderate and it is easy to handle.
  • the alkoxy groups those having a smaller number of carbon atoms have higher reactivity, and the reactivity increases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group.
  • 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 ], a trialkoxysilyl group [—Si (OR) 3 ] is preferable in terms of high reactivity, and a trimethoxysilyl group is more preferable.
  • R is an alkyl group such as a methyl group or an ethyl group.
  • the crosslinkable silicon group may be used alone or in combination of two or more.
  • the crosslinkable silicon group can be present in the main chain, the side chain, or both.
  • the crosslinkable silicon group shown by several general formula (1) may mutually be connected.
  • 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, the number of silicon atoms is preferably 20 or less.
  • the photo-radically polymerizable vinyl group include a group containing a (meth) acryloyl group such as a (meth) acryloyloxy group.
  • Each of the organic polymer having a crosslinkable silicon group and the organic polymer having a crosslinkable silicon group and a photoradically polymerizable vinyl group may have a straight chain or a branch, and the number average molecular weight is In terms of polystyrene in GPC, it is about 500 to 100,000, more preferably 1,000 to 50,000, and particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be inconvenient in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.
  • a crosslinkable silicon group, a crosslinkable silicon group and a photo-radical polymerizable polymer contained in the organic polymer having a crosslinkable silicon group are used.
  • the crosslinkable silicon group and photoradically polymerizable vinyl group contained in the organic polymer having a vinyl group average 0.8 or more, preferably 1.0 or more, more in one polymer molecule. Preferably 1.1 to 5 are present. If the number of crosslinkable silicon groups and radically polymerizable vinyl groups contained in the molecule is less than 0.8 on average, the curability will be insufficient and good rubber elastic behavior will not be exhibited. Become.
  • the crosslinkable silicon group and the photoradically polymerizable vinyl group may be at the end of the main chain of the organic polymer molecular chain, at the end of the side chain, or at both.
  • the crosslinkable silicon group is only at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that the high strength, high elongation, A rubber-like cured product having a low elastic modulus is easily obtained.
  • the polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the general formula (2).
  • -R 2 -O- (2) In the general formula (2), 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 having 2 to 4 carbon atoms.
  • the linear or branched alkylene group is more preferable.
  • repeating unit represented by the general formula (2) 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— and the like can be mentioned.
  • 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.
  • Examples of the method for synthesizing the polyoxyalkylene polymer include, but are not limited to, a polymerization method using an alkali catalyst such as KOH, a polymerization method using a double metal cyanide complex catalyst, and the like. According to the polymerization method using a double metal cyanide complex catalyst, a polyoxyalkylene polymer having a number average molecular weight of 6,000 or more and a high molecular weight of Mw / Mn of 1.6 or less and a narrow molecular weight distribution 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 is obtained from a reaction between an aromatic polyisocyanate such as toluene (tolylene) diisocyanate and diphenylmethane diisocyanate; an aliphatic polyisocyanate such as isophorone diisocyanate and a polyoxyalkylene polymer having a hydroxyl group. Ingredients can be mentioned.
  • hydrosilylation or mercaptoization is carried out by reacting an unsaturated group-containing polyoxyalkylene polymer with a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group.
  • examples thereof include a method for obtaining a polyoxyalkylene polymer having a group.
  • An unsaturated group-containing polyoxyalkylene-based 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.
  • a polyoxyalkylene polymer having a hydroxyl group at the terminal is reacted with an isocyanate group and a compound having a crosslinkable silicon group and / or a radically polymerizable vinyl group.
  • a method of reacting a polyoxyalkylene polymer having an isocyanate group at a terminal with a compound having an active hydrogen group such as a hydroxyl group or an amino group, and a crosslinkable silicon group and / or a photoradically polymerizable vinyl group can be mentioned.
  • an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group and / or a photoradically polymerizable vinyl group can be easily obtained.
  • the polyoxyalkylene polymer having a crosslinkable silicon group and / or a radical photopolymerizable vinyl group may be used alone or in combination of two or more.
  • the saturated hydrocarbon polymer is a polymer that does not substantially contain other carbon-carbon unsaturated bonds other than aromatic rings.
  • the polymer forming the skeleton is either (1) polymerizing an olefinic compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene or isobutylene as a main monomer, or (2) a diene such as butadiene or isoprene. It can be obtained by homopolymerizing the system compound or by hydrogenating the diene compound and the olefin compound after copolymerization.
  • the isobutylene polymer and the hydrogenated polybutadiene polymer are preferable because it is easy to introduce a functional group at the terminal, easily control the molecular weight, and can increase the number of terminal functional groups, and the isobutylene polymer is particularly preferable. preferable.
  • the main chain skeleton is a saturated hydrocarbon polymer
  • the main chain skeleton has 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. From the viewpoint of rubber properties, a polymer containing 50% by mass or more of repeating units derived from isobutylene is preferred, a polymer containing 80% by mass or more is more preferred, and a polymer containing 90 to 99% by mass is particularly preferred.
  • a polymerization method As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods may be mentioned. In particular, various living polymerizations have been developed. In the case of saturated hydrocarbon polymers, particularly isobutylene polymers, the inifer polymerization found by Kennedy et al. (J. P. Kennedy et al., J. Polymer Sci., Polymer Chem. Page). According to this polymerization method, a polymer having a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends.
  • saturated hydrocarbon polymers particularly isobutylene polymers
  • the inifer polymerization found by Kennedy et al. J. P. Kennedy et al., J. Polymer Sci., Polymer Chem. Page.
  • a polymer having a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less,
  • Examples of a method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a photoradically polymerizable vinyl group include, for example, a combination of an organic halogen compound that generates a stable carbon cation and a Friedelcraft acid catalyst. And cationic polymerization method using as a copolymerization initiator.
  • An example is the inifer method disclosed in Japanese Patent Publication No. 4-69659.
  • the saturated hydrocarbon polymer having a crosslinkable silicon group and / or a radical photopolymerizable vinyl group may be used alone or in combination of two or more.
  • (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer.
  • (meth) acrylic acid monomers such as acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl ester monomers such as stearyl acid; alicyclic (meth) acrylic acid ester monomers; aromatic (meth) acrylic acid ester monomers; (meth) acrylic acid 2-methoxyethyl (meth) ) Acrylic acid ester monomers; silyl group-containing (meth) acrylic acid ester monomers such as ⁇ - (methacryloyloxypropyl) trimethoxysilane, ⁇ - (methacryloyloxypropyl) dimethoxymethylsilane; (meth) acrylic acid alkyl ester mono
  • the following vinyl monomers can be copolymerized with the (meth) acrylate monomer.
  • vinyl monomers include styrene, maleic anhydride, vinyl acetate and the like.
  • acrylic acid and glycidyl acrylate may be contained as monomer units (hereinafter also referred to as other monomer units).
  • a polymer composed of a (meth) acrylic acid monomer is preferred.
  • the (meth) acrylic acid ester type polymer which used the 1 type (s) or 2 or more types (meth) acrylic-acid alkylester monomer and used together with the other (meth) acrylic acid monomer as needed is more preferable.
  • the number of silicon groups in the (meth) acrylic acid ester polymer (A) can be controlled by using a silyl group-containing (meth) acrylic acid ester monomer in combination.
  • a methacrylic acid ester polymer comprising a methacrylic acid ester monomer is particularly preferred because of its good adhesion.
  • (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
  • the method for producing the (meth) acrylate polymer is not particularly limited, and for example, a radical polymerization method using a radical polymerization reaction can be used.
  • a radical polymerization method a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, a reactive silyl group and / or a photo radical at a controlled position such as a terminal, etc.
  • examples thereof include a controlled radical polymerization method capable of introducing a polymerizable vinyl group.
  • a polymer obtained by a free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator generally has a large molecular weight distribution value of 2 or more and a high viscosity. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high rate 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. Further, a reaction using a thiol compound having a reactive silyl group and a reaction using a thiol compound having a reactive silyl group and a metallocene compound are also suitable.
  • RAFT addition-cleavage transfer reaction
  • Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferable.
  • the (meth) acrylic acid ester polymer having a crosslinkable silicon group and / or a radically polymerizable vinyl group may be used alone or in combination of two or more.
  • organic polymers having a crosslinkable silicon group and / or a radical photopolymerizable vinyl group may be used alone or in combination of two or more.
  • a polyoxyalkylene polymer having a crosslinkable silicon group and / or a photoradically polymerizable vinyl group, and a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a photoradically polymerizable vinyl group and an organic polymer obtained by blending two or more selected from the group consisting of a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group and / or a radically polymerizable vinyl group can also be used.
  • 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 For example, it has a crosslinkable silicon group and the molecular chain is substantially the general formula (3): —CH 2 —C (R 3 ) (COOR 4 ) — (3) (Wherein R 3 represents a hydrogen atom or a methyl group, and R 4 represents an alkyl group having 1 to 5 carbon atoms) and a general formula (4): —CH 2 —C (R 3 ) (COOR 5 ) — (4) (Wherein R 3 is the same as described above, and R 5 represents an alkyl group having 6 or more carbon atoms) A copolymer composed of a (meth) acrylic acid ester monomer unit is represented by a crosslinkable silicon group And a method of blending and producing a polyoxyalkylene-based polymer having.
  • R 4 in the general formula (3) for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group and the like have 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, An alkyl group having 1 to 2 carbon atoms is preferable.
  • the alkyl group of R 4 may alone, or may be a mixture of two or more.
  • R 5 in the general formula (4) is, for example, a long group having 6 or more carbon atoms such as 2-ethylhexyl group, lauryl group or stearyl group, usually 7 to 30 carbon atoms, preferably 8 to 20 carbon atoms. Chain alkyl groups.
  • the alkyl group of R 5 is as in the case of R 4, may be alone or in admixture.
  • the molecular chain of the (meth) acrylic acid ester copolymer is substantially composed of monomer units of the formulas (3) and (4).
  • “substantially” means that the total of the monomer units of the formula (3) and the formula (4) present in the copolymer exceeds 50% by mass.
  • the total of the monomer units of the formula (3) and the formula (4) is preferably 70% by mass or more.
  • the abundance ratio of the monomer unit of the formula (3) and the monomer unit of the formula (4) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40 by mass ratio.
  • (Meth) having a crosslinkable silicon group used in a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group with a (meth) acrylic acid ester polymer having a crosslinkable silicon group
  • the acrylate polymer include, for example, a (meth) acrylic acid alkyl ester monomer unit having a crosslinkable silicon group and a molecular chain substantially having (1) an alkyl group having 1 to 8 carbon atoms.
  • (meth) acrylic acid ester-based copolymers such as (meth) acrylic acid ester-based copolymers containing (meth) acrylic acid alkyl ester monomer units having an alkyl group having 10 or more carbon atoms Coalescence 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 is 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 a crosslinkable silicon group and the (meth) acrylic acid ester polymer having a crosslinkable silicon group is not particularly limited, but the (meth) acrylic acid ester polymer and The (meth) acrylic acid ester polymer is preferably in the range of 10 to 60 parts by mass, more preferably in the range of 20 to 50 parts by mass with respect to 100 parts by mass in total with the polyoxyalkylene polymer. More preferably, it is in the range of 25 to 45 parts by mass.
  • 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 addition, in the presence of an organic polymer having a crosslinkable silicon group A method of polymerizing a (meth) acrylic acid ester monomer can be used.
  • the photobase generator (B) When irradiated with light, the photobase generator (B) acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer.
  • the photobase generator (B) generates bases and / or radicals by the action of active energy rays such as ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays.
  • active energy rays such as ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays.
  • a known photobase generator (B) such as a compound to be released or (3) a compound that causes a predetermined chemical reaction to emit a base upon irradiation with energy rays such as ultraviolet rays, visible light, and infrared rays can be used.
  • the base generated from the photobase generator (B) has a function of curing the component (A).
  • an organic base such as an amine compound is preferable.
  • examples thereof include primary alkylamines, primary aromatic amines described in WO2015-088021, Secondary alkyl amines, amines having secondary amino groups and tertiary amino groups, tertiary alkyl amines, tertiary heterocyclic amines, tertiary aromatic amines, amidines, phosphazene derivatives Can be mentioned. Of these, amine compounds having a tertiary amino group are preferred, and amidines and phosphazene derivatives which are strong bases are more preferred.
  • amidines both acyclic amidines and cyclic amidines can be used, and cyclic amidines are more preferable. These bases may be used alone or in combination of two or more.
  • non-cyclic amidines examples include guanidine compounds and biguanide compounds described in WO2015-088021.
  • a photobase generator for generating an aryl-substituted guanidine compound or an aryl-substituted biguanide compound described in WO2015-088021 is used as a catalyst for the polymer (A). It is preferable because it shows a tendency to improve the curability of the surface, and a tendency to improve the adhesion of the resulting cured product.
  • cyclic amidines include cyclic guanidine compounds, imidazoline compounds, imidazole compounds, tetrahydropyrimidine compounds, triazabicycloalkene compounds, and diazabicycloalkene compounds described in WO2015-088021. It is done.
  • 1,8-diazabicyclo [5.4.0] undecene is known because it is easily available industrially, and has a pKa value of 12 or more for the conjugate acid and exhibits high catalytic activity.
  • -7 (DBU) and 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) are particularly preferred.
  • photobase generator (B) various photobase generators can be used. Photolatent amine compounds that generate amine compounds by the action of active energy rays are preferred.
  • 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. Any of the photolatent secondary amine that is generated and the photolatent tertiary amine that generates an amine compound having a tertiary amino group by the action of active energy rays can be used. In view of the high catalytic activity of the generated base, a photolatent tertiary amine is more preferable.
  • photolatent primary amines and photolatent secondary amines include orthonitrobenzylurethane compounds described in WO2015 / 088021, dimethoxybenzylurethane compounds, benzoins carbamates, o-acyloximes O-carbamoyl oximes; N-hydroxyimide carbamates; formanilide derivatives; aromatic sulfonamides; cobalt amine complexes and the like.
  • photolatent tertiary amines examples include ⁇ -aminoketone derivatives, ⁇ -ammonium ketone derivatives, benzylamine derivatives, benzylammonium salt derivatives, ⁇ -aminoalkene derivatives, ⁇ -ammonium alkene derivatives described in WO2015-088021.
  • Examples of the ⁇ -aminoketone compound include 5-naphthoylmethyl-1,5-diazabicyclo [4.3.0] nonane, 5- (4′-nitro) phenacyl-1,5-diazabicyclo [4.3.0].
  • ⁇ -aminoketone compounds that generate amidines such as nonane, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane (Irgacure 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone (Irgacure 369), 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone (Irgacure 379), etc., a tertiary amine composed of one nitrogen atom And ⁇ -aminoketone compounds that generate tertiary amines having a group.
  • amidines such as nonane, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane (Irgacure 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone (Irga
  • Examples of ⁇ -ammonium ketone derivatives include 1-naphthoylmethyl- (1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate, 5- (4′-nitro) phenacyl- (5 -Azonia-1-azabicyclo [4.3.0] -5-nonene) tetraphenylborate and the like.
  • benzylamine derivatives examples include 5-benzyl-1,5-diazabicyclo [4.3.0] nonane, 5- (anthracen-9-yl-methyl) -1,5-diazabicyclo [4.3.0].
  • Nonane, benzylamine derivatives such as 5- (naphth-2-yl-methyl) -1,5-diazabicyclo [4.3.0] nonane, and the like.
  • benzylammonium salt derivative examples include (9-anthryl) methyl 1-azabicyclo [2.2.2] octanium tetraphenylborate, 5- (9-anthrylmethyl) -1,5-diazabicyclo [4.3. .0] -5-nonenium tetraphenylborate and the like.
  • Examples of the ⁇ -aminoalkene derivative include 5- (2 ′-(2 ′′ -naphthyl) allyl) -1,5-diazabicyclo [4.3.0] nonane.
  • Examples of the ⁇ -ammonium alkene derivative include 1- (2′-phenylallyl)-(1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate.
  • Examples of the salt of carboxylic acid and tertiary amine include ammonium ⁇ -ketocarboxylic acid and ammonium carboxylate described in WO2015-088021.
  • a photolatent tertiary amine is preferable from the viewpoint that the generated base exhibits a high catalytic activity, and the base generation efficiency is high and the storage stability as a composition is good.
  • Benzylammonium salt derivatives, benzyl-substituted amine derivatives, ⁇ -aminoketone derivatives, ⁇ -ammonium ketone derivatives are preferred.
  • ⁇ -aminoketone derivatives and ⁇ -ammonium ketone derivatives are more preferable due to better base generation efficiency, and ⁇ -aminoketone derivatives are more preferable than the solubility in the blend.
  • ⁇ -aminoketone derivatives ⁇ -aminoketone compounds that generate amidines based on the basic strength of the generated base are preferred, and tertiary amines having a tertiary amine group composed of one nitrogen atom are more readily available. And ⁇ -aminoketone compounds that generate aldehydes.
  • photobase generators (B) may be used alone or in combination of two or more.
  • the blending ratio of the photobase generator (B) is not particularly limited, but is preferably 0.01 to 50 parts by weight, and preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the (A) crosslinkable silicon group-containing organic polymer. Part by mass is more preferable, and 0.5 to 30 parts by mass is even more preferable.
  • the silicon compound having a Si—F bond acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer.
  • various compounds containing a silicon group having a Si—F bond (hereinafter sometimes referred to as a fluorosilyl group) can be used, and there is no particular limitation. Either a low molecular compound or a high molecular compound can be used. An organosilicon compound having a fluorosilyl group is preferable, and an organic polymer having a fluorosilyl group is more preferable because of high safety. Moreover, the low molecular organosilicon compound which has a fluoro silyl group from the point from which a compound becomes low viscosity is preferable.
  • (C1) silicon compounds having a Si—F bond include fluorosilanes described in WO2015-088021 represented by formula (5), and WO2015-088021 represented by formula (6).
  • Preferred examples include compounds having a fluorosilyl group described below (hereinafter also referred to as fluorinated compounds) and organic polymers having a fluorosilyl group described below in WO2015-088021 (hereinafter also referred to as fluorinated polymers). As mentioned.
  • each R 6 is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 7 SiO— (R 7 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 6 And a plurality of R 7 may be the same or different.
  • R 6 and d are the same as those in Formula (5), Z is each independently a hydroxyl group or other hydrolyzable group excluding fluorine, and e is any one of 0 to 2) F is any one of 0 to 2, and d + e + f is 3.
  • R 6 , R 7 and Z are present, they may be the same or different.
  • fluorosilanes represented by the formula (5) include fluorosilanes represented by the formula (5).
  • fluorosilanes represented by the formula (5) examples include fluorodimethylphenylsilane, vinyl trifluorosilane, ⁇ -methacryloxypropyl trifluorosilane, octadecyl trifluorosilane, and the like.
  • the hydrolyzable group represented by Z is preferably an alkoxy group from the viewpoint of mild hydrolyzability and easy handling, and R 6 is a methyl group. preferable.
  • the compound having a fluorosilyl group represented by the formula (6) is not particularly limited, and either a monomolecular compound or a polymer compound can be used.
  • inorganic silicon compounds low molecular organic silicon compounds such as vinyl difluoromethoxysilane, vinyl trifluorosilane, phenyldifluoromethoxysilane, and phenyltrifluorosilane; fluorinated poly having a fluorosilyl group represented by formula (6) at the terminal
  • examples thereof include polymer compounds such as siloxane, and preferred are fluorosilanes represented by the formula (5) and polymers having a fluorosilyl group represented by the formula (6) at the terminal of the main chain or side chain.
  • organic polymer having a fluorosilyl group (hereinafter also referred to as a fluorinated polymer)
  • various organic polymers having a Si—F bond can be used.
  • the fluorinated polymer is a single polymer in which the main chain skeleton is the same as a fluorosilyl group, that is, the number of fluorosilyl groups per molecule, the bonding position thereof, and the number of Fs that the fluorosilyl group has, and
  • 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. Any of these fluorinated polymers can be suitably used as a resin component of a curable composition exhibiting rapid curability.
  • 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 mixing ratio of the silicon compound (C1) having a Si—F bond is not particularly limited, but when a polymer compound having a number average molecular weight of 3,000 or more such as a fluorinated polymer is used as the component (C1), (A)
  • the amount is preferably 0.01 to 80 parts by weight, more preferably 0.01 to 30 parts by weight, and still more preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the crosslinkable silicon group-containing organic polymer.
  • a low molecular compound having a fluorosilyl group having a number average molecular weight of less than 3,000 as the component (C1) for example, a low molecular organic compound having a fluorosilane group represented by the formula (5) or a fluorosilyl group represented by the formula (6)
  • the amount is preferably 0.01 to 10 parts by weight, preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the (A) crosslinkable silicon group-containing organic polymer. 5 parts by mass is more preferable.
  • the blending ratio of the photobase generator (B) used as the curing catalyst and the silicon compound (C1) having a Si—F bond is such that (B) :( C1) is in a mass ratio of 1: 0.008 to 1: 300. Is preferable, and 1: 0.016 to 1:40 is more preferable.
  • the fluorine compound is selected from the group consisting of boron trifluoride, boron trifluoride complex, fluorinating agent, and alkali metal salt of polyvalent fluoro compound described in WO2015-088021, for example.
  • One or more fluorine-based compounds may be mentioned.
  • the fluorine-based compound functions as a compound that promotes the hydrolysis-condensation reaction of the crosslinkable silicon group and acts as a curing catalyst for the crosslinkable silicon group-containing organic polymer.
  • boron trifluoride complexes examples include boron trifluoride amine complexes, alcohol complexes, ether complexes, thiol complexes, sulfide complexes, carboxylic acid complexes, and water complexes.
  • amine complexes having both stability and catalytic activity are particularly preferred.
  • examples of the amine compound used for the boron trifluoride amine complex include monoethylamine.
  • the blending ratio of the (C2) fluorine-based compound is not particularly limited, but is preferably 0.001 to 10 parts by mass, and 0.001 to 5 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. Part is more preferable, and 0.001 to 2 parts by mass is still more preferable.
  • These fluorine compounds may be used alone or in combination of two or more.
  • the photocurable composition may contain one or more selected from the group consisting of (C1) a silicon compound having a Si—F bond and (C2) a fluorine-based compound.
  • C1 a silicon compound having a Si—F bond
  • C2 a fluorine-based compound.
  • the photocurable composition according to the present embodiment in order to improve the effect as a composition to be post-cured (that is, made into an adhesive), it contains a crosslinkable silicon group-containing organic polymer and has an Si—F bond. It is preferable that the silicon compound which has this is included.
  • (D) polyfunctional compound As a polyfunctional compound having more than one (meth) acryloyl group in one molecule, a compound having more than one (meth) acryloyloxy group in one molecule or more than one in one molecule Examples include compounds having a (meth) acrylamide group. From the viewpoint of storage stability, a compound having more than one (meth) acryloyloxy group in one molecule is preferable. From the viewpoint of reactivity, a compound having more than one (meth) acrylamide group in one molecule is preferable.
  • the (D) polyfunctional compound has more than one (meth) acryloyl group in one molecule, preferably 1.5 or more (meth) acryloyl groups in one molecule.
  • the compound having more than one (meth) acryloyloxy group in one molecule either a monomer (hereinafter also referred to as a monomer) or a polymer can be used. From the viewpoint of viscosity, a monomer having a (meth) acryloyloxy group is preferred. From the viewpoint of curability, a polymer having a (meth) acryloyloxy group is preferred. In the present embodiment, the oligomer and the polymer are collectively referred to as a polymer.
  • a monomer having more than one (meth) acryloyloxy group in one molecule a monomer having two or more (meth) acryloyloxy groups in one molecule is preferable.
  • polyfunctional (meth) acrylates, etc. Is mentioned.
  • polyfunctional acrylates examples include 1,6-hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2, 2-functional (meth) acrylate monomers such as 2-bis (4- (meth) acryloxydiethoxyphenyl) propane or 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, trimethylolpropane tri Trifunctional (meth) acrylate monomers such as (meth) acrylate and tris [(meth) acryloyloxyethyl] isocyanurate, dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, or pentaerythritol Tokishitetora (meth) acrylate such as 4
  • a bifunctional (meth) acrylate monomer is preferable from the viewpoint of maintaining the flexibility of the photocurable adhesive, and a trifunctional (meth) acrylate monomer and a tetrafunctional or higher (meth) acrylate monomer from the viewpoint of good reactivity. Is preferred.
  • the polymer having more than one (meth) acryloyloxy group in one molecule is not particularly limited as long as it is a polymer having an average of more than one (meth) acryloyloxy group in one molecule.
  • a polymer having an average of 1.5 or more (meth) acryloyloxy groups in one molecule is preferable.
  • polyether urethane (meth) acrylate for example, “UV-3700B”, “UV-6100B” manufactured by Nippon Gosei Co., Ltd.
  • polyester Urethane (meth) acrylate for example, “UV-2000B”, “UV-3000B”, “UV-7000B” manufactured by Nihon Gosei Co., Ltd., “KHP-11”, “KHP-17” manufactured by Negami Kogyo Co., Ltd.
  • non-aromatic Group polycarbonate urethane (meth) acrylate for example, “Art Resin UN-9200A” manufactured by Negami Kogyo Co., Ltd.
  • acrylic (meth) acrylate for example, “RC-300”, “RC-100C”, “RC manufactured by Kaneka Corporation) -200C "), 1,2-polybutadiene-terminated urethane (meth) acrylate (for example,” T "
  • 1,2-polybutadiene-terminated urethane (meth) acrylate hydrogenated product for example,“ TEAI-1000 ”manufactured by Nippon Soda Co., Ltd.
  • 1,4-polybutadiene-terminated urethane (meth) examples thereof include acrylates (for example, “BAC-45” manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene-terminated (meth) acrylates, bisphenol A type epoxy (meth) acrylates, and the like.
  • polyether urethane (meth) acrylate From the viewpoint of compatibility with the component (A), polyether urethane (meth) acrylate, acrylic (meth) acrylate, polyester urethane (meth) acrylate, and non-aromatic polycarbonate urethane (meth) acrylate are preferred. ) Good compatibility with the component, and from the viewpoint of ensuring flexibility of the cured product, polyether urethane (meth) acrylate and acrylic (meth) acrylate are more preferable, and polyether urethane (meth) acrylate is more preferable. .
  • the compound having more than one (meth) acrylamide group in one molecule is preferably a compound having two or more (meth) acrylamide groups in one molecule.
  • methylene bisacrylamide, ethylene bisacrylamide, methylene bis Examples include methacrylamide, oxydimethylene bisacrylamide, ethylene dioxybis (N-methylene acrylamide) and the like.
  • the blending ratio of the polyfunctional compound (D) is not particularly limited, but is preferably 0.01 to 100 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. Is more preferable, and 0.2 to 100 parts by mass is still more preferable.
  • These (D) polyfunctional compounds can be used alone or in combination of two or more.
  • the photocurable composition according to this embodiment comprises (E) a crosslinkable silicon group that generates one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups by light. A compound may further be included. (E) The crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by light improves adhesion performance.
  • the primary amino group and the primary amino group can be obtained by light irradiation. Any compound that generates an aminosilane compound having at least one amino group selected from the group consisting of secondary amino groups and a crosslinkable silicon group can be used.
  • the crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by light is also referred to as a photoaminosilane generating compound.
  • the aminosilane compound generated by light irradiation a compound having a crosslinkable silicon group and a substituted or unsubstituted amino group is used.
  • substituent of the substituted amino group include an alkyl group, an aralkyl group, and an aryl group.
  • an alkyl group is preferable from the viewpoint of improving adhesiveness.
  • the crosslinkable silicon group is preferably a silicon-containing group to which a hydrolyzable group is bonded.
  • alkoxy groups such as a methoxy group and an ethoxy group are preferable because they are mildly hydrolyzable and easy to handle.
  • a hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, preferably 2 or more, particularly preferably 3.
  • the aminosilane compound generated by light irradiation is not particularly limited, and an aminosilane compound having a primary amino group (—NH 2 ) is preferable from the viewpoint of adhesion, and ⁇ -aminopropyltrimethoxysilane from the viewpoint of availability, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, and ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane are preferable, and ⁇ -aminopropyltrimethoxysilane and ⁇ -aminopropyl are preferable in terms of adhesiveness and curability. Triethoxysilane is more preferred.
  • Examples of the photoaminosilane generating compound include silicon compounds having a photofunctional group, aromatic sulfonamide derivatives, O-acyloxime derivatives, and trans- described in WO2015-088021 represented by formulas (7) to (8). Examples thereof include O-coumaric acid derivatives.
  • n is an integer of 1 to 3
  • Y represents a hydroxyl group or a hydrolyzable group, and an alkoxy group is preferable.
  • R 8 represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, vinyl group, allyl group, unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, unsubstituted or substituted aryl group Is preferred.
  • R 8 represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, vinyl group, allyl group, unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, unsubstituted or substituted aryl group Is preferred.
  • R 8 represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, vinyl group, allyl group, unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, un
  • R 9 is a hydrogen atom or an organic group, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, and more preferably a hydrogen atom.
  • h is an integer of 1 to 5
  • j is an integer of 1 to 6.
  • R 10 is a substituted or unsubstituted hydrocarbon group bonded to a silicon atom and a nitrogen atom at h + j different carbon atoms, and a plurality of substituted or unsubstituted groups bonded to each other via one or more ether oxygen atoms. It is an h + j-valent group selected from the group consisting of hydrocarbon groups and has a molecular weight of 1,000 or less.
  • R 9 and R 10 may be bonded to each other to form a cyclic structure, and may include a hetero atom bond.
  • Z is an oxygen atom or a sulfur atom, preferably an oxygen atom.
  • Q represents a photofunctional group.
  • R 12 is a divalent group selected from the group consisting of a substituted or unsubstituted hydrocarbon group and a plurality of substituted or unsubstituted hydrocarbon groups bonded to each other via one or more ether oxygen atoms.
  • . t is an integer of 1 or more, and 1 or 2 is preferable. When t is 2 or more, t groups bonded to R 11 may be the same or different.
  • R 11 is a hydrogen atom or an organic group, preferably a hydrogen atom or a substituted or unsubstituted t-valent hydrocarbon group, more preferably a hydrogen atom or a substituted or unsubstituted t-valent alkyl group.
  • R 11 and R 12 may be bonded to each other to form a cyclic structure, and may include a hetero atom bond.
  • the photofunctional group Q is a known photosensitive group and is not particularly limited. Examples thereof include a group having a cyclic structure described in WO2015-088021, an oxime residue, and these substituted groups. A group having a cyclic structure is preferred.
  • Examples of the group having a cyclic structure include an aromatic group described in WO2015-088021, a group having a heterocyclic structure, and a substituted group, and an aromatic group is preferable. Further, groups in the photofunctional group may be bonded to each other to form a cyclic structure.
  • aromatic group examples include nitro such as o-nitrobenzyl group described in WO2015-088021, m-nitrobenzyl group described in WO2015-088021, and p-nitrobenzyl group described in WO2015-088021.
  • aromatic group examples include nitro such as o-nitrobenzyl group described in WO2015-088021, m-nitrobenzyl group described in WO2015-088021, and p-nitrobenzyl group described in WO2015-088021.
  • examples thereof include benzyl group, benzyl group described in WO2015-088021, and benzoyl group and substituted groups thereof, nitrobenzyl group is preferable, o-nitrobenzyl group and p-nitrobenzyl group are more preferable, o A nitrobenzyl group is particularly preferred.
  • groups in the photofunctional group may be bonded to each other to form a cyclic structure.
  • Examples of the group having a heterocyclic structure include a coumarin derivative residue described in WO2015-088021 and an imide group or a substituted group thereof.
  • Examples of the —OQ group in which the photofunctional group Q is an o-nitrobenzyl group include (2,6-dinitrobenzyl) oxy group, (2-nitrobenzyl) oxy group, (3,4-dimethoxy-2-nitro group) And nitrobenzyloxy groups such as (benzyl) oxy group.
  • Examples of the —OQ group in which the photofunctional group Q is a p-nitrobenzyl group include (2,4-dinitrobenzyl) oxy group, (4-nitrobenzyl) oxy group, and [1- (4-nitronaphthalene) methyl. Nitrobenzyloxy group such as oxy group.
  • the photofunctional group Q is a benzyl group
  • 3,5-dimethoxybenzyloxy group for example, 3,5-dimethoxybenzyloxy group, [1- (3,5-dimethoxyphenyl) -1-methylethyl] oxy group, 9-anthryl Benzyloxy groups such as methyloxy group, 9-phananthrylmethyloxy group, 1-pyrenylmethyloxy group, [1- (anthraquinone-2-yl) ethyl] oxy group, 9-phenylxanthen-9-yloxy group Can be mentioned.
  • examples of the residues excluding the ZQ group include 3- (trimethoxysilyl) propylaminocarbonyl group, 3- (triethoxysilyl) propylaminocarbonyl group, 3- (methyl Monoaminocarbonyl groups such as dimethoxysilyl) propylaminocarbonyl group, 3- (methyldiethoxysilyl) propylaminocarbonyl group; N- [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group, N, N′-bis And diaminocarbonyl groups such as [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group; and aminocarbonyl groups such as triaminocarbonyl group such as N- [3- (trimethoxysilyl) propyl] diethylenetriaminocarbonyl group.
  • aminocarbonyl groups an aminocarbonyl group having an amino group (—NH 2 ) is preferable from the viewpoint of adhesion, and 3- (trimethoxysilyl) propylaminocarbonyl group, 3- (triethoxysilyl) propylaminocarbonyl group , 3- (methyldimethoxysilyl) propylaminocarbonyl group and N- [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group are more preferable, and 3- (trimethoxysilyl) propylaminocarbonyl group is preferred in view of adhesiveness and curability. 3- (triethoxysilyl) propylaminocarbonyl group is most preferred.
  • the blending ratio of the photoaminosilane generating compound is not particularly limited, but is preferably 0.01 to 50 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. More preferred is 0.1 to 20 parts by mass.
  • These photoaminosilane generating compounds may be used alone or in combination of two or more.
  • the photocurable composition according to this embodiment preferably further comprises (F) a monofunctional compound having a photopolymerizable unsaturated group.
  • the viscosity of the photocurable compound can be lowered by the monofunctional compound (F).
  • various monofunctional compounds having a photopolymerizable unsaturated group can be used, and there is no particular limitation. For example, a (meth) acryloyl group And one N-vinyl compound in which a vinyl group is directly bonded to a nitrogen atom.
  • Examples of the compound having one (meth) acryloyl group in one molecule include a compound having one (meth) acryloyloxy group in one molecule and a compound having one (meth) acrylamide group in one molecule. From the viewpoint of storage stability, a compound having one (meth) acryloyloxy group in one molecule is preferable. Moreover, the compound which has one (meth) acrylamide group in 1 molecule from a reactive viewpoint is preferable.
  • any of a monomer, an oligomer and a polymer can be used. From the viewpoint of viscosity, a monomer having a (meth) acryloyloxy group is preferred. From the viewpoint of curability, an oligomer having a (meth) acryloyloxy group is preferable.
  • the monomer having one (meth) acryloyloxy group in one molecule is not particularly limited as long as it is a compound having one (meth) acryloyloxy group.
  • monofunctional (meth) acrylates, etc. Is mentioned.
  • (meth) acrylate As monofunctional (meth) acrylate, as hydroxyl-containing (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono And (meth) acrylate 2-hydroxy-3-octyloxypropyl acrylate.
  • the (meth) acrylate having an alkoxy group include methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
  • Examples of the aromatic (meth) acrylate include phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, and benzyl (meth) acrylate.
  • Examples of the long-chain hydrocarbon (meth) acrylate having 8 to 20 carbon atoms include 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, and isostearyl (meth) acrylate. From the viewpoint of availability, long-chain hydrocarbon (meth) acrylates having 8 to 18 carbon atoms are preferred.
  • Examples of the alicyclic (meth) acrylate include cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate.
  • Examples of the (meth) acrylate having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate. Further, N- (meth) acryloyloxyethyl hexahydrophthalimide and the like can be mentioned.
  • Examples of the (meth) acrylate having a crosslinkable silicon group include 3- (trimethoxysilyl) propyl (meth) acrylate. When flexibility is required, monofunctional (meth) acrylates are preferably used.
  • a polymer having one (meth) acryloyloxy group in one molecule a polymer having one (meth) acryloyloxy group can be used.
  • an acrylic polymer having an acrylic polymer having one (meth) acryloyloxy group as a skeleton, a urethane (meth) acrylate polymer, a polyester (meth) acrylate polymer, a polyether (meth) acrylate polymer examples thereof include an epoxy polymer and an epoxy (meth) acrylate polymer.
  • Examples of the compound having one (meth) acrylamide group in one molecule include N-methyl (meth) acrylamide and (meth) acryloylmorpholine.
  • N-vinyl compound examples include N-vinyl pyrrolidone and N-vinyl caprolactam.
  • the N-vinyl compound is preferred from the viewpoint of reactivity and resistance to oxygen inhibition.
  • the blending ratio of the monofunctional compound (F) is not particularly limited, but is preferably 0.01 to 100 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. Part is more preferable, and 1 to 100 parts by weight is still more preferable.
  • These (F) monofunctional compounds may be used alone or in combination of two or more.
  • the photocurable composition according to this embodiment preferably further comprises (G) a tackifying resin.
  • G There is no restriction
  • the tackifying resin when used for an adherend having a low polarity, it is preferable to use a tackifying resin having a low polarity.
  • a tackifying resin having a high polarity is used. Is preferred.
  • the blending ratio of the (G) tackifying resin is not particularly limited, but is preferably 0.1 to 100 parts by weight, preferably 1 to 80 parts by weight with respect to 100 parts by weight of the (A) crosslinkable silicon group-containing organic polymer. More preferred. These tackifier resins may be used alone or in combination of two or more.
  • the formulation according to the present embodiment includes, as necessary, a compound having a (meth) acrylamide group, a compound having an epoxy group, a silane coupling agent, a base-growing aminosilane, a photoradical polymerization initiator, a photosensitizer, Extenders, diluents, plasticizers, moisture absorbers, silanol condensation catalysts, physical property modifiers that improve tensile properties, reinforcing agents, colorants, flame retardants, sagging inhibitors, antioxidants, anti-aging agents, UV absorption
  • Various additives such as an agent, a solvent, a fragrance, a pigment, a dye, a conductive powder, a heat conductive powder, a phosphor, a wax, and a resin filler can be further included.
  • Examples of the compound having an N-methyl (meth) acrylamide group include N-methyl (meth) acrylamide, N- (meth) acryloylmorpholine, etc., and have a good balance between curability, physical properties, and safety. Therefore, acryloylmorpholine is preferable.
  • Examples of the compound having an epoxy group include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, aliphatic cyclic epoxy resin, brominated epoxy resin, and rubber.
  • Examples include modified epoxy resins, urethane modified epoxy resins, glycidyl ester compounds, epoxidized polybutadiene, and epoxidized SBS (SBS represents a styrene-butadiene-styrene copolymer).
  • SBS represents a styrene-butadiene-styrene copolymer.
  • the compound according to the present embodiment can improve the adhesion to general adherends such as metal, plastic, glass, etc. by compounding a silane coupling agent.
  • silane coupling agents include amino group-containing silanes; ketimine type silanes; epoxy group-containing silanes; mercapto group-containing silanes; vinyl type unsaturated group-containing silanes; chlorine atom-containing silanes; Alkyl silanes; phenyl group-containing silanes; isocyanurate group-containing silanes, and the like, but are not limited thereto.
  • modified amino group-containing silanes in which amino groups are modified by reacting amino group-containing silanes with epoxy group-containing compounds, isocyanate group-containing compounds, and (meth) acryloyl group-containing compounds containing the above silanes are used. May be.
  • a silane coupling agent may be added for the purpose of crosslinking the tackifier resin and the crosslinkable silicon group-containing organic polymer.
  • a tackifying resin containing phenol or carboxylic acid for example, by adding an epoxy silane, the crosslinkable silicon group-containing organic polymer and the tackifying resin can be cross-linked.
  • the blending ratio of the silane coupling agent is not particularly limited, but is preferably 0.2 to 20 parts by weight, and 0.3 to 15 parts by weight with respect to 100 parts by weight of the (A) crosslinkable silicon group-containing organic polymer. More preferred is 0.5 to 10 parts by mass.
  • These silane coupling agents may be used alone or in combination of two or more.
  • the compound according to this embodiment may further contain a base-growing aminosilane for the purpose of improving the adhesion performance.
  • the base-growing aminosilane include compounds that are base-growing amine compounds and have a crosslinkable silicon group in the amine residue (a compound that generates an amine compound having a crosslinkable silicon group when decomposed).
  • a compound that generates an amine compound having a crosslinkable silicon group when decomposed As such a compound, 9-fluorenylmethyl ester of carbamic acid having a crosslinkable silicon group (C 13 H 9 CH 2 OCONR 13 R 14 , wherein R 13 and R 14 are hydrogen atoms or hydrocarbon groups, etc.
  • R 13 and R 14 is an organic group such as a hydrocarbon group having a crosslinkable silicon group), 2-arylsulfonylethyl ester of carbamic acid having a crosslinkable silicon group (ArSO 2 CH 2 CH 2 OCONR 13 R 14 , wherein Ar is an aromatic group which may have a substituent, R 13 and R 14 are the same as above, and 3-nitropentane of carbamic acid having a crosslinkable silicon group 2- yl ester (CH 3 CH 2 CH (NO 2) CH (CH 3) OCONR 13 R 14, wherein, R 13, R 14 are as defined above Etc.
  • 2-arylsulfonylethyl ester of carbamic acid having a crosslinkable silicon group ArSO 2 CH 2 CH 2 OCONR 13 R 14 , wherein Ar is an aromatic group which may have a substituent, R 13 and R 14 are the same as above
  • 3-nitropentane of carbamic acid having a crosslinkable silicon group 2- yl ester CH 3 CH
  • photo radical polymerization initiator examples include arylalkyl ketones such as benzoin ether derivatives and acetophenone derivatives, oxime ketones, acylphosphine oxides, S-phenyl thiobenzoates, titanocenes, and high molecular weights thereof. Derivatives.
  • the formulation according to this embodiment can further contain a diluent.
  • a diluent By blending a diluent, physical properties such as viscosity can be adjusted.
  • various diluents can be used, and there is no particular limitation.
  • saturated hydrocarbon solvents such as normal paraffin and isoparaffin, ⁇ -olefin derivatives such as HS dimer (trade name of Toyokuni Oil Co., Ltd.), aromatic hydrocarbon solvents, alcohol solvents such as diacetone alcohol, ester solvents And various solvents such as citrate ester solvents such as acetyltriethyl citrate and ketone solvents.
  • the flash point of the diluent is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher.
  • the flash point of the mixed diluent is 70 degreeC or more.
  • the flash point is preferably 250 ° C. or lower.
  • a saturated hydrocarbon solvent is preferable as the diluent, and normal paraffin and isoparaffin are more preferable.
  • Normal paraffins and isoparaffins preferably have 10 to 16 carbon atoms, and more preferably have 14 to 16 carbon atoms due to the influence on the use environment (VOC).
  • the mixing ratio of the diluent is not particularly limited, but 0 to 25% of the diluent is blended with respect to the unit weight of the blend according to the present embodiment from the viewpoint of the balance between the improvement of coating workability and the decrease in physical properties due to blending. It is preferable to add 0.1 to 15%, more preferably 1 to 7%.
  • a diluent may be used independently or may use 2 or more types together.
  • the resin filler a particulate filler made of an organic resin or the like can be used.
  • organic fine particles such as polyethyl acrylate resin, polyurethane resin, polyethylene resin, polypropylene resin, urea resin, melamine resin, benzoguanamine resin, phenol resin, acrylic resin, and styrene resin can be used.
  • the resin filler (resin fine powder) is preferably a true spherical material that can be easily obtained by suspension polymerization of a monomer (for example, methyl methacrylate). Moreover, since a resin filler is suitably contained as a filler in the solution composition, a spherical crosslinked resin filler is preferable.
  • a urethane resin filler and an acrylic resin filler are preferable, and a urethane resin filler is more preferable in terms of good compatibility with the formulation according to the present embodiment.
  • the average particle size of the resin filler is preferably 1 to 150 ⁇ m, more preferably 5 to 30 ⁇ m.
  • the average particle diameter is a 50% cumulative particle diameter measured by a laser diffraction scattering method. If the average particle size is smaller than 1 ⁇ m, it may be difficult to disperse in the conductive adhesive system. On the other hand, if it is larger than 150 ⁇ m, it tends to be clogged with an application nozzle.
  • the blending ratio of the resin filler is preferably 0.5 to 200 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A).
  • a resin filler may be used independently and may use 2 or more types together.
  • the resin filler preferably contains a black resin filler.
  • a black resin filler having an average particle size of 1 to 150 ⁇ m good deep curability can be obtained even when a single wavelength LED lamp or the like is used, and excellent light shielding properties and deep curability are obtained. Can be achieved.
  • the method for producing the photocurable composition is not particularly limited.
  • the components (A) to (D) are mixed in a predetermined amount, and if necessary, other compounding materials are mixed and deaerated and stirred. Can be manufactured.
  • the order of blending each component and other compounding substances is not particularly limited and can be determined as appropriate.
  • the photocurable composition can be a one-component type or a two-component type as required, but can be suitably used particularly as a one-component type.
  • the photocurable composition according to this embodiment is a photocurable composition that is cured by light irradiation, can be cured at room temperature (for example, 23 ° C.), and is preferably used as a room temperature photocurable curable composition. However, if necessary, curing may be accelerated by heating.
  • cured material which concerns on this embodiment is a method of forming hardened
  • the cured product according to the present embodiment is a cured product obtained by this method.
  • the manufacturing method of the product which concerns on this embodiment is a method of manufacturing using the photocurable composition which concerns on this embodiment.
  • the product according to the present embodiment is a product obtained by using this method, and can be suitably used for various products such as an electronic circuit, an electronic component, a building material, and an automobile.
  • an active energy ray As an active energy ray, ultraviolet rays, visible rays, infrared rays, etc.
  • electromagnetic waves such as light rays, X-rays, and ⁇ rays, electron beams, proton beams, neutron beams, and the like can be used.
  • the ultraviolet ray includes 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, and includes, 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, and a metal halide depending on the properties of the photobase generator used.
  • a light emitting diode is preferred.
  • the irradiation energy is preferably 10 to 20,000 mJ / cm 2, more preferably 20 to 10,000 mJ / cm 2, and still more preferably 50 to 5,000 mJ / cm 2 . If it is less than 10 mJ / cm 2 , the curability may be insufficient, and if it is greater than 20,000 mJ / cm 2 , even if light is irradiated more than necessary, time and cost are wasted and the substrate is damaged. There is.
  • the method for applying the photocurable composition according to the present embodiment to the adherend is not particularly limited, but screen printing, stencil printing, roll printing, dispenser coating, jet dispenser coating, spray coating, spin coating, and other coating methods. Are preferably used.
  • a photocurable composition is apply
  • the photocurable composition according to the present embodiment is a fast-curing photocurable composition excellent in workability, and is particularly useful as an adhesive / adhesive composition, and is an adhesive, a sealing material, and an adhesive. , Coating materials, potting materials, paints, putty materials, primers, gaskets, and the like.
  • the photocurable composition according to the present embodiment 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 a peripheral portion of the panel, and the like; Sealing agents, sealing agents for vehicles, etc .; architectural and industrial sealing agents; 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; Materials for forming a molded article; pressure-sensitive adhesive; adhesive; elastic adhesive; contact adhesive; use requiring rework or repair; use for liquid gaskets and the like.
  • the liquid gasket for example, it can be used for Formed In Place Gasket (FIPG) for electronic equipment. That is, the photocurable composition according to this embodiment is liquid before curing. Therefore, the photocurable composition according to the present embodiment is a FIPG for electronic equipment, and it can be secured even when exposed to the air before irradiation with active energy rays, so that a sufficient working time can be secured, and the active energy rays After irradiation, it can be used as a liquid gasket for electronic device products that has a sufficient bonding time and is cured in a short time.
  • FIPG Formed In Place Gasket
  • the photocurable composition when the housing member is sandwiched after the active energy ray irradiation, the photocurable composition is applied to a portion where the seal of the housing member is not desired.
  • the liquid gasket formed using the object does not protrude, and the housing member can be removed with a small force.
  • the removal of the housing member is not limited to the initial stage of curing, and the housing member can be removed with a small force even after curing.
  • a housing member can be recombined using this liquid gasket as it is, and sealing performances, such as an initial waterproof performance, can be maintained even after recombination.
  • a photoaminosilane generating compound, an aminosilane compound, etc. it can be designed so that it can be removed after a certain period of time even if it can be removed within a certain period of time.
  • the liquid gasket of the photocurable composition according to the present embodiment is applied to one or both of the plurality of housing members such as the main body and the lid, and irradiated with active energy rays, and then the housing member is applied. Can be used in combination. Since the crosslinkable silicon group-containing organic polymer is cured by moisture in the air after irradiation with active energy rays, curing proceeds if the housing members are left after being combined. Heating may be performed to increase the curing rate.
  • FT-NMR measuring device JNM-ECA500 (500 MHz) manufactured by JEOL Ltd.
  • FT-IR measuring device FT-IR460Plus manufactured by JASCO Corporation
  • Synthesis Example 1 Synthesis of polyoxyalkylene polymer A1 having a trimethoxysilyl group at its terminal Polyoxypropylene was reacted with propylene oxide in the presence of zinc hexacyanocobaltate-glyme complex catalyst using ethylene glycol as an initiator. Diol was obtained. According to the method of Synthesis Example 2 of WO2015-088021, a polyoxyalkylene polymer having an allyl group at the terminal of the obtained polyoxypropylene diol was obtained.
  • trimethoxysilane which is a silicon hydride compound
  • trimethoxysilane which is a silicon hydride compound
  • platinum vinyl siloxane complex isopropanol solution to react with the polyoxyalkylene having a trimethoxysilyl group at the end.
  • a polymer A1 was obtained.
  • the peak top molecular weight was 25,000 and the molecular weight distribution was 1.3.
  • the number of terminal trimethoxysilyl groups was 1.7 per molecule.
  • Synthesis Example 2 Synthesis of polyoxyalkylene polymer A2 having a trimethoxysilyl group at its terminal Polyoxypropylene was reacted with propylene oxide in the presence of zinc hexacyanocobaltate-glyme complex catalyst using ethylene glycol as an initiator. Diol was obtained. According to the method of Synthesis Example 2 of WO2015-088021, a polyoxyalkylene polymer having an allyl group at the terminal of the obtained polyoxypropylene diol was obtained.
  • trimethoxysilane which is a silicon hydride compound
  • trimethoxysilane which is a silicon hydride compound
  • 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.
  • (Synthesis Example 3) Synthesis of (meth) acrylic polymer A3 having a trimethoxysilyl group 70.00 g of methyl methacrylate, 30.00 g of 2-ethylhexyl methacrylate, 12.00 g of 3-methacryloxypropyltrimethoxysilane, as a metal catalyst
  • Synthesis Example 4 of WO2015-088021 using 0.10 g of titanocene dicylide, 8.60 g of 3-mercaptopropyltrimethoxysilane, and 20.00 g of a benzoquinone solution (95% THF solution) as a polymerization terminator.
  • the (meth) acrylic polymer A3 having a trimethoxysilyl group was obtained.
  • the (meth) acrylic polymer A3 had a peak top molecular weight of 4,000 and a molecular weight distribution of 2.4.
  • the number of trimethoxysilyl groups contained by 1 H-NMR measurement was 2.00 per molecule.
  • Synthesis Example 4 Synthesis of fluorinated polymer C1-1 Polyoxypropylene diol having a molecular weight of about 2,000 is used as an initiator, and propylene oxide is reacted in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to obtain a molecular weight in terms of hydroxyl value. A polyoxypropylene diol having a molecular weight distribution of 1.3 was obtained. According to the method of Synthesis Example 2 of WO2015-088021, a polyoxyalkylene polymer having an allyl group at the terminal of the obtained polyoxypropylene diol was obtained.
  • the polyoxyalkylene polymer having an allyl group at the terminal is reacted with methyldimethoxysilane, which is a silicon hydride compound, by adding a platinum vinylsiloxane complex isopropanol solution, and the polyoxyalkylene having a methyldimethoxysilyl group at the terminal is reacted.
  • a polymer A4 was obtained.
  • the peak top molecular weight was 15,000 and the molecular weight distribution was 1.3. According to 1 H-NMR measurement, the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.
  • urethane prepolymer A 0.5 equivalent of 3-mercaptopropyltrimethoxysilane is reacted with urethane prepolymer A with respect to the NCO group of this urethane prepolymer A, and on average, it has a trimethoxysilyl group at one end and an NCO group at the other end.
  • a polymer was obtained. With respect to the NCO group of the obtained polymer, an equivalent amount of 4-hydroxybutyl acrylate is reacted with this polymer, and an average polymer A4 having a trimethoxysilyl group at one end and an acryloyloxy group at the other end is obtained. Obtained.
  • Examples 1 to 12 and Comparative Examples 1 to 7 Each compounding substance was added at the blending ratio shown in Table 1, mixed and stirred to prepare a photocurable composition.
  • the compounding amount of each compounding substance is indicated by g
  • the polyoxyalkylene polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, and the acrylic polymer.
  • A3 is the acrylic polymer A3 obtained in Synthesis Example 3
  • the organic polymer A4 having a crosslinkable silicon group and a photoradically polymerizable vinyl group in the molecule is the polymer A4 obtained in Synthesis Example 6.
  • the fluorinated polymer C1-1 is the fluorinated polymer C1-1 obtained in Synthesis Example 4
  • the photoaminosilane generating compound E1 is the photoaminosilane generating compound E1 obtained in Synthesis Example 5
  • details of other compounding substances are as follows. It is as follows.
  • Photobase generator B1 Irgacure (registered trademark) 379EG [trade name, manufactured by BASF, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Morpholinyl) phenyl] -1-butanone] in 70% PC (propylene carbonate) solution.
  • Photobase generator B2 SA-2 [trade name of San Apro Co., Ltd.] 5% PC solution.
  • Multifunctional compound D1 1,6-hexanediol diacrylate, trade name “SR238NS” (manufactured by Sartomer), bifunctional acrylate monomer.
  • Multifunctional compound D2 trimethylolpropane, trade name “Light Acrylate TMP-A” (manufactured by Kyoeisha Chemical Co., Ltd.), trifunctional acrylate monomer.
  • Polyfunctional compound D3 dipentaerythritol hexaacrylate, trade name “Light acrylate DPE-6A” (manufactured by Kyoeisha Chemical Co., Ltd.), hexafunctional acrylate monomer.
  • Polyfunctional compound D4 urethane acrylate, trade name “NK Oligo U-15HA” (manufactured by Shin-Nakamura Chemical Co., Ltd.), polymer having 15 acryloyloxy groups.
  • Polyfunctional compound D5 acrylic acrylate, trade name “RC100C” (manufactured by Kaneka Corporation), polymer having two acryloyloxy groups.
  • Monofunctional compound F1 Methoxydipropylene glycol acrylate, trade name “Light acrylate DPM-A” (manufactured by Kyoeisha Chemical Co., Ltd.), monofunctional acrylate.
  • Monofunctional compound F2 Phenoxyethyl acrylate, trade name “Light Acrylate PO-A” (manufactured by Kyoeisha Chemical Co., Ltd.).
  • Tackifying resin G1 Trade name “Pine Crystal KE-100” (manufactured by Arakawa Chemical Industries, Ltd.). * 11) Compound having an epoxy group: bisphenol A type epoxy resin, trade name “JER828” (manufactured by Mitsubishi Plastics). * 12) Cleavage type photo radical generator: Trade name “Irgacure (registered trademark) 1173” (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) * 13) Tin catalyst: 33% PC solution of Neostan U-100 [trade name, manufactured by Nitto Kasei Co., Ltd.]
  • a creep test and a tensile shear bond strength test were performed on the obtained photocurable composition by the following methods. The results are shown in Table 1.
  • 1) Creep test The obtained photocurable composition was applied to an adherend [acrylic resin] with an area of 5 mm ⁇ 25 mm and a thickness of 100 ⁇ m, and UV irradiation [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance 1000 mW / cm 2 ), integrated light quantity: 3000 mJ / cm 2 ].
  • the adherend [acrylic resin] was bonded together, pressed with a small eyeball clip, cured in a dark room at 23 ° C. and 50% RH for 30 seconds, and then subjected to a creep test (weight: 10 g). Evaluation was made based on evaluation criteria. ⁇ : The adherend did not fall, ⁇ : The adherend dropped.
  • the compounding amount of each compounding substance is indicated by g
  • the polyoxyalkylene polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, and the acrylic polymer.
  • A3 is the acrylic polymer A3 obtained in Synthesis Example 3
  • the fluorinated polymer C1-1 is the fluorinated polymer C1-1 obtained in Synthesis Example 4.
  • the compounds annotated the same as in Table 1 indicate the same compounds as in Table 1. Details of other compounding substances are as follows.
  • Photobase generator B3 Irgacure (registered trademark) 379EG (manufactured by BASF, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl 1-butanone), diluted to 50% by mass with a propylene carbonate solution.
  • Irgacure registered trademark
  • 379EG manufactured by BASF, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl 1-butanone
  • Polyfunctional compound D6 Light acrylate DPM-A (Kyoeisha Chemical Co., Ltd., trade name, methoxydipropylene glycol acrylate) * 16) Polyfunctional compound D7: UV3700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., polymer having urethane acrylate and two acryloyloxy groups) * 17) Sagging stop material: AEROSIL (registered trademark) R972 (Nippon Aerosil Co., Ltd., hydrophobic silica)
  • a dispenser robot (hereinafter referred to as “dispenser robot A”) having a needle with an inner diameter of 0.84 mm as a discharge needle under the condition of a fluorescent lamp with a film that cuts a wavelength of 500 nm or less and having a temperature of 23 ° C. and 50% RH. was used to test the workability of the composition prepared in Example 13 when not irradiated with UV. In an environment of 23 ° C. and 50% RH, the film was continuously applied to a PET film, and the time during which dispensing can be applied by finger touch was measured.
  • Comparative Example 8 was cured to a state where it could not be bonded, and Comparative Examples 10 and 11 could not be evaluated because they were uncured.
  • Example 14 to 15 Comparative Examples 8 to 11
  • a photocurable composition and a curable composition were prepared by the same method as in Example 13 except that the compounding substances were changed. And like Example 13, the sclerosing
  • the liquid gaskets of Comparative Examples 9 to 11 had poor shape retention, spread when the glass plates were bonded together, and could not be used as gaskets.
  • the liquid gasket according to the example does not cure when not irradiated with active energy rays, has excellent shape retention, and has sufficient time for bonding after irradiation with active energy rays. It was shown that Moreover, in the housing member joined using the liquid gasket according to the embodiment, the housing member can be removed with a small force even at the initial stage of curing and after curing, without protruding to a portion where sealing is not desired. It was shown that the housing member can be recombined using the gasket as it is, and the sealing performance such as the initial waterproof performance is maintained after the recombination.

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
PCT/JP2015/086413 2014-12-26 2015-12-25 光硬化性組成物 WO2016104787A1 (ja)

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