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WO2019189664A1 - Procédé de fabrication d'objet durci de type durcissable par chauffage, et composition durcissable de type durcissable par chauffage - Google Patents

Procédé de fabrication d'objet durci de type durcissable par chauffage, et composition durcissable de type durcissable par chauffage Download PDF

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WO2019189664A1
WO2019189664A1 PCT/JP2019/013797 JP2019013797W WO2019189664A1 WO 2019189664 A1 WO2019189664 A1 WO 2019189664A1 JP 2019013797 W JP2019013797 W JP 2019013797W WO 2019189664 A1 WO2019189664 A1 WO 2019189664A1
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Prior art keywords
polymer
group
curable composition
hydrolyzable silyl
weight
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English (en)
Japanese (ja)
Inventor
達郎 春増
彰 小川
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Kaneka Corp
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Kaneka Corp
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Priority to JP2020511036A priority Critical patent/JPWO2019189664A1/ja
Priority to CN201980021398.8A priority patent/CN111902485A/zh
Publication of WO2019189664A1 publication Critical patent/WO2019189664A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to a method for producing a cured product obtained by heat-curing a curable composition containing a hydrolyzable silyl group-containing polymer at 120 ° C. or higher, and the heat-curable curable composition.
  • a polymer having a hydrolyzable silyl group is known as a moisture-reactive polymer.
  • Polymers having hydrolyzable silyl groups are included in many industrial products such as adhesives, sealing materials, coating materials, paints and pressure-sensitive adhesives, and are used in a wide range of fields (uses).
  • Patent Document 1 a polymer having a hydrolyzable silyl group as a heat-curing type, and a monoalkyltin compound carboxylate is used as a catalyst.
  • JP 2001-031870 A WO2017 / 188185 JP 2011-153309 A JP 2014-084881 A WO2016 / 027475 JP 2017-1112030 A JP 59-071364 A
  • One embodiment of the present invention is a method for producing a cured product obtained by heat-curing a thermosetting curable composition containing a polymer having a hydrolyzable silyl group, and the thermosetting curable composition.
  • An object of the present invention is to obtain a cured product that does not swell regardless of the type of hydrolyzable silyl group and has a fast curing start-up upon heating.
  • a hydrolyzable silyl group whose main chain is at least one selected from the group consisting of a polyoxyalkylene polymer, a (meth) acrylic polymer, and a hydrocarbon polymer.
  • a curable composition obtained by heating a thermosetting curable composition containing 100 parts by weight of the polymer (A) having the above and 0.1 to 10 parts by weight of the alkyltin oxide compound (B) at 120 ° C. or higher.
  • the present invention relates to a method for producing a cured product, which has a curing step of curing the material.
  • a hydrolyzable silyl group whose main chain is at least one selected from the group consisting of a polyoxyalkylene polymer, a (meth) acrylic polymer, and a hydrocarbon polymer.
  • the present invention relates to a heat-curable curable composition containing 100 parts by weight of a polymer (A) having an alkyl group and 0.1 to 10 parts by weight of an alkyltin oxide compound (B).
  • One embodiment of the present invention is a method for producing a cured product obtained by heat-curing a thermosetting curable composition containing a polymer having a hydrolyzable silyl group, and the thermosetting curable composition.
  • the composition does not swell at the time of curing, does not cure at room temperature, and is heated. Then, the inventor has found that it hardens immediately.
  • the technique described in Patent Document 2 has limited hydrolyzable silyl groups, and there is room for improvement in terms of adjusting the curing balance.
  • one embodiment of the present invention does not cause swelling regardless of the type of hydrolyzable silyl group, and can provide a cured product having a rapid rise in curing upon heating, and a method for producing a cured product and curability It is an object to provide a composition.
  • the curing condition is moisture curing at room temperature. That is, the curable compositions described in Patent Documents 3 to 5 are not heat curable.
  • Patent Document 6 relates to a conductive paste having a coating thickness of 100 microns.
  • Patent Document 7 relates to addition to heat kneading using polyethylene having a hydrolyzable silyl group.
  • silane condensation curing
  • swelling does not occur. That is, in the techniques of Patent Documents 6 and 7, there is no problem of swelling.
  • the main chain has a hydrolyzable silyl group that is at least one selected from the group consisting of a polyoxyalkylene polymer, a (meth) acrylic polymer, and a hydrocarbon polymer.
  • a curable composition containing 100 parts by weight of the polymer (A) and 0.1 to 10 parts by weight of the alkyltin oxide compound (B) is heated at 120 ° C. or higher to obtain a curable composition.
  • the present invention relates to a method for producing a cured product having a curing step of curing.
  • a hydrolyzable silyl group whose main chain is at least one selected from the group consisting of a polyoxyalkylene polymer, a (meth) acrylic polymer, and a hydrocarbon polymer.
  • the present invention relates to a heat-curable curable composition containing 100 parts by weight of a polymer (A) having an alkyl group and 0.1 to 10 parts by weight of an alkyltin oxide compound (B).
  • the swelling does not occur regardless of the type of hydrolyzable silyl group. Further, it is possible to provide a cured product having a rapid rise in curing upon heating.
  • curable composition by heating intends to cure the curable composition by heating.
  • Each R 1 independently represents a hydrocarbon group having 1 to 10 carbon atoms which may have a heteroatom-containing group, or a carbon atom having 1 to 10 carbon atoms which may have a substituent consisting of a halogen atom. Represents a hydrogen group.
  • R 1 examples include an alkyl group such as a methyl group or an ethyl group; a cycloalkyl group; an aryl group; an aralkyl group; a halogenated methyl group such as a chloromethyl group; an alkoxymethyl group such as a methoxymethyl group; .
  • R 1 is preferably a methyl group, an ethyl group, a chloromethyl group or a methoxymethyl group, more preferably a methyl group or a methoxymethyl group.
  • Examples of X include a hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group and the like.
  • X since hydrolyzability is moderate and it is easy to handle, as X, an alkoxy group is more preferable, and a methoxy group and an ethoxy group are particularly preferable.
  • A is 1, 2 or 3. a is preferably 2 or 3.
  • hydrolyzable silyl group examples include trimethoxysilyl group, triethoxysilyl group, tris (2-propenyloxy) silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, (chloromethyl) dimethoxysilyl group, ( Methoxymethyl) dimethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group, and the like.
  • a trimethoxysilyl group, a triethoxysilyl group, a (methoxymethyl) dimethoxysilyl group and a dimethoxymethylsilyl group are preferable.
  • Polymer (A) having hydrolyzable silyl group The number of hydrolyzable silyl groups contained in one molecule is preferably 0.5 or more on average, and 1.0 or more. Is more preferable, and 1.2 or more is more preferable. Polymer (A) having hydrolyzable silyl group The upper limit of the number of hydrolyzable silyl groups contained in one molecule is preferably 4.0 or less, and preferably 3.0 or less. More preferred.
  • the main chain skeleton of the polymer (A) having a hydrolyzable silyl group is at least one selected from polyoxyalkylene polymers, (meth) acrylic polymers, and hydrocarbon polymers.
  • the “main chain skeleton” can be said to be a “main chain”.
  • the terms “backbone backbone” and the term “backbone” are interchangeable.
  • the main chain skeleton of the polymer (A) having a hydrolyzable silyl group is (a) polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene.
  • Polyoxyalkylene polymers such as copolymers; (b) (meth) acrylic polymers obtained by radical polymerization of monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate And (c) ethylene-propylene copolymer, polyisobutylene, copolymers of isobutylene and isoprene, polybutadiene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers. It is at least one selected from hydrocarbon-based polymers such as coalescence.
  • the main chain of the polymer (A) having a hydrolyzable silyl group is preferably a polyoxyalkylene polymer.
  • the curable composition When the main chain of the polymer (A) having a hydrolyzable silyl group is a polyoxyalkylene polymer, the curable composition has a relatively low viscosity at room temperature and is easy to handle, and is also obtained after the reaction. Objects also have the advantage of exhibiting good elasticity.
  • the polymer (A) having a hydrolyzable silyl group may be a mixture of polymers having different main chain skeletons.
  • the main chain structure of the polymer (A) having a hydrolyzable silyl group may be linear or branched.
  • the main chain structure intends a main chain skeleton structure.
  • the number average molecular weight of the polymer (A) having a hydrolyzable silyl group is 3,000 to 100,000, more preferably 3,000 to 50, in terms of polystyrene in terms of gel permeation chromatography (GPC). 000, particularly preferably 3,000 to 30,000. If the number average molecular weight is less than (a) 3,000, the amount of reactive silicon groups introduced is increased, which may be inconvenient in terms of production cost. Therefore, it tends to be inconvenient in terms of workability.
  • the molecular weight of the polymer (A) having a hydrolyzable silyl group can also be represented by a terminal group equivalent molecular weight.
  • the molecular weight in terms of end groups was based on the principle of the method for measuring the hydroxyl value of JIS K 1557 and the method for measuring the elementary value as defined in JIS K 0070 for the organic polymer precursor before introduction of the reactive silicon group. By performing titration analysis, the end group concentration of the organic polymer precursor is directly measured, and the end group concentration obtained and the structure of the organic polymer (the degree of branching determined by the polymerization initiator used) are taken into account. Can be sought.
  • the molecular weight distribution (Mw / Mn) of the polymer (A) having a hydrolyzable silyl group is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, and 1.5 or less. Is more preferable, 1.4 or less is particularly preferable, and 1.3 or less is most preferable.
  • the molecular weight distribution of the polymer (A) having a hydrolyzable silyl group can be determined from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.
  • ⁇ Polyoxyalkylene polymer having hydrolyzable silyl group> When a polyoxyalkylene polymer is used as the main chain of the polymer (A) having a hydrolyzable silyl group, the main chain of the polymer (A) having a hydrolyzable silyl group is represented by —R 2 —O. - (wherein, R 2 is a is straight-chain or branched alkylene group having 1 to 14 carbon atoms) having a repeating unit represented by, R 2 is a linear or branched alkylene group having 2 to 4 carbon atoms Is more preferable.
  • the polymer (A) having the hydrolyzable silyl group is a polymer having a hydrolyzable silyl group. It can be said that it is an oxyalkylene polymer.
  • Examples of a method for synthesizing a polyoxyalkylene polymer having a hydrolyzable silyl group include the following (i) to (iii): (I) A hydroxyl group-terminated polyoxyalkylene polymer is obtained by using a double metal cyanide complex catalyst and polymerizing an epoxy compound with an initiator having a hydroxyl group. Thereafter, the hydroxyl group of the obtained hydroxyl-terminated polyoxyalkylene polymer is converted to a carbon-carbon unsaturated group.
  • a method of adding a silane compound to the obtained polymer by a hydrosilylation reaction (Ii) a method of reacting a hydroxyl group-terminated polyoxyalkylene polymer with a compound having both a group capable of reacting with a hydroxyl group and a hydrolyzable silyl group; (Iii) A hydroxyl group-terminated polyoxyalkylene polymer and an excess polyisocyanate compound are reacted to form a polymer having an isocyanate group at the terminal. Thereafter, a method of reacting a compound having both a group that reacts with an isocyanate group and a hydrolyzable silyl group with a polymer having an isocyanate group at the terminal.
  • (meth) acrylic polymer having hydrolyzable silyl group When a (meth) acrylic polymer is used as the main chain of the polymer (A) having a hydrolyzable silyl group, the monomer is not particularly limited, and various (meth) acrylic acid ester monomers may be used. it can. Specific examples of (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, n-octyl (meth) acrylate, and (meth) acrylic.
  • 2-ethylhexyl acid nonyl (meth) acrylate, decyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic
  • examples include glycidyl acid, ethylene oxide adduct of (meth) acrylic acid, and the like.
  • acrylic acid polymer a polymer obtained by copolymerizing a (meth) acrylic acid ester monomer and a vinyl monomer copolymerizable therewith can also be used.
  • the polymer (A) having the hydrolyzable silyl group has a hydrolyzable silyl group. It can be said that it is an acrylic polymer.
  • a compound having a polymerizable unsaturated group and a reactive functional group is copolymerized with a monomer having a (meth) acrylic structure. Thereafter, the obtained polymer is reacted with a compound having a hydrolyzable silyl group and a functional group that reacts with a reactive functional group (for example, an isocyanate silane compound).
  • ⁇ Hydrocarbon polymer having hydrolyzable silyl group When a hydrocarbon polymer is used as the main chain of the polymer (A) having a hydrolyzable silyl group, a saturated hydrocarbon polymer that substantially does not contain a carbon-carbon unsaturated bond other than an aromatic ring is preferable. .
  • a method for synthesizing a saturated hydrocarbon polymer includes (1) a method of polymerizing an olefin compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene as a main monomer, (2) butadiene, It can be obtained by homopolymerizing a diene compound such as isoprene or by copolymerizing the diene compound and the olefin compound and then hydrogenating. Among these, isobutylene polymers and hydrogenated polybutadiene polymers are preferable, and isobutylene polymers are more preferable.
  • the curable composition which concerns on one Embodiment of this invention contains the alkyl tin oxide compound (B).
  • alkyl tin oxide compound (B) may be referred to as “alkyl tin oxide (B)” or “(B) component”.
  • alkyl tin oxide compound (B) examples include dialkyl tin oxide and / or monoalkyl tin oxide from the viewpoint of catalytic activity.
  • the alkyltin oxide compound (B) is more preferably dibutyltin oxide, dioctyltin oxide and / or monobutyltin oxide from the viewpoint of catalytic activity.
  • the monoalkyltin oxide is more preferably monobutyltin oxide. It can be said that the dialkyltin oxide is more preferably dibutyltin oxide.
  • Alkyl tin oxide (B) may be used alone or in combination of two or more.
  • the amount of the alkyl tin oxide (B) used is 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A) having a hydrolyzable silyl group. More preferred is 10 parts by weight.
  • the curable composition preferably contains 0.5 to 10 parts by weight of the alkyltin oxide compound (B), and more preferably 3 to 10 parts by weight. According to the said structure, it has the advantage that sclerosis
  • the curable composition according to one embodiment of the present invention includes a filler, an adhesion-imparting agent, a plasticizer.
  • An agent, an antioxidant, a light stabilizer, an ultraviolet absorber, and the like may be added.
  • additives include, for example, silanol condensation catalysts other than the component (B), solvents, diluents, sagging inhibitors, physical property modifiers, tackifier resins, photocurable substances, oxygen curable substances, surfaces Property improvers, epoxy resins, other resins, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, fungicides, etc. Is mentioned.
  • silanol condensation catalysts other than the component (B) solvents, diluents, sagging inhibitors, physical property modifiers, tackifier resins, photocurable substances, oxygen curable substances, surfaces Property improvers, epoxy resins, other resins, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, fungicides, etc. Is mentioned.
  • Fillers include heavy calcium carbonate, colloidal calcium carbonate, precipitated calcium carbonate, calcium oxide, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous
  • Examples thereof include silicic acid, hydrous silicic acid, carbon black, ferric oxide, aluminum fine powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber, filament, organic balloon, and inorganic balloon.
  • calcium oxide can further suppress foaming during heat curing without delaying curing, it is preferable to add to the curable composition.
  • the amount of filler used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, per 100 parts by weight of the polymer (A) having a hydrolyzable silyl group.
  • Adhesive agent An adhesiveness imparting agent can be added to the curable composition.
  • a silane coupling agent and / or a reaction product of the silane coupling agent can be added.
  • silane coupling agent examples include: (a) ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl Amino group-containing silanes such as ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, and (2-aminoethyl) aminomethyltrimethoxysilane; (b) ⁇ -isocyanatopropyltrimethoxysilane Isocyanate group-containing silanes such as ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatomethyltrimethoxysilane, ⁇ -iso
  • the above-mentioned adhesion imparting agent may be used alone or in combination of two or more.
  • the reaction material of various silane coupling agents can also be used.
  • the amount of the silane coupling agent used is preferably from 0.1 to 20 parts by weight, particularly preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A) having a hydrolyzable silyl group.
  • a plasticizer can be added to the curable composition.
  • the plasticizer include (a) phthalic acid ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; ) Terephthalic acid ester compounds such as bis (2-ethylhexyl) -1,4-benzenedicarboxylate; (c) non-phthalic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; (d) dioctyl adipate; Aliphatic polycarboxylic acid ester compounds such as dioctyl sebacate, dibutyl sebacate, diisodecyl succinate and tributyl acetylcitrate;
  • epoxy plasticizers are preferable in terms of paint adhesion.
  • the amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight with respect to 100 parts by weight of the polymer (A) having a hydrolyzable silyl group. preferable. If the amount of the plasticizer used is less than (a) 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds (b) 150 parts by weight, the mechanical strength of the cured product will be insufficient.
  • a plasticizer may be used individually by 1 type and may use 2 or more types together.
  • An antioxidant can be used for the curable composition. If an antioxidant is used, the weather resistance of the cured product can be increased. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.
  • the amount of the antioxidant used is preferably 0.1 to 15 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polymer (A) having a hydrolyzable silyl group.
  • a light stabilizer can be used for the curable composition. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred.
  • the amount of the light stabilizer used is preferably from 0.1 to 10 parts by weight, particularly preferably from 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a hydrolyzable silyl group.
  • An ultraviolet absorber can be used for the curable composition. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced.
  • ultraviolet absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds.
  • a benzotriazole compound is particularly preferable.
  • the benzotriazole compounds include commercially available names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329 and Tinuvin 571 (above, manufactured by BASF).
  • the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polymer (A) having a hydrolyzable silyl group.
  • the curable composition is a curable composition that is cured by heating, and is preferably prepared as a one-component component obtained by mixing all the blending components.
  • the curable composition uses a catalyst that does not cure immediately at room temperature even with moisture, and does not need to be completely sealed. In the case of long-term storage, the curable composition is preferably stored in a closed container such as a cartridge.
  • the alkyl tin oxide compound (B) In the preparation of the curable composition, when the alkyl tin oxide compound (B) is added as a solid, the alkyl tin oxide compound (B) preferably has a smaller particle size. If the particle size of the alkyltin oxide compound (B) is too large, the resulting curable composition will be insufficiently cured, and the surface of the resulting cured product will have an irregularity due to the alkyltin oxide compound (B) ( Convex part) may appear.
  • the particle diameter of the alkyltin oxide compound (B) is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, further preferably 20 ⁇ m or less, and particularly preferably 10 ⁇ m or less as the average particle diameter.
  • the curable composition containing the polymer (A) having a hydrolyzable silyl group is cured by being heated at 120 ° C. or higher after being applied.
  • the heating temperature is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, and still more preferably 180 ° C. or higher.
  • the heating temperature is 160 ° C. or higher, a cured product that is sufficiently cured in a shorter time can be obtained. If the heating temperature is less than 120 ° C., curing may be slow.
  • the upper limit of the temperature when heating is preferably 250 ° C. or less. When the heating temperature is higher than 250 ° C., the cured product may be thermally deteriorated.
  • the heat-curable curable composition is preferably heat-cured at 140 ° C. or higher, more preferably heat-cured at 160 ° C. or higher, and further preferably heat-cured at 180 ° C. or higher. According to the said structure, the hardened
  • the heating time is not particularly limited, but is preferably from 1 minute to 5 hours, more preferably from 2 minutes to 3 hours, and even more preferably from 5 minutes to 2 hours.
  • heating method conventionally known means such as hot air drying and infrared heating can be used.
  • a curable composition according to an embodiment of the present invention includes a sealing material, an adhesive, a waterproof material, a waterproof coating material, a mold preparation, a vibration proof material, a vibration damping material, a soundproof material, a foam material, a paint, and a spray material. Can be used for etc.
  • the use part of the curable composition according to one embodiment of the present invention includes car bodies / parts of automobiles, car bodies / parts of large vehicles such as trucks and buses, train vehicles / parts, parts for aircraft, and parts for ships.
  • Examples include parts, containers, electrical / electronic parts, home appliances, various machine parts, and building materials such as sashes.
  • the present invention relates to a method for producing a cured product obtained by heat-curing a heat-curable curable composition containing 100 parts by weight and an alkyltin oxide compound (B) 0.1 to 10 parts by weight at 120 ° C. or higher.
  • the present invention relates to a thermosetting curable composition containing 100 parts by weight and 0.1 to 10 parts by weight of an alkyltin oxide compound (B).
  • thermosetting curable composition according to any one of [9] to [12], wherein the main chain of the polymer (A) having a hydrolyzable silyl group is a polyoxyalkylene polymer. About.
  • an embodiment of the present invention may have the following configuration.
  • a curing step of curing the curable composition by heating a thermosetting curable composition containing 100 parts by weight and 0.1 to 10 parts by weight of the alkyltin oxide compound (B) at 120 ° C. or higher.
  • a method for producing a cured product A method for producing a cured product.
  • thermosetting curing according to any one of [X9] to [X12], wherein the main chain of the polymer (A) having a hydrolyzable silyl group is a polyoxyalkylene polymer. Sex composition.
  • the number average molecular weight and molecular weight distribution in the examples are GPC molecular weight and molecular weight distribution measured under the following conditions.
  • Liquid feeding system HLC-8220GPC manufactured by Tosoh Corporation Column: Tosoh TSK-GEL H type Solvent: THF Molecular weight: Polystyrene conversion Measurement temperature: 40 ° C
  • the molecular weight in terms of end groups in the examples is determined by measuring the hydroxyl value by the measuring method of JIS K 1557 and the iodine value by the measuring method of JIS K 0070, and calculating the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). This is the molecular weight determined in consideration.
  • polyoxypropylene (Q-1) having an allyl group at the terminal was obtained.
  • Q-1 50 ⁇ l of platinum divinyldisiloxane complex solution (3% by weight isopropanol solution in terms of platinum) was added to the reaction solution containing polyoxypropylene (Q-1). While stirring the obtained reaction solution, 14.6 g of triethoxysilane was slowly dropped into the reaction solution.
  • polyoxypropylene (A-1) having a number average molecular weight of about 16400 having a triethoxysilyl group at the terminal. .
  • the polymer (A-1) was found to have an average of 0.7 triethoxysilyl groups at one end and an average of 2.2 per molecule.
  • polyoxypropylene (A-1), polyoxypropylene (A-2) and polyoxypropylene (A-3) obtained in Synthesis Examples 1 to 3 are hydrolyzable silyl groups according to an embodiment of the present invention. It is a polymer (A) which has this. Polyoxypropylene (A-1), polyoxypropylene (A-2) and polyoxypropylene (A-3) are listed in the polymer column in Table 1.
  • Examples 1 to 14, Comparative Examples 1 to 3 100 parts by weight of the polymer shown in Table 1 or 2 and 100 parts by weight of the polymer, 40 parts by weight of PPG 3000 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name: Actol P-23), Saisizer E-PS (New Nippon Rika Co., Ltd .: 4,2-epoxyhexahydrophthalate di-2-ethylhexyl) 10 parts by weight, Neolite SP (Takehara Chemical Industries, Ltd .: precipitated calcium carbonate) 160 parts by weight, LM2200 (Maruo Calcium) Co., Ltd .: Heavy calcium carbonate 54 parts by weight, Hi-Black 10 (Orion Engineered Carbons Co., Ltd., carbon black) 0.2 parts by weight, and the catalyst described in Table 1 or Table 2
  • the mixture was uniformly mixed using a rotation and revolution mixer to obtain a curable composition.
  • the obtained curable composition was sealed in a cartridge.
  • the following evaluation was performed using the obtained
  • PPG 3000 and Saisizer E-PS are plasticizers.
  • Neolite SP, LM2200, and Hi-Black 10 are fillers.
  • dibutyltin oxide, monobutyltin oxide and dioctyltin oxide are alkyltin oxide compounds (B) according to an embodiment of the present invention.
  • SCAT-24 is not an alkyl tin oxide compound (B) according to one embodiment of the present invention.
  • the curable composition is packed from the cartridge into an ointment can (depth 4.5 mm, diameter 46 mm), cured in a dryer adjusted to the temperature shown in Table 1 or Table 2, and the cured state is measured by a hardness meter (Asker A type) Confirmed by The results are shown in the hardness column of Table 1 or Table 2.
  • Curing the curable composition in a dryer adjusted to the temperature shown in Table 1 or Table 2 can be said to be a step of heat-curing the curable composition.
  • Examples 1 to 3 in which dibutyltin oxide was used as a catalyst for the polymer (A-1) having a triethoxysilyl group, the catalyst amount was 120 ° C. and 40 minutes at 4 parts by weight and 120 ° C. at 2 parts by weight. It is completely cured at 120 ° C. and 180 ° C. and 20 min, and 1 part by weight at 180 ° C. and 20 min. Therefore, it can be seen that Examples 1 to 3 are faster in curing than Comparative Example 1. Similarly, when the polymer (A-2) having a dimethoxymethylsilyl group was used, Example 4 using dibutyltin oxide was completely cured at 120 ° C.
  • Example 5 using dibutyltin oxide was completely completed at 120 ° C. and 20 min as compared with Comparative Example 3 using SCAT-24. It is cured. Therefore, in Examples 4 and 5, it can be seen that the rise of curing is faster. Even when monobutyltin oxide or dioctyltin oxide is used, a cured product that is completely cured at 180 ° C. and 60 minutes and does not swell is obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention a pour objet de fournir un objet durci peu susceptible de produire des cloques indépendamment de la sorte d'un groupe silyle hydrolisable, et présentant un début de durcissement rapide lors de son chauffage. Ce but est atteint à l'aide d'un procédé de fabrication de l'objet durci obtenu par chauffage et durcissement d'une composition durcissable qui comprend un polymère (A) possédant au moins une sorte de groupe silyle hydrolisable choisi parmi un polymère (méth)acrylique et un polymère à base d'hydrocarbure, et un composé alkyle étain (B).
PCT/JP2019/013797 2018-03-28 2019-03-28 Procédé de fabrication d'objet durci de type durcissable par chauffage, et composition durcissable de type durcissable par chauffage Ceased WO2019189664A1 (fr)

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CN201980021398.8A CN111902485A (zh) 2018-03-28 2019-03-28 加热固化型的固化物的制造方法和加热固化型的固化性组合物

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