Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • 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
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5397—Phosphine oxides
• • 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
  • C08G2190/00—Compositions for sealing or packing joints
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking
  • C08L2312/06—Crosslinking by radiation

Definitions

• the present invention relates to a photocurable urethane gel and a method for producing the same.
• Polyurethane is a general term for polymers with urethane bonds, and is used in various forms such as foams, elastomers, adhesives, paints, binders, and synthetic leather.
• polyurethane elastomers are excellent in elasticity, mechanical strength, oil resistance, abrasion resistance, weather resistance, etc., and are used for cushioning materials, automobile seats, sealing materials, industrial roll materials, packing materials, etc. there is
• polyurethane There are a wide variety of types of polyurethane, including those with properties such as thermoplasticity, thermosetting, or photocuring.
• a method for producing polyurethane a method of polymerizing by dual curing combining photocuring and heat curing is known (see, for example, Patent Document 1).
• existing thread standards for pipe joints include types such as parallel threads and tapered threads depending on the application, and the number of threads, the angle of the threads, etc. may differ.
• types of screws vary widely depending on the economic zone, and for this reason, conversion joints are required when there is no compatibility between the male thread side and the female thread side.
• JP 2013-213175 A Japanese Patent Application Laid-Open No. 2005-120820
• the above-mentioned conversion joint is a convenient joint that enables connection of male and female threads with different standards, it has the disadvantages of tight mounting space, an increase in the weight of the object, and an increase in the number of parts. Therefore, when the number of connection points increases, the demerit cannot be ignored.
• one-touch joints make it easy to attach and detach tubes or hoses, they are similar to conversion joints in terms of screw connection work.
• the joint itself requires at least 5 or more parts, and when used for liquids, liquid pools occur in the joint, so it can be said that the structure is unsuitable for sites that require cleaning inside the pipe.
• UV-curable FRP sheets can greatly simplify multiple processes by reducing the labor of preparing raw materials at the repair site. become necessary.
• the present inventor considered using the dual-curing urethane-based composition described in Patent Document 1, but due to the following problems, the composition was not used. Decided not to use. One is the low flexibility during the first stage curing.
• the dual-curing urethane composition described in Patent Document 1 lacks flexibility, although it can be slightly deformed when the first stage of curing (photocuring) is performed. Another is the low hardness during the second stage curing.
• the dual-curing urethane composition described in Patent Document 1 has a low hardness when the second-stage curing (thermal curing) is performed after the first-stage curing (photocuring). Ta. For this reason, the dual-curing urethane-based composition described in Patent Document 1 is not suitable for specifications in which the joint opening is filled and completely cured, or as a substitute for an ultraviolet-curing FRP sheet.
• the present invention has been made in view of the above problems. It is an object of the present invention to obtain a photocurable urethane gel-like body which becomes a polyurethane with high hardness while maintaining its self-molded shape by photocuring.
• a photocurable urethane gel-like body A photocurable composition (A) containing a polyfunctional urethane (meth)acrylate and a photopolymerization initiator; Polyurethane (B); A photocurable gel-like body containing at least The photocurable composition (A):polyurethane (B) is in a mass ratio of 25:75 to 55:45,
• the polyfunctional urethane (meth)acrylate is a photocurable urethane gel that does not have residual hydroxyl groups.
• the photocurable composition (A):polyurethane (B) preferably has a mass ratio of 41:59 to 50:50. is within the range of (3)
• the weight average molecular weight (Mw) of the polyfunctional urethane (meth)acrylate is preferably 1500 or more and 2000 or less.
• the photopolymerization initiator is preferably a bisacylphosphine oxide-based photopolymerization initiator.
• the gel has a hardness of E3 or more and E10 or less by a type E durometer based on JIS K 6253, and After photocuring, the hardness by type E durometer based on JIS K 6253 becomes E75 or more.
• thermosetting composition containing at least a polyol compound, an isocyanate compound and an acrylate monomer as a hydroxyl group imparting additive; A method for producing any of the photocurable urethane gel-like materials described above,
• the photocurable composition the thermosetting composition is in a mass ratio of 25:75 to 55:45, A mixing step of mixing the thermosetting composition and the photocurable composition; A thermosetting step of thermosetting the mixture after the mixing step; including.
• the photocurable composition:the thermosetting composition preferably has a mass ratio of 41:59 to 50: 50 is in the range.
• the acrylate monomer is preferably hydroxyethyl acrylate and/or pentaerythritol (tri/tetra)acrylate.
• the first-stage curing results in a gummy shape and self-molding properties that match the shape of the surface to be used, and the second-stage photocuring maintains the self-molding shape while maintaining high hardness. It is possible to obtain a photocurable urethane gel-like body that becomes a polyurethane of
• the photocurable urethane gel-like material according to this embodiment is composed of a photo It contains at least a curable composition (A) and a polyurethane (B).
• the weight ratio of photocurable composition:polyurethane is in the range of 25:75 to 55:45.
• Polyfunctional urethane (meth)acrylates are oligomers or monomers with no residual hydroxyl groups.
• the photocurable composition is a composition that can be cured by irradiating the gel with light.
• the photocurable composition is in an uncured state in the gel.
• polyurethane forms a polymer in a gel-like body.
• the gel-like material is a so-called gel-like semi-cured material in which an uncured photocurable composition is impregnated into a cured polyurethane.
• ⁇ is used so as to include the numerical values before and after it.
• the photocurable composition according to this embodiment contains at least a polyfunctional urethane (meth)acrylate and a photopolymerization initiator (also referred to as “photoinitiator”).
• a polyfunctional urethane (meth)acrylate and a photopolymerization initiator (also referred to as “photoinitiator”).
• Polyfunctional Urethane (Meth)acrylate Polyfunctional urethane (meth)acrylate has a urethane bond formed by reacting an isocyanate group and a hydroxy group, and an acrylic group.
• the acrylic group is at least one of an acryloyl group and a methacryloyl group (also referred to as "methacryloyl group”).
• Polyfunctional urethane (meth)acrylates are preferably oligomers rather than monomers.
• An oligomer means a polymer having relatively small linking units of monomers (also referred to as monomers) and having about 2 or more and 1000 or less monomers.
• the polyfunctional urethane (meth)acrylate is "polyfunctional" and thus means one having 2 or more, preferably 3 or more functional groups (acrylic groups, acryloyl groups).
• a polyfunctional urethane (meth)acrylate can be produced, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or polyester polyol with an isocyanate compound with (meth)acrylic acid.
• Polyfunctional urethane (meth)acrylates may be aliphatic urethane (meth)acrylates or aromatic urethane (meth)acrylates.
• polyether polyols examples include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polypentamethylene glycol, and polyhexamethylene glycol, and random or block copolymerization of these polyalkylene glycols. A coalescence etc. are mentioned.
• polyester polyols include condensation polymers of polyhydric alcohols and polycarboxylic acids or anhydrides thereof; and ring-opening polymers of cyclic esters (lactones).
• Polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin, trimethylol Examples include propane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, etc.), bisphenols, and sugar alcohols.
• Polyvalent carboxylic acids or anhydrides thereof include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, and trimellitic acid.
• cyclic esters include propiolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -caprolactone and the like.
• isocyanate compounds include one or more of aliphatic or aromatic diisocyanates and polyisocyanates.
• Exemplary isocyanate compounds include TDI (eg, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI)), MDI (eg, 4,4 '-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), Aromatic polyisocyanates such as tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; hexamethylene
• XDI, TDI, MDI, TMHDI, NDI, H 6 XDI, H 12 MDI, TMXDI, HDI, IPDI and NBDI are more preferred as isocyanate compounds, and among them, XDI, TDI, MDI, TMXDI and HDI is even more preferred.
• the polyfunctional urethane (meth)acrylate used in this embodiment does not have residual hydroxyl groups. If the polyfunctional urethane (meth)acrylate has residual hydroxyl groups, it is not preferable because gelation tends to be inhibited during the production of the photocurable urethane gel.
• the weight average molecular weight (Mw) of the polyfunctional urethane (meth)acrylate is not particularly limited, but is preferably 1500 or more and 2000 or less, more preferably 1500 or more and 1800 or less.
• the photopolymerization initiator is a composition capable of initiating radical polymerization of urethane (meth)acrylate by irradiation with light typified by visible light or ultraviolet light in the presence of urethane (meth)acrylate. It is a substance (ingredient).
• photopolymerization initiators include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2 -methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-[4-(methylthio)phenyl]-2 - Acetophenone compounds such as morpholino-1-propanone and 2,2-dimethoxy-2-phenylacetophenone; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone and benzoylbenzoic acid , methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone,
• a particularly preferred photopolymerization initiator is an acylphosphine oxide compound, and a more preferred photopolymerization initiator is a bisacylphosphine oxide-based photopolymerization initiator. (2,4,6-Trimethylbenzoyl)phenylphosphine oxide.
• Polyurethane is a polymer having urethane bonds corresponding to a solid matter of a photocurable urethane gel. Polyurethane can be synthesized by heating the following thermosetting composition.
• Thermosetting composition includes at least a polyol compound (also simply referred to as “polyol”), an isocyanate compound (simply referred to as “isocyanate”) and It contains at least an acrylate monomer as a hydroxylating additive.
• any diol containing two hydroxyl groups or a polyol containing three or more hydroxyl groups can be used without particular limitation.
• a polyol such as a polyol may be used alone, or these may be used in combination.
• the weight average molecular weight of the polyol is preferably in the range of 200-10,000.
• polyether polyols examples include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose; aliphatic polyols such as ethylenediamine; Amine compounds; Aromatic amine compounds such as toluenediamine and diphenylmethane-4,4-diamine; Alkanolamines such as ethanolamine and diethanolamine; Examples thereof include polyols obtained by adding thereto an alkylene oxide represented by ethylene oxide, propylene oxide, butylene oxide or polyoxytetramethylene oxide.
• polyester polyols include at least one selected from ethylene glycol, propylene glycol, butanediol pentanediol, hexanediol, glycerin, 1,1,1-trimethylolpropane and other low-molecular-weight polyols, glutaric acid, Condensation polymer with at least one selected from adipic acid, pimelic acid, suberic acid, sebacic acid, dimer acid, other low-molecular-weight aliphatic carboxylic acids and oligomeric acids; ring-opening polymers such as propionlactone or valerolactone etc.
• polystyrene resin examples include, for example, polymer polyols, polycarbonate polyols; polybutadiene polyols; hydrogenated polybutadiene polyols; acrylic polyols; Molecular polyols are included.
• the acrylate monomer used in this embodiment is also referred to as a hydroxy group-containing acrylic acid ester.
• the acrylate monomers may be monofunctional or polyfunctional.
• Examples of the acrylate monomer include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone or alkylene oxide adducts of the above (meth)acrylates, glycerin mono(meth)acrylate, Glycerin di(meth)acrylate, glycidyl methacrylate-acrylic acid adduct, trimethylolpropane mono(meth)acrylate, trimethylol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipenta erythritol penta(meth)acrylate, ditrimethylol
• amine compounds triethylenediamine, bis(2-dimethylaminoethyl) ether, N,N,N',N'-tetramethylhexamethylenediamine, etc.
• metal catalysts dibutyltin dilaurate , stannus octoate, etc.
• plasticizers for example, inorganic fillers
• colorants for example, inorganic fillers
• stabilizers for example, preservatives, antioxidants, and fluorine additives
• fluorine additives may be added.
• the mass ratio of the photocurable composition (A) and the polyurethane (B) constituting the photocurable urethane gel is 25 (A):75 (B) ) to 55(A):45(B). A more preferred mass ratio is within the range of 41(A):59(B) to 50(A):50(B).
• Polyurethane (B) is synthesized by a polyaddition reaction between a reaction product of a polyol compound (b1) and an acrylate monomer (b3) as a hydroxyl-imparting additive, and an isocyanate compound (b2). Therefore, the mass of polyurethane (B) can be considered equal to the sum of the masses of polyol compound (b1), isocyanate compound (b2) and acrylate monomer (b3).
• the amount of the polyfunctional urethane (meth)acrylate (a1) contained in the photocurable composition is It is preferably 95.0 parts by mass or more and 99.9 parts by mass or less, more preferably 97.0 parts by mass or more and 99.7 parts by mass or less, still more preferably 98.0 parts by mass or more and 99.5 parts by mass or less. be.
• the amount of the photopolymerization initiator (a2) contained in the photocurable composition is preferably 0 with respect to 100 parts by mass of the total amount of the polyfunctional urethane (meth)acrylate (a1) and the photopolymerization initiator (a2). .1 parts by mass or more and 5.0 parts by mass or less, more preferably 0.3 parts by mass or more and 3.0 parts by mass or less, and even more preferably 0.5 parts by mass or more and 2.0 parts by mass or less.
• each component before curing of polyurethane in photocurable urethane gel i.e., polyol compound (b1), isocyanate compound (b2) and hydroxyl group imparting additive
• Preferred amounts of the acrylate monomer (b3) are as follows.
• the polyol compound (b1) The isocyanate compound (b2) preferably has a ratio (OH:NCO) at which a urethane bond (--NH--CO--O--) is established in a situation where the hydroxyl group imparting additive is added. That is, the isocyanate compound preferably has an equivalent ratio (NCO/OH) to the hydroxyl value of the polyol compound added with the hydroxyl-imparting additive of 0.5 to 2.0, more preferably 0.8 to 1.7.
• the amount of the acrylate monomer (b3) is preferably 0.5 parts by mass or more and 10.0 parts by mass or less, more preferably 1.0 parts by mass or more and 8.0 parts by mass when the polyol compound (b1) is 100 parts by mass. Part by mass or less, more preferably 1.5 to 6.6 parts by mass.
• the hardness of the photocurable urethane gel is preferably E1 or more and E30 or less, more preferably E3 or more and E10, as measured by a type E durometer based on JIS K 6253. It is below.
• the photo-curing urethane gel-like material having the above hardness range is suitable for filling screw holes and using it as a joint for pipes, or as a substitute for an ultraviolet curable FRP sheet.
• the gel-like body has appropriate hardness, does not liquefy, and can ensure sealing performance with tubes and screw holes, and is therefore suitable for use as pipe joints.
• a method for producing a photocurable urethane gel-like material in the method for producing a photocurable urethane gel-like material according to this embodiment, a photocurable composition containing a polyfunctional urethane (meth)acrylate and a photopolymerization initiator, and a polyol compound , and a thermosetting composition containing at least an isocyanate compound and an acrylate monomer as a hydroxyl-imparting additive.
• the manufacturing method includes a mixing step of mixing the thermosetting composition and the photocurable composition, and a thermosetting step of thermosetting the mixture after the mixing step.
• the photocurable composition:thermosetting composition is in the range of 25:75 to 55:45 by weight.
• thermocurable composition is preferably in the range of 41:59 to 50:50 by weight.
• Acrylate monomers belonging to thermosetting compositions are preferably hydroxyethyl acrylate and/or pentaerythritol (tri/tetra) acrylate.
• a photopolymerization initiator is dissolved in dehydrated acetone as a solvent.
• the melt is added to polyfunctional urethane (meth)acrylate.
• a mixture of a photopolymerization initiator, polyfunctional urethane (meth)acrylate and dehydrated acetone is heated at a temperature of 90-100°C.
• a photocurable composition is completed.
• a hydroxyl group-imparting additive (acrylate monomer) is added to a polyol compound, which is the main ingredient of polyurethane, and mixed.
• acryloyl groups are introduced into the polyol compound.
• an isocyanate compound as a curing agent is added to the mixture and stirred.
• thermosetting composition is completed.
• the above photocurable composition and thermosetting composition are stirred and mixed and heated.
• the heating temperature is not limited as long as the thermosetting composition can be cured, but is preferably 80°C or higher and 120°C or lower, more preferably 90°C or higher and 110°C or lower.
• the mixture of photocurable composition and thermosetting composition is preferably placed in a mold and then heated.
• a photocurable urethane gel is completed.
• the photocurable urethane gel is cured using a light irradiation device capable of irradiating visible light or ultraviolet rays to form polyurethane.
• the photocurable urethane gel that has been thermally cured in the mold can be cured by light irradiation from the exposed surface of the gel while still in the mold. The deeper the hardening depth, the better. For pipe fitting applications, the hardening depth is preferably 15 mm or more.
• the light irradiation device a device capable of irradiating visible light and having a small size is more preferable.
• the hardness of the polyurethane after curing the photocurable urethane gel is preferably E60 or more and E100 or less (E100 is the measurement limit) as measured by a type E durometer based on JIS K 6253. More preferably E70 or more and E100 or less, still more preferably E75 or more and E100 or less. If the polyurethane has the hardness described above, for example, after the screw hole is filled with a photocurable urethane gel, a tube is inserted, and the gel is photocured, the tube and the photocured product can be easily pulled out. It is possible to obtain a tough pipe joint that can withstand long-term use.
• the polyol compound is polyoxypolyalkylene polyol.
• the isocyanate compound is hexamethylene diisocyanate and its derivatives.
• the acrylate monomer as a hydroxyl group-imparting additive includes pentaerythritol (tri/tetra) acrylate (name: PETRA) manufactured by Daicel-Ornex Co., Ltd. or hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.). Name: 2-HEA) was used.
• PETRA pentaerythritol
• 2-HEA hydroxyethyl acrylate
• 2-HEA hydroxyethyl acrylate
• the hardness is in the range of E1 to E30, it is suitable for filling screw holes and using it as a pipe joint, or as a substitute for an ultraviolet curing FRP sheet.
• the gel when the gel is used to attach a tube instead of a one-touch joint, it is easy to fill the screw hole of the attachment with the gel, and the tube can be inserted and penetrated through the gel. is also easy.
• the gel-like body has appropriate hardness, does not liquefy, and can ensure sealing performance between the tube and the screw hole, and is therefore suitable for use as a pipe joint.
• the E hardness of the urethane cured product after photocuring of the photocurable urethane gel was evaluated as E60 or more as acceptable, and as less than E60 as unacceptable.
• E60 or more for example, after filling a screw hole with a photocurable urethane gel, inserting a tube and photocuring the gel, the tube and the photocured product can be easily removed. This is because it is possible to obtain a strong pipe joint that can withstand long-term use without falling out.
• Example 1 The photocurable composition:thermosetting composition was adjusted to a mass ratio of 50:50. 49.75 parts by weight of polyfunctional urethane (meth) acrylate (KRM8904), 0.25 parts by weight of photoinitiator (Omnirad 819), 48.46 parts by weight of "set of polyol compound and isocyanate compound (PC- 15)”, 1.54 parts by mass of a hydroxyl group imparting additive (PETRA) and 0.74 parts by mass of dehydrated acetone as a solvent were mixed and heated to prepare a photocurable urethane gel.
• 1 part by mass is 10 g.
• a specific method for producing a photocurable urethane gel is as follows. First, a photopolymerization initiator was dissolved in dehydrated acetone, and the dissolved product was added to polyfunctional urethane (meth)acrylate. A mixture of the photopolymerization initiator, polyfunctional urethane (meth)acrylate, and dehydrated acetone was heated at a temperature of 95° C. in the air while being stirred until bubbles due to volatilization of the dehydrated acetone were no longer visually confirmed. Also, a hydroxyl group-imparting additive was added to the polyol compound, which is the main ingredient of the polyurethane, and the mixture was stirred at room temperature.
• the mixture was mixed with an isocyanate compound as a curing agent and stirred.
• the compounding ratio of the main agent and the curing agent was approximately 100:108 in mass ratio.
• a photocurable composition obtained by mixing the above photopolymerization initiator and polyfunctional urethane (meth)acrylate, and a thermosetting composition obtained by mixing a hydroxyl group-imparting additive, a polyol compound, and an isocyanate compound. were stirred and mixed, poured into a mold made of silicone resin, and cured by heating at 100° C. for 2 hours. Next, the gel-like body after heating was removed from the mold, and the hardness of the gel-like body was measured.
• the hardness of the photocurable urethane gel obtained by heat curing was E3, which was acceptable.
• a light irradiation device manufactured by Iris Ohyama Co., Ltd. (model number: LWK-1300Z, visible light LED light used, illuminance: 1300 lm, irradiation time: 120 seconds, see Table 1 for details) was applied from above the gel-like body.
• the photocurable urethane gel was photocured by irradiating with light. After photocuring, the depth of curing from the top surface of the gel (referred to as curing depth) was measured. As a result, the hardening depth was 15 mm, which was acceptable. Moreover, the hardness was E81, and it was accepted.
• Example 2 The photocurable composition:thermosetting composition was adjusted to a mass ratio of 50:50.
• the mixture of polyol compound and isocyanate compound was changed from PC-15 to PC-30.
• a photocurable urethane gel was prepared under the same conditions as in Example 1 except for the above changes, and the gel was photocured under the same conditions as in Example 1.
• the hardness of the photocurable urethane gel obtained by heat curing was E10.
• the curing depth after photocuring was 15 mm as in Example 1.
• the hardness of the cured body after photocuring was E94. Both hardness and hardening depth were acceptable levels.
• the photocurable composition:thermosetting composition was 30:70 in mass ratio.
• the amounts of polyfunctional urethane (meth)acrylate (KRM8904), photopolymerization initiator (Omnirad 819), mixture of polyol compound and isocyanate compound (PC-15), and hydroxyl group imparting additive (PETRA) are shown in Table 1. Street.
• the thermal curing conditions and the subsequent photocuring conditions were the same as in Example 1, respectively.
• the hardness of the photocurable urethane gel obtained by heat curing was E6.
• the curing depth after photocuring was 15 mm as in Example 1.
• the hardness of the cured body after photocuring was E70. Both hardness and hardening depth were acceptable levels.
• the photocurable composition:thermosetting composition was in a weight ratio of 35:65.
• the amounts of polyfunctional urethane (meth)acrylate (KRM8904), photopolymerization initiator (Omnirad 819), mixture of polyol compound and isocyanate compound (PC-15), and hydroxyl group imparting additive (PETRA) are shown in Table 1. Street.
• the thermal curing conditions and the subsequent photocuring conditions were the same as in Example 1, respectively.
• the hardness of the photocurable urethane gel obtained by heat curing was E5.
• the curing depth after photocuring was 15 mm as in Example 1.
• the hardness of the cured body after photocuring was E79. Both hardness and hardening depth were acceptable levels.
• the photocurable composition:thermosetting composition was 40:60 in mass ratio.
• the amounts of polyfunctional urethane (meth)acrylate (KRM8904), photopolymerization initiator (Omnirad 819), mixture of polyol compound and isocyanate compound (PC-15), and hydroxyl group imparting additive (PETRA) are shown in Table 1. Street.
• the thermal curing conditions and the subsequent photocuring conditions were the same as in Example 1, respectively.
• the hardness of the photocurable urethane gel obtained by heat curing was E4.
• the curing depth after photocuring was 15 mm as in Example 1.
• the hardness of the cured body after photocuring was E84. Both hardness and hardening depth were acceptable levels.
• the photocurable composition:thermosetting composition was in a weight ratio of 45:55.
• the amounts of polyfunctional urethane (meth)acrylate (KRM8904), photopolymerization initiator (Omnirad 819), mixture of polyol compound and isocyanate compound (PC-15), and hydroxyl group imparting additive (PETRA) are shown in Table 1. Street.
• the thermal curing conditions and the subsequent photocuring conditions were the same as in Example 1, respectively.
• the hardness of the photocurable urethane gel obtained by heat curing was E3.
• the curing depth after photocuring was 15 mm as in Example 1.
• the hardness of the cured body after photocuring was E85. Both hardness and hardening depth were acceptable levels.
• Example 7 The photocurable composition:thermosetting composition was adjusted to a mass ratio of 50:50.
• Polyfunctional urethane (meth)acrylate was changed from KRM8904 to EBECRYL4738.
• a photocurable urethane gel was prepared under the same conditions as in Example 1 except for the above changes, and the gel was photocured under the same conditions as in Example 1.
• the hardness of the photocurable urethane gel obtained by heat curing was E1.
• the curing depth after photocuring was 15 mm as in Example 1.
• the hardness of the cured body after photocuring was E88. Both hardness and hardening depth were acceptable levels.
• Example 8 The photocurable composition:thermosetting composition was adjusted to a mass ratio of 50:50.
• Polyfunctional urethane (meth)acrylate was changed from KRM8904 to EBECRYL9260.
• a photocurable urethane gel was prepared under the same conditions as in Example 1 except for the above changes, and the gel was photocured under the same conditions as in Example 1.
• the hardness of the photocurable urethane gel obtained by heat curing was E3.
• the curing depth after photocuring was 15 mm as in Example 1.
• the hardness of the cured body after photocuring was E79. Both hardness and hardening depth were acceptable levels.
• Example 9 The photocurable composition:thermosetting composition was adjusted to a mass ratio of 50:50. 49.00 parts by mass of polyfunctional urethane (meth)acrylate (EBECRYL9260), 1.00 parts by mass of photopolymerization initiator (TPO), 49.63 parts by mass of "mixture of polyol compound and isocyanate compound (PC-15) , 0.37 parts by mass of a hydroxyl group imparting additive (HEA) and 0.74 parts by mass of dehydrated acetone as a solvent were mixed and heated to prepare a photocurable urethane gel.
• the hardness of the photocurable urethane gel obtained by heat curing was E3.
• the curing depth after photocuring was 15 mm as in Example 1.
• a light irradiation device (model number: ALE/1.1, light wavelength: 435 nm) manufactured by KLV Co., Ltd., which has a larger light output than the light irradiation device used in Example 1, irradiation intensity: 455 mW / cm 2.
• Photocuring of the photocurable urethane gel was performed under the conditions of irradiation time: 60 seconds and integrated light quantity: 27J/cm 2 .
• the hardness of the cured body after photocuring was E76. Both hardness and hardening depth were acceptable levels.
• Example 10 The photocurable composition:thermosetting composition was adjusted to a mass ratio of 50:50.
• Polyfunctional urethane (meth)acrylate was changed from EBECRYL9260 to KRM8904.
• a photocurable urethane gel was prepared under the same conditions as in Example 9 except for the above changes.
• the hardness of the photocurable urethane gel obtained by heat curing was E3.
• the curing depth after photocuring was 15 mm as in Example 1.
• irradiation intensity 455 mW/cm 2
• irradiation time 70 seconds
• integrated light amount 32 J/cm.
• Photocuring of the photocurable urethane gel was performed under the conditions of No.2 .
• the hardness of the cured body after photocuring was E84. Both hardness and hardening depth were acceptable levels.
• Example 11 The photocurable composition:thermosetting composition was adjusted to a mass ratio of 50:50.
• a photocurable urethane gel was prepared under the same conditions as in Example 9.
• the hardness of the photocurable urethane gel obtained by heat curing was E3.
• the curing depth after photocuring was 15 mm as in Example 1.
• using a light irradiation device manufactured by Iris Ohyama Co., Ltd. model number: LWK-1300Z, visible light LED light used, illuminance: 1300 lm, irradiation time: 240 seconds, see Table 1 for details
• the above photocurable urethane Photocuring of the gel was performed.
• the hardness of the cured body after photocuring was E73. Both hardness and hardening depth were acceptable levels.
• Example 12 The photocurable composition:thermosetting composition was adjusted to a mass ratio of 50:50.
• a photocurable urethane gel was prepared under the same conditions as in Example 10.
• the hardness of the photocurable urethane gel obtained by heat curing was E3.
• the curing depth after photocuring was 15 mm as in Example 1.
• the photocurable urethane gel was photocured.
• the hardness of the cured body after photocuring was E89. Both hardness and hardening depth were acceptable levels.
• the photocurable composition:thermosetting composition was 40:60 in mass ratio.
• the amounts of polyfunctional urethane (meth)acrylate (EBECRYL9260), photopolymerization initiator (TPO), mixture of polyol compound and isocyanate compound (PC-15), and hydroxyl group imparting additive (HEA) are shown in Table 1. is.
• the hardness of the photocurable urethane gel obtained by heat curing was E2.
• the curing depth after photocuring was 15 mm as in Example 1. After that, using the apparatus used in Example 11, the photocurable urethane gel was photocured under the irradiation conditions shown in Table 1.
• the hardness of the cured product after photocuring was E67. Both hardness and hardening depth were acceptable levels.
• Example 14 The photocurable composition:thermosetting composition was adjusted to a mass ratio of 50:50.
• a photocurable urethane gel was prepared under the same conditions as in Example 9.
• the hardness of the photocurable urethane gel obtained by heat curing was E3.
• the curing depth after photocuring was 15 mm as in Example 1.
• the photocurable urethane gel was photocured.
• the hardness of the cured body after photocuring was E74. Both hardness and hardening depth were acceptable levels.
• Comparative Example Table 2 shows the production conditions and hardness evaluation results for each comparative example.
• the photocurable composition:thermosetting composition was 5:95 in mass ratio.
• the amounts of polyfunctional urethane (meth)acrylate (KRM8904), photoinitiator (Omnirad 819), mixture of polyol compound and isocyanate compound (PC-15), and hydroxyl group imparting additive (PETRA) are shown in Table 2. Street.
• the thermal curing conditions and the subsequent photocuring conditions were the same as in Example 1, respectively.
• the hardness of the photocurable urethane gel obtained by heat curing was E15.
• the curing depth after photocuring was 15 mm as in Example 1.
• the gel-like body satisfied the acceptance criteria. However, the hardness of the cured body after photocuring was E38, which did not reach the acceptable level.
• the photocurable composition:thermosetting composition was 10:90 in mass ratio.
• the amounts of polyfunctional urethane (meth)acrylate (KRM8904), photoinitiator (Omnirad 819), mixture of polyol compound and isocyanate compound (PC-15), and hydroxyl group imparting additive (PETRA) are shown in Table 2. Street.
• the thermal curing conditions and the subsequent photocuring conditions were the same as in Example 1, respectively.
• the hardness of the photocurable urethane gel obtained by heat curing was E12.
• the curing depth after photocuring was 15 mm as in Example 1.
• the gel-like body satisfied the acceptance criteria. However, the hardness of the cured body after photocuring was E50, which did not reach the acceptable level.
• the photocurable composition:thermosetting composition was 65:35 in mass ratio.
• the amounts of polyfunctional urethane (meth)acrylate (KRM8904), photoinitiator (Omnirad 819), mixture of polyol compound and isocyanate compound (PC-15), and hydroxyl group imparting additive (PETRA) are shown in Table 2. Street.
• the heat curing conditions were the same as in Example 1, but the composition did not cure even when heated (there was fluidity). Therefore, subsequent light irradiation was not performed.
• the photocurable composition:thermosetting composition was 70:30 in mass ratio.
• the amounts of polyfunctional urethane (meth)acrylate (KRM8904), photoinitiator (Omnirad 819), mixture of polyol compound and isocyanate compound (PC-15), and hydroxyl group imparting additive (PETRA) are shown in Table 2. Street.
• the heat curing conditions were the same as in Example 1, but the composition did not cure even when heated (there was fluidity). Therefore, subsequent light irradiation was not performed.
• Example 5 The photocurable composition:thermosetting composition was adjusted to a mass ratio of 50:50.
• Polyfunctional urethane (meth)acrylate was changed from KRM8904 to EBECRYL5129.
• the conditions were the same as in Example 1 except for the above changes.
• the heat curing conditions were the same as in Example 1, but the composition did not cure even when heated (there was fluidity). Therefore, subsequent light irradiation was not performed.
• Example 7 The photocurable composition:thermosetting composition was adjusted to a mass ratio of 50:50.
• Polyfunctional urethane (meth)acrylate was changed from KRM8904 to EBECRYL1290.
• the conditions were the same as in Example 1 except for the above changes.
• the heat curing conditions were the same as in Example 1, but the composition did not cure even when heated (there was fluidity). Therefore, subsequent light irradiation was not performed.
• the photocurable composition:thermosetting composition was 55:45 in mass ratio.
• the amounts of polyfunctional urethane (meth)acrylate (KRM8904), photoinitiator (Omnirad 819), mixture of polyol compound and isocyanate compound (PC-15), and hydroxyl group imparting additive (PETRA) are shown in Table 2. Street.
• the heat curing conditions were the same as in Example 1, but the composition did not cure even when heated (there was fluidity). Therefore, subsequent light irradiation was not performed.
• the photocurable composition:thermosetting composition was 60:40 in mass ratio.
• the amounts of polyfunctional urethane (meth)acrylate (KRM8904), photoinitiator (Omnirad 819), mixture of polyol compound and isocyanate compound (PC-15), and hydroxyl group imparting additive (PETRA) are shown in Table 2. Street.
• the heat curing conditions were the same as in Example 1, but the composition did not cure even when heated (there was fluidity). Therefore, subsequent light irradiation was not performed.
• the photocurable composition:thermosetting composition was 20:80 in mass ratio. 19.60 parts by mass of polyfunctional urethane (meth)acrylate (EBECRYL9260), 0.40 parts by mass of photoinitiator (TPO), 79.41 parts by mass of "mixture of polyol compound and isocyanate compound (PC-15) , 0.59 parts by mass of a hydroxyl group-imparting additive (HEA) and 0.74 parts by mass of dehydrated acetone as a solvent were mixed and heated in the same manner as in Example 1 to prepare a photocurable urethane gel. did.
• the hardness of the photocurable urethane gel obtained by heat curing was E4.
• the curing depth after photocuring was 15 mm as in Example 1.
• the gel-like body satisfied the acceptance criteria.
• the photocurable urethane gel was photocured.
• the hardness of the cured body after photocuring was E51, which did not reach the acceptable level.
• thermosetting composition was 70:30 in mass ratio.
• the types of raw materials were the same as in Comparative Example 10, and the amount of each raw material was changed as shown in Table 2. After that, even if it was heated under the same conditions as in Example 1, it did not cure (has fluidity). Therefore, subsequent light irradiation was not performed.
• the photocurable composition:thermosetting composition was 60:40 in mass ratio.
• the types of raw materials were the same as in Comparative Example 10, and the amount of each raw material was changed as shown in Table 2. After that, it was heated under the same conditions as in Example 1, but the hardness was too soft to reach E1. For this reason, the hardness of the gelled body did not reach an acceptable level. After that, as a result of light irradiation under the same conditions as in Comparative Example 10, the hardness of the cured product was E83.
• the present invention can be used, for example, as a repair member for pipes and building materials in addition to pipe joints.

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