WO2017110925A1 - 複合体の製造方法および複合体 - Google Patents
複合体の製造方法および複合体 Download PDFInfo
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- WO2017110925A1 WO2017110925A1 PCT/JP2016/088212 JP2016088212W WO2017110925A1 WO 2017110925 A1 WO2017110925 A1 WO 2017110925A1 JP 2016088212 W JP2016088212 W JP 2016088212W WO 2017110925 A1 WO2017110925 A1 WO 2017110925A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Definitions
- the present invention relates to a method for producing a composite comprising a substrate, a cured product of a curable composition containing a polymer having a hydrolyzable silyl group, and a coating film of a thermosetting paint, and the production method. To a complex that can be made.
- Polymers with hydrolyzable silyl groups are known as moisture-reactive polymers and are used in a wide range of fields, including in many industrial products such as adhesives, sealants, coatings, paints, and adhesives. ing.
- a methyldimethoxysilyl group or a trimethoxysilyl group has been mainly used.
- An organic polymer having a methyldimethoxysilyl group is stable in the long term without reacting with silyl groups even in the presence of moisture in the absence of a curing catalyst, and the curing reaction proceeds from that point when the curing catalyst is mixed. This is to show a desirable behavior.
- trimethoxysilyl group is a functional group having a higher activity than the methyldimethoxysilyl group, it is suitable for applications that require rapid curing.
- the present invention is a method for producing a composite comprising applying a curable composition containing a polymer having a hydrolyzable silyl group to a substrate, and then applying a thermosetting paint onto the curable composition. Then, it aims at providing the manufacturing method of a composite_body
- the present invention (1).
- a method for producing a composite of a substrate, a cured product of a curable composition, and a coating film of a heat-curable coating After applying the curable composition to the substrate, applying a heat curable coating, and then heating.
- the curable composition includes a polyoxyalkylene polymer (A) having a hydrolyzable silyl group,
- the hydrolyzable silyl group has the following general formula (1): -SiR a (OR 1 ) 3-a (1) (R each independently represents a heteroatom-containing group or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent consisting of a halogen atom, and R 1 each independently represents a hydrocarbon having 2 to 10 carbon atoms.
- A represents 0, 1, 2) Represented by the manufacturing method, (2).
- (1) The method for producing a composite according to any one of (1) to (3), wherein heating is performed after the curable composition is applied to the substrate and before the curable composition is cured.
- (5) The method for producing a complex according to any one of (1) to (4), wherein R 1 is an ethyl group, (6).
- the curable composition further contains a silane coupling agent whose hydrolyzable group is a methoxy group, and the content of the silane coupling agent is a polyoxyalkylene polymer (A) having a hydrolyzable silyl group 100 weight
- a silane coupling agent whose hydrolyzable group is a methoxy group
- the content of the silane coupling agent is a polyoxyalkylene polymer (A) having a hydrolyzable silyl group 100 weight
- the hydrolyzable silyl group of the compound having a hydrolyzable silyl group contained in the curable composition is only the hydrolyzable silyl group represented by the general formula (1).
- the curable composition includes a polyoxyalkylene polymer (A) having a hydrolyzable silyl group,
- the hydrolyzable silyl group has the following general formula (1): -SiR a (OR 1 ) 3-a (1) (R each independently represents a heteroatom-containing group or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent consisting of a halogen atom, and R 1 each independently represents a hydrocarbon having 2 to 10 carbon atoms.
- A represents 0, 1, 2)
- a complex represented by About
- a composite comprising: applying a curable composition containing a polymer having a hydrolyzable silyl group to a substrate, and then applying a thermosetting paint on the curable composition. It is a method, Comprising: Even if it passes through heating, the manufacturing method of the composite_body
- the present invention relates to a method for producing a composite of a base material, a cured product of a curable composition, and a coating film of a thermosetting paint.
- the manufacturing method includes applying a curable composition to a substrate, applying a thermosetting paint, and then heating the curable composition used for manufacturing the composite is a hydrolyzable silyl group.
- the polyoxyalkylene polymer (A) having The hydrolyzable silyl group has the following general formula (1): -SiR a (OR 1 ) 3-a (1) (R each independently represents a heteroatom-containing group or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent consisting of a halogen atom, and R 1 each independently represents a hydrocarbon having 2 to 10 carbon atoms. A represents 0, 1, 2) It is represented by
- the curable composition used for the production of the composite has the following general formula (1): -SiR a (OR 1 ) 3-a (1) (R each independently represents a heteroatom-containing group or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent consisting of a halogen atom. R 1 each independently represents a hydrocarbon having 2 to 10 carbon atoms.
- A represents 0, 1, 2
- the polyoxyalkylene polymer (A) having a hydrolyzable silyl group is also referred to as component (A).
- the polyoxyalkylene polymer (A) has the following general formula (1): -SiR a (OR 1 ) 3-a (1) (R each independently represents a heteroatom-containing group or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent consisting of a halogen atom. R 1 each independently represents a hydrocarbon having 2 to 10 carbon atoms. A represents 0, 1, 2) It has a hydrolyzable silyl group represented by.
- R is each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom-containing group or a substituent composed of a halogen atom.
- R include alkyl groups such as methyl and ethyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; aralkyl groups such as benzyl groups; methyl halides such as chloromethyl groups; A group; an alkoxymethyl group such as a methoxymethyl group; and the like.
- R is preferably a methyl group, an ethyl group, a chloromethyl group or a methoxymethyl group, more preferably a methyl group, a chloromethyl group or a methoxymethyl group, still more preferably a methyl group.
- R 1 is a hydrocarbon group having 2 to 10 carbon atoms.
- R 1 include alkyl groups such as ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group; cycloalkyl groups such as cyclohexyl group, and the like. be able to.
- R 1 is preferably an ethyl group, a propyl group, or a butyl group, and more preferably an ethyl group.
- A is 0, 1, or 2, but is preferably 0 or 1 and more preferably 0 in terms of high curing activity.
- hydrolyzable silyl groups include triethoxysilyl group, diethoxymethylsilyl group, tripropoxysilyl group, dipropoxymethylsilyl group, (chloromethyl) diethoxysilyl group, (chloromethyl) dipropoxysilyl group. , (Methoxymethyl) diethoxysilyl group, (methoxymethyl) dipropoxysilyl group, (N, N-diethylaminomethyl) diethoxysilyl group, (N, N-diethylaminomethyl) dipropoxysilyl group, and the like. However, it is not limited to these.
- methyldiethoxysilyl group, triethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) diethoxysilyl group have higher activity. It is preferable because a cured product having good mechanical properties can be obtained while suppressing the occurrence of swelling. From the viewpoints of stability and safety, a methyldiethoxysilyl group and a triethoxysilyl group are more preferable, and a triethoxysilyl group is more preferable.
- the number of hydrolyzable silyl groups contained in one molecule of the polyoxyalkylene polymer (A) having hydrolyzable silyl groups is preferably 0.5 or more on average, 1.2 More preferably, it is more preferably 1.5 or more, and most preferably 1.8 or more.
- the upper limit is preferably 4 or less, and more preferably 3 or less.
- the number of silyl groups is preferably 1.8 to 3.0.
- the main chain structure of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group may be linear or branched.
- the branched structure is preferable because foaming can be suppressed.
- the main chain of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group is —R 2 —O— (wherein R 2 is a linear or branched alkylene group having 1 to 14 carbon atoms) R 2 is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.
- R 2 is a linear or branched alkylene group having 1 to 14 carbon atoms
- R 2 is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.
- Specific examples of the repeating unit represented by —R 2 —O— 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 ) (CH 3 ) O—, —CH 2 CH 2 CH 2 CH 2 O— and the like.
- the main chain structure of the polyoxyalkylene polymer may consist of only one type of repeating unit or may consist of two or more types of repeating units.
- those comprising a polyoxypropylene polymer having a repeating unit of oxypropylene of 50% by weight or more, preferably 80% by weight or more of the polymer main chain structure It is preferable from the point of being crystalline and having a relatively low viscosity.
- the polyoxyalkylene polymer (A) having a hydrolyzable silyl group may have any one main chain skeleton among the various main chain skeletons described above, and may have a heavy chain having a different main chain skeleton. It may be a mixture of coalescence. Moreover, about a mixture, what manufactured each polymer separately may be mixed, and you may manufacture simultaneously so that it may become arbitrary mixed compositions.
- the number average molecular weight determined by GPC measurement is used as the number average molecular weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group.
- the number average molecular weight of the polyoxyalkylene polymer (A) is preferably from 3,000 to 100,000, more preferably from 3,000 to 50,000, and more preferably from 3,000 to 30,000 as the polystyrene-equivalent molecular weight in GPC. Is particularly preferred. If the number average molecular weight is less than 3,000, the introduction amount of the reactive silicon group may be inconvenient in terms of production cost, and if it exceeds 100,000, the curable composition has a high viscosity. Therefore, the operation of applying the curable composition to the substrate may be difficult.
- the organic polymer precursor before introduction of the hydrolyzable silyl group is obtained by measuring the hydroxyl value of JIS K 1557 and JIS K 0070.
- the end group concentration is directly measured by titration analysis based on the principle of the iodine value measurement method specified in 1. and is determined in consideration of the structure of the organic polymer (the degree of branching determined by the polymerization initiator used).
- the molecular weight can also be expressed in terms of terminal group equivalent molecular weight.
- a calibration curve of the number average molecular weight determined by GPC measurement and the end group equivalent molecular weight of the organic polymer precursor is prepared, It is also possible to calculate the terminal group equivalent molecular weight of the polymer precursor by converting it to the number average molecular weight of GPC of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group.
- the molecular weight distribution (Mw / Mn) of the polyoxyalkylene 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, 1.5 or less is more preferable, 1.4 or less is particularly preferable, and 1.2 or less is most preferable.
- the molecular weight distribution of the polyoxyalkylene 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.
- a method of reacting a compound having both a group that reacts with an isocyanate group and a hydrolyzable silyl group after the polymer has been preferred is preferable.
- the method (i) is more preferable because the reaction is simple, the adjustment of the amount of the hydrolyzable silyl group introduced, and the physical properties of the resulting reactive silicon group-containing polymer are stable.
- Examples of the initiator having a hydroxyl group used in the method (i) and (ii) include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polypropylene glycol, polyoxypropylene triol, allyl alcohol, polypropylene monoallyl ether, polypropylene Examples thereof include those having one or more hydroxyl groups such as monoalkyl ether.
- Examples of the epoxy compound used in the methods (i) and (ii) include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Of these, propylene oxide is preferable.
- Examples of the carbon-carbon unsaturated group used in the method (i) include a vinyl group, an allyl group, and a methallyl group. Among these, an allyl group is preferable.
- an alkali metal salt is allowed to act on the hydroxyl-terminated polymer, and then a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted. It is preferable to use the method of making it.
- halogenated hydrocarbon compound used in the method (i) examples include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. It is done. From the viewpoint of reactivity with the hydrosilane compound, allyl chloride and methallyl chloride are preferred.
- hydrosilane compound triethoxysilane, diethoxymethylsilane, tripropoxysilane, dipropoxymethylsilane, (chloromethyl) diethoxysilane, (chloromethyl) dipropoxysilane, (methoxymethyl) di Ethoxysilane, (methoxymethyl) didipropoxysilane, (N, N-diethylaminomethyl) diethoxysilane, (N, N-diethylaminomethyl) dipropoxysilane, and the like can be used.
- the hydrosilylation reaction used in the method (i) is accelerated by various catalysts.
- the hydrosilylation catalyst known catalysts such as various complexes such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium may be used.
- platinum supported on a carrier such as alumina, silica, carbon black, chloroplatinic acid; chloroplatinic acid complex composed of chloroplatinic acid and alcohol, aldehyde, ketone, etc .
- platinum - vinylsiloxane complex [Pt ⁇ (vinyl) Me 2 SiOSiMe 2 (vinyl) ⁇ , Pt ⁇ Me (vinyl) SiO ⁇ 4 ]
- platinum-phosphine complex [Ph (PPh 3 ) 4 , Pt (PBu 3 ) 4 ]
- platinum-phosphite complex [Pt ⁇ P (OPh) 3 ⁇ 4 ] and the like
- isocyanate silanes such as 3-isocyanatopropyltriethoxysilane and isocyanatemethyltriethoxysilane
- Mercaptosilanes such as ethoxysilane
- epoxysilanes such as 3-glycidoxypropyltriethoxysilane
- aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate can be used as the polyisocyanate compound. It is.
- Examples of the compound having both an isocyanate group-reactive group and a hydrolyzable silyl group that can be used in the method (iii) include ⁇ -aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltri Amino group-containing silanes such as ethoxysilane, ⁇ - (N-phenyl) aminopropyltriethoxysilane, N-ethylaminoisobutyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane Hydroxy group-containing silanes such as ⁇ -hydroxypropyltriethoxysilane; mercapto group-containing silanes such as ⁇ -mercaptopropyltriethoxysilane;
- the curable composition includes, as an additive, a polymer other than a polyoxyalkylene polymer having a hydrolyzable silyl group, a silanol condensation catalyst, Filler, Adhesiveness imparting agent, Plasticizer, Solvent, Diluent, Anti-sagging agent, Antioxidant, Light stabilizer, Ultraviolet absorber, Physical property modifier, Tackifying resin, Epoxy group-containing compound, Photo-curing property Substances, oxygen curable substances, surface property improvers, epoxy resins, other resins, and flame retardants may be added.
- additives to a curable composition as needed for the purpose of adjustment of various physical properties of a curable composition or hardened
- additives include, for example, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, fungicides, and the like. It is done.
- a foaming agent is not substantially added to the curable composition.
- the foaming agent content is preferably less than 1 part by weight per 100 parts by weight of component (A).
- the curable composition contains the component (A) described above, it is easy to suppress swelling of the cured product of the curable composition in the composite without adding a highly heat-resistant polymer to the curable composition. .
- epoxy resin, tackifying resin, etc. with high heat resistance may be added in a small amount, or may not be added.
- the addition amount of the epoxy resin or tackifier having high heat resistance is preferably less than 1 part by weight with respect to 100 parts by weight of component (A), and more preferably not substantially added.
- the hydrolyzable silyl group has the general formula (1): -SiR a (OR 1 ) 3-a (1)
- R each independently represents a heteroatom-containing group or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent consisting of a halogen atom
- R 1 each independently represents a hydrocarbon having 2 to 10 carbon atoms.
- A represents 0, 1, 2
- It is preferable that only the hydrolyzable silyl group represented by the formula is because methanol that causes swelling during curing does not occur.
- the curable composition has the following general formula (2): -SiR 3 b (OR 4 ) 3-b (2)
- R 3 represents each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom-containing group or a substituent consisting of a halogen atom.
- R 4 each independently represents a carbon atom having 1 to 10 carbon atoms. Represents a hydrogen group, b is 0, 1, 2).
- the main chain skeleton of the non-polyoxyalkylene polymer is not particularly limited as long as it is other than the polyoxyalkylene polymer, and those having various main chain skeletons can be used.
- ethylene-propylene copolymers polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymers of butadiene and acrylonitrile and / or styrene, polybutadiene, Copolymers of isoprene or butadiene with acrylonitrile and styrene, hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; dibasic acids such as adipic acid and glycols Polyester polymers obtained by condensation with lactones or ring-opening polymerization of lactones; obtained by radical polymerization of monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate Acrylic polymer; acetic acid Vinyl polymer obtained by radical polymerization of monomers such as methyl (me
- the amount of the non-polyoxyalkylene polymer used is preferably 1 to 500 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the polymer (A) having a hydrolyzable silyl group. More preferred.
- ⁇ Silanol condensation catalyst> In the curable composition, for the purpose of accelerating the reaction of hydrolyzing and condensing the hydrolyzable silyl group of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group, and extending or crosslinking the polymer.
- a silanol condensation catalyst may be blended.
- silanol condensation catalyst it is already known that many catalysts can be used, and examples thereof include organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids and the like.
- organic tin compound examples include dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis ( Ethyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (Ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin dimethoxide, dibutyl tin bis (nonyl phenoxide), dibutenyl tin oxide, dibuty
- carboxylate metal salt examples include tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, Examples thereof include manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, and cerium carboxylate.
- carboxylic acid group the following carboxylic acid and various metals can be combined.
- the metal species divalent tin, bismuth, divalent iron, trivalent iron, zirconium and titanium are preferable because of high activity, and divalent tin is most preferable.
- amine compound examples include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, Aliphatic primary amines such as cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine Aliphatic secondary amines such as, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; Aliphatic tertiary
- amidines such as 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU and DBN
- guanidines such as guanidine, phenylguanidine and diphenylguanidine
- butylbiguanide, 1 Biguanides such as -o-tolyl biguanide and 1-phenyl biguanide are preferable because they exhibit high activity, and aryl group-substituted biguanides such as 1-o-tolyl biguanide and 1-phenyl biguanide can be expected to have high adhesiveness.
- aryl group-substituted biguanides such as 1-o-tolyl biguanide and 1-phenyl biguanide can be expected to have high adhesiveness.
- aryl group-substituted biguanides such as 1-o-tolyl biguanide and 1-phenyl biguanide can be expected to have high adhesiveness. preferable.
- an amino group-containing silane coupling agent (sometimes referred to as aminosilane) or a ketimine compound that generates the amine compound by hydrolysis can also be used.
- carboxylic acid examples include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, pivalic acid, 2,2-dimethylbutyric acid, 2,2-diethylbutyric acid, Examples include 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid and the like.
- 2-Ethylhexanoic acid, neodecanoic acid, and versatic acid have high activity and are preferable from the viewpoint of availability.
- carboxylic acid derivatives such as carboxylic acid anhydrides, alkyl carboxylates, amides, nitriles, and acyl halides can also be used.
- alkoxy metals include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate), Aluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate, zirconium compounds such as zirconium tetrakis (acetylacetonate), hafnium compounds such as tetrabutoxyhafniumkind.
- titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylace
- silanol condensation catalysts include organic sulfonic acids such as trifluoromethanesulfonic acid; inorganic acids such as hydrochloric acid, phosphoric acid and boronic acid; boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride ethylamine complex, etc.
- Boron trifluoride complex ammonium fluoride, tetrabutylammonium fluoride, potassium fluoride, cesium fluoride, ammonium hydrogen fluoride, 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane (MEC81 , Commonly known as Ishikawa reagent), potassium hexafluorophosphate, Na 2 SiF 6 , K 2 SiF 6 , (NH 4 ) 2 SiF 6 and other fluorine anion-containing compounds.
- MEC81 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane
- a photoacid generator or photobase generator that generates an acid or a base by light can also be used as a silanol condensation catalyst.
- the photoacid generator include triarylsulfonium salts such as p-phenylbenzylmethylsulfonium salt, p-hydroxyphenylbenzylmethylsulfonium salt, triphenylsulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt, 4,4 -Bis [di ( ⁇ -hydroxyethoxy) phenylsulfonio] phensulfide bishexafluoroantimonate, diphenyliodonium salt, bis (4-tert-butylphenyl) iodonium salt, (4-tert-butoxyphenyl) phenyliodonium salt, Onium salt photoacid generators such as iodonium salts such as (4-methoxyphenyl) pheny
- the silanol condensation catalyst may be used in combination of two or more different types of catalysts.
- the amine compound and carboxylic acid in combination, an effect of improving the reactivity may be obtained.
- the catalytic activity can also be increased by using an acid such as carboxylic acid in combination with a phosphonium salt compound such as tetrabutylphosphonium hydroxide.
- a halogen-substituted aromatic compound such as pentafluorophenol or pentafluorobenzaldehyde and an amine compound in combination.
- the amount of the silanol condensation catalyst used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight per 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group. Part is more preferable, and 0.01 to 10 parts by weight is particularly preferable.
- the amount of the silanol condensation catalyst is less than 0.001 part by weight, it may take a long time to cure the curable composition or it may be difficult to cure the curable composition to a desired level.
- the blending amount of the silanol condensation catalyst exceeds 20 parts by weight, the time that can be used without curing the composition is shortened as the reaction speeds up. The storage period during which the composition can be stored stably may be shortened.
- Fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, Resin powder such as magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, PVC powder, PMMA powder Fillers; fibrous fillers such as asbestos, glass fibers and filaments.
- reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black
- heavy calcium carbonate, colloidal calcium carbonate, Resin powder such as magnesium carbonate, diatomaceous earth, calcined clay, clay, tal
- the amount of the filler used is preferably 1 to 300 parts by weight, particularly preferably 10 to 250 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group.
- Organic balloons and inorganic balloons may be added to improve the workability of the composition (such as sharpness). These fillers can be surface-treated, and may be used alone or in combination of two or more.
- the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, it is preferably 5 to 300 ⁇ m.
- the balloon is a spherical filler with a hollow interior.
- the balloon can be added for the purpose of reducing the weight (lowering the specific gravity) of the composition.
- the balloon material include, but are not limited to, inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran.
- a plurality of types of balloon materials may be mixed, a composite material of an inorganic material and an organic material, or a laminated material composed of a plurality of layers.
- Adhesive agent An adhesiveness imparting agent can be added to the composition of the present invention.
- a silane coupling agent As the adhesion-imparting agent, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added.
- silane coupling agent examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltris (2-propoxy) silane, ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -aminopropyl.
- Methyldiethoxysilane N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldiethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltriisopropoxysilane, N- ⁇ - ( ⁇ -aminoethyl) aminoethyl- ⁇ -aminopropyltri Methoxysilane, N-6-aminohexyl- ⁇ -amino Propyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, ⁇ -ureidopropyltrime
- these partial condensates and derivatives thereof such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc. It can be used as a ring agent.
- a silane coupling agent containing a methoxy group as a hydrolyzable group generates methanol during curing. Since the generation of methanol causes the occurrence of blistering in the composite, it is better that it is as small as possible.
- the content of the silane coupling agent that contains a methoxy group as the hydrolyzable group is preferably 2 parts by weight or less.
- the hydrolyzable silyl group has the general formula (1): -SiR a (OR 1 ) 3-a (1) (R each independently represents a heteroatom-containing group or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent consisting of a halogen atom, and R 1 each independently represents a hydrocarbon having 2 to 10 carbon atoms.
- A represents 0, 1, 2 It is preferable that it is the silane coupling agent which is.
- ⁇ -aminopropyltriethoxysilane ⁇ -aminopropyltris (2-propoxy) silane, ⁇ -aminopropylmethyldiethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane, N - ⁇ -aminoethyl- ⁇ -aminopropylmethyldiethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltriisopropoxysilane, ⁇ -ureidopropyltriethoxysilane, N-vinylbenzyl- ⁇ -aminopropyltriethoxy Amino group-containing silanes such as silane and N-cyclohexylaminomethyltriethoxysilane; Isocyanate group-containing silanes such as ⁇ -isocyanatopropyltriethoxysilane and ⁇ -isocyanatoprop
- the above silane coupling agents may be used alone or in combination.
- reaction products of various silane coupling agents can be used.
- a reaction product a reaction product of isocyanate silane and a hydroxyl group-containing compound; a reaction product of isocyanate silane and an amino group-containing compound; a reaction product of amino silane and an acrylic group-containing compound; a reaction product of amino silane and a methacryl group-containing compound ( Michael addition reaction product); reaction product of aminosilane and epoxy group-containing compound; reaction product of epoxysilane and carboxylic acid group-containing compound; reaction product of epoxysilane and amino group-containing compound.
- Silane coupling agents such as a reaction product of isocyanate silane and aminosilane, a reaction product of aminosilane and (meth) acrylic group-containing silane, a reaction product of aminosilane and epoxysilane, a reaction product of aminosilane and acid anhydride-containing silane, etc. These reactants can also be used.
- adhesion-imparting agent other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates.
- the adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved.
- the amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, particularly 0.5 to 10 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group. Is preferred.
- a plasticizer can be added to the curable composition.
- a plasticizer By adding a plasticizer, the viscosity, slump property of the composition, and mechanical properties such as hardness, tensile strength, and elongation of the cured product obtained by curing the curable composition can be adjusted.
- plasticizer examples include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, and the like; bis (2-ethylhexyl) ) Terephthalic acid ester compounds such as 1,4-benzenedicarboxylate (specifically, trade name: EASTMAN 168 (manufactured by EASTMAN CHEMICAL)); non-phthalic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester ( Specifically, trade name: Hexamol DINCH (manufactured by BASF)); dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, tributy acetyl citrate Aliphatic
- a polymeric plasticizer can be used.
- the initial physical properties can be maintained over a long period of time compared to the case where a low molecular plasticizer is used.
- the drying property (paintability) when the alkyd paint is applied to the cured product can be improved.
- the polymer plasticizer include vinyl polymers, ester compounds, polyester plasticizers, polyether polyols, polyether polyol derivatives, polystyrene plasticizers, and the like.
- the vinyl polymer is a polymer obtained by polymerizing various vinyl monomers by various methods.
- the vinyl polymer may be a single monomer homopolymer or a copolymer of two or more monomers.
- ester compound examples include aliphatic alcohol ester compounds having two or more alcoholic hydroxyl groups such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester.
- polyester plasticizer examples include a polyester plasticizer obtained from a dibasic acid and a dihydric alcohol. Examples of the dibasic acid include sebacic acid, adipic acid, azelaic acid, and phthalic acid. Examples of the dihydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
- the number average molecular weight of the polyether polyol is preferably 500 or more, and more preferably 1000 or more.
- the polyether polyol derivatives include derivatives obtained by converting the hydroxy groups of these polyether polyols into ester groups, ether groups, and the like.
- polystyrene plasticizers include polystyrene and poly- ⁇ -methylstyrene.
- polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like can be mentioned.
- Various polymers can be provided with physical properties by copolymerizing a reactive group-containing monomer. For example, it is known that the adhesion improvement effect and the elastic recovery rate are improved by using polybutadiene grafted with maleic acid.
- the amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, especially 20 to 20 parts by weight based on 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group. 100 parts by weight is preferred. If it is less than 5 parts by weight, it may be difficult to obtain a desired effect by using a plasticizer. If it exceeds 150 parts by weight, it may be difficult to form a cured product having good mechanical strength.
- a plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.
- a solvent or a diluent can be added to the curable composition.
- Aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ester, ketone, ether etc. can be used.
- the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher because of the problem of air pollution when the composition is used indoors.
- the said solvent or diluent may be used independently and may be used together 2 or more types.
- the amount of the solvent and diluent used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, particularly 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group. 20 to 100 parts by weight are preferred. On the other hand, since it may cause foaming, the amount is preferably 5 parts by weight or less than 1 part by weight with respect to 100 parts by weight of the polymer (A).
- An anti-sagging agent may be added to the curable composition as needed to prevent sagging and improve workability.
- the sagging inhibitor is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when rubber powder having a particle diameter of 10 to 500 ⁇ m as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained.
- These anti-sagging agents may be used alone or in combination of two or more.
- the amount of the sagging inhibitor used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group.
- 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, with hindered phenols being particularly preferred.
- Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by Ciba Japan Co., Ltd.); All are manufactured by ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.)
- Hindered amine light stabilizers can also be used. 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 from 0.1 to 10 parts by weight, particularly preferably from 2 to 7 parts by weight, based on 100 parts by weight of the polyoxyalkylene 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-based, hindered amine-based, and benzoate-based compounds, and hindered amine-based compounds are particularly preferable.
- the amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, particularly 0.2 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group. preferable.
- 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, with benzotriazole being particularly preferred, and commercially available names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571 (above, manufactured by BASF) can be mentioned.
- 2- (2H-1,2,3-benzotriazol-2-yl) -phenolic compounds are particularly preferred.
- the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, particularly 0.2 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group. preferable.
- alkyl alkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane
- Arylalkoxysilanes such as; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, alkylisopropenoxysilane such as ⁇ -glycidoxypropylmethyldiisopropenoxysilane; tris (trimethylsilyl) borate, tris (triethyl) And trialkylsilyl borates such as si
- the hardness of the cured product of the curable composition can be increased, or conversely, the hardness can be decreased and elongation at break can be produced.
- the said physical property modifier may be used independently and may be used together 2 or more types.
- a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product.
- Particularly preferred are compounds that produce trimethylsilanol. Examples of the compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis include compounds described in JP-A-5-117521.
- derivatives of alkyl alcohols such as hexanol, octanol, decanol, etc., which produce silicon compounds that produce silane monools such as trimethylsilanol by hydrolysis, and trimethylol described in JP-A-11-241029
- Mention may be made, for example, of derivatives of polyhydric alcohols having 3 or more hydroxyl groups, such as propane, glycerin, pentaerythritol and sorbitol, which produce silicon compounds that produce silane monools by hydrolysis.
- the amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group. preferable.
- a tackifying resin can be added to the curable composition for the purpose of enhancing the adhesion and adhesion to the substrate, or as necessary.
- the tackifying resin is not particularly limited, and those that are usually used can be used.
- terpene resins aromatic modified terpene resins and hydrogenated terpene resins obtained by hydrogenation thereof
- terpene-phenol resins obtained by copolymerizing terpenes with phenols
- phenol resins modified phenol resins
- xylene-phenols terpene resins
- Resin cyclopentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon) Resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, DCPD resin and the like. These may be used alone or in combination of two or more.
- the styrenic block copolymer and its hydrogenated product are not particularly limited.
- styrene-butadiene-styrene block copolymer SBS
- SIS styrene-isoprene-styrene block copolymer
- SEBS butylene-styrene block copolymer
- SEPS styrene-ethylenepropylene-styrene block copolymer
- SIBS styrene-isobutylene-styrene block copolymer
- terpene-phenol resins are preferred because they are highly compatible with the polyoxyalkylene polymer (A) having a hydrolyzable silyl group and provide a high adhesion effect.
- a hydrocarbon resin is preferable.
- the amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group. More preferred is 30 parts.
- the amount is less than 2 parts by weight, it is difficult to obtain adhesion and adhesion effects to the substrate, and when the amount exceeds 100 parts by weight, the viscosity of the composition may be too high and handling may be difficult.
- the curable composition contains the component (A) described above, it is easy to suppress swelling of the cured product of the curable composition in the composite without adding a highly heat-resistant polymer to the curable composition. .
- a high heat-resistant tackifier resin may be added in a small amount or may not be added.
- the addition amount of the tackifying resin having high heat resistance is preferably less than 1 part by weight with respect to 100 parts by weight of the component (A), and more preferably not substantially added.
- a compound containing an epoxy group can be used in the curable composition.
- the restorability of the cured product can be improved.
- the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof.
- E-PS epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate.
- E-PS is particularly preferred.
- the epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group.
- a photocurable material can be used for the curable composition.
- a photocurable material is used, a film of a photocurable material is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved.
- a photocurable substance is a substance in which the molecular structure undergoes a chemical change in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Typical examples include unsaturated acrylic compounds, polyvinyl cinnamates, or azide resins.
- Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) dimethacrylate and oligoesters having a molecular weight of 10,000 or less.
- Aronix M-210 special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M305 , Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400, etc., particularly compounds containing an acrylic functional group
- a compound containing an average of 3 or more functional groups in one molecule is preferable (all Aronix is a product of Toa Gosei Chemical Co., Ltd.).
- polyvinyl cinnamates examples include a photosensitive resin having a cinnamoyl group as a photosensitive group, in which polyvinyl alcohol is esterified with cinnamic acid, and many polyvinyl cinnamate derivatives are exemplified.
- the azide resin is known as a photosensitive resin having an azide group as a photosensitive group.
- a photosensitive resin in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972).
- publishing, publishing society of printing society publication, page 93-, page 106-, page 117- These can be used alone or in combination, and sensitizers can be added if necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.
- the amount of the photocurable substance used is preferably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group. More preferred. If it is less than 0.1 part by weight, it is difficult to increase the weather resistance of the cured product to a desired level. If it exceeds 20 parts by weight, a hardened and easily cracked cured product may be formed even if the weather resistance of the cured product can be improved.
- An oxygen curable substance can be used for the curable composition.
- the oxygen curable substance include unsaturated compounds that can react with oxygen in the air.
- the oxygen curable substance reacts with oxygen in the air to form a cured film in the vicinity of the surface of the cured product, and has an effect of preventing stickiness of the surface and adhesion of dust and dust to the cured product surface.
- oxygen curable substance examples include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with drying oils , Silicone resin; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymer obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
- drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds
- acrylic polymers and epoxy resins modified with drying oils Silicone resin
- 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymer obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
- Liquid polymers liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound
- various modified products thereof maleinized modified products, boiled oil modified products, etc.
- drill oil and liquid diene polymers are particularly preferable.
- the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination.
- catalysts and metal dryers examples include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds.
- the amount of the oxygen curable substance used is preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group. 0.5 to 10 parts by weight. If the amount used is less than 0.1 parts by weight, it may be difficult to obtain the desired effect of improving the contamination. If the amount used exceeds 20 parts by weight, it may be difficult to form a cured product having good tensile properties. As described in JP-A-3-160053, an oxygen curable substance is preferably used in combination with a photocurable substance.
- a surface property improving agent can be added to the curable composition.
- surface property improvers include long-chain alkylamines such as laurylamine, 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, tris (2,4-di-tert-butylphenyl) ) Phosphorus compounds such as phosphites, oxazolidine compounds and the like.
- the amount of the surface property improving agent used is preferably in the range of 0.3 to 10 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene polymer (A) having hydrolyzable silyl groups.
- Epoxy resin can be used in combination with the curable composition.
- the epoxy resin is defined as a compound having an epoxy group in an uncured state.
- the curable composition to which the epoxy resin has been added preferably acts as an adhesive, particularly an adhesive for exterior wall tiles, in relation to the substrate.
- Epoxy resins include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A Propylene oxide adduct glycidyl ether type epoxy resin, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N , N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether Glycidyl ethers of polyhydric alcohols such as glycerin, hydantoin type epoxy resins,
- the epoxy resin is not limited to these, and generally used epoxy resins can be used. Those containing at least two epoxy groups in the molecule are preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. More preferred are bisphenol A type epoxy resins or novolak type epoxy resins.
- the use ratio of these epoxy resins and the component (A) is such that a cured product having good impact strength and toughness can be easily formed. A range of 1/100 is preferred.
- the curable composition contains the component (A) described above, it is easy to suppress swelling of the cured product of the curable composition in the composite without adding a highly heat-resistant polymer to the curable composition. For this reason, in a curable composition, the epoxy resin with high heat resistance may be added in a small amount or may not be added. Specifically, the addition amount of the epoxy resin can be suppressed to less than 1 part by weight with respect to 100 parts by weight of the component (A), and there is no problem even if it is not substantially added.
- the amount used is in the range of 0.1 to 300 parts by weight per 100 parts by weight of the epoxy resin.
- Ketimine can be used as a curing agent for epoxy resin. Ketimine is stably present in the absence of moisture, and is decomposed into primary amines and ketones by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin.
- ketimine When ketimine is used, a one-component composition can be obtained. Such a ketimine can be obtained by a condensation reaction between an amine compound and a carbonyl compound.
- a known amine compound or carbonyl compound may be used for the synthesis of ketimine.
- amine compounds include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, and p-phenylene.
- Diamines such as diamine and p, p'-biphenylenediamine; polyvalent amines such as 1,2,3-triaminopropane, triaminobenzene, tris (2-aminoethyl) amine and tetra (aminomethyl) methane; diethylenetriamine, Polyalkylene polyamines such as triethylenetriamine and tetraethylenepentamine; polyoxyalkylene polyamines; ⁇ -aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysila , Aminosilanes such as N-(beta-aminoethyl)-.gamma.-aminopropyl methyl dimethoxy silane; and may be used.
- carbonyl compounds examples include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal, and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, and trimethylcyclohexanone; acetone, methyl ethyl ketone , Aliphatic ketones such as methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, malon ⁇ -dicarbony
- the imino group When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like.
- ketimines may be used alone or in combination of two or more, and are used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin.
- the amount used is the kind of epoxy resin and ketimine It depends on.
- a flame retardant such as a phosphorus compound such as ammonium polyphosphate or tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite can be added to the curable composition.
- the said flame retardant may be used independently and may be used together 2 or more types.
- the flame retardant is used in an amount of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group.
- the curable composition can be prepared as a one-component type in which all the components are pre-blended and stored in a sealed state and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as water are blended and the compounding material and the organic polymer composition are mixed before use. From the viewpoint of workability, a one-component type is preferable.
- the curable composition When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred.
- the curable composition When the curable composition is a two-component type, it is not necessary to add a silanol condensation catalyst to the main component containing an organic polymer having a reactive silicon group, so even if some moisture is contained in the compounding agent There is little concern about the increase in viscosity of the product or gelation, but dehydration drying is preferred when long-term storage stability is required.
- a heat drying method is preferable for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there.
- a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration.
- an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration.
- lower alcohols such as methanol and ethanol
- silicates such as methyl silicate and ethyl silicate further improves storage stability.
- A represents 0, 1, 2
- the amount of the dehydrating agent, particularly the silicon compound capable of reacting with water is 0.1 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group. A range of 5 to 10 parts by weight is preferred.
- thermosetting coating is applied, followed by heating to form a composite. Manufacture the body.
- the substrate is not particularly limited as long as it can withstand the temperature at the time of heating, for example, metal such as iron, steel plate, stainless steel, aluminum, tinplate, zinc, copper, acrylic resin, phenolic resin, polypropylene, Examples thereof include resins such as polycarbonate, polyamide, melanin resin, epoxy resin, polyurethane, FRP (fiber reinforced resin), and CFRP (carbon fiber reinforced resin), and inorganic substrates such as glass, cement, mortar, tile, and brick.
- metal such as iron, steel plate, stainless steel, aluminum, tinplate, zinc, copper, acrylic resin, phenolic resin, polypropylene
- resins such as polycarbonate, polyamide, melanin resin, epoxy resin, polyurethane, FRP (fiber reinforced resin), and CFRP (carbon fiber reinforced resin)
- inorganic substrates such as glass, cement, mortar, tile, and brick.
- the temperature at which the curable composition is applied to the substrate is not particularly limited, is preferably 0 ° C. to 50 ° C., more preferably 10 ° C. to 40 ° C., and particularly preferably room temperature.
- the heating step is preferably performed before the curable composition is cured.
- the term “before curing” means that the inside of the curable composition is completely cured, and heating is preferably performed on the same day that the curable composition is applied to the substrate. More preferred is 10 minutes or more and 5 hours or less.
- the gel fraction of the curable composition in the middle of curing can also be evaluated, and the gel fraction is preferably 1% or more and 80% or less, and more preferably 5% or more and 50% or less.
- the heating temperature is preferably 140 to 250 ° C, more preferably 150 to 250 ° C.
- the heating time is not particularly limited, but is preferably from 1 minute to 5 hours, more preferably from 2 minutes to 2 hours, and even more preferably from 5 minutes to 1 hour.
- Examples of the composite include a composite in which a curable composition is applied to a base material and a plurality of base materials are bonded together, and a composite in which a curable composition is applied to fill a gap between the base material and the base material.
- a usage method as an adhesive is a usage method as an adhesive, and the later description is a usage method as a sealing material.
- the heating step may be a step for heating and curing the curable composition to produce a composite, a heating and curing step for curing the curable composition, a primer for heating and curing the composite, a paint, Examples thereof include a heat curing step after applying a sealer, a potting material, a coating material, and the like.
- Examples of the heat-curing process after applying a paint or the like include a baking process after applying the baking paint, a heat-drying process after electrodeposition coating, and the like.
- the heating step is a heat curing step after applying a primer, paint, sealer, potting material, coating material, etc. that is heat-cured to the composite in terms of fully utilizing the effects of the present invention. More preferably, it is a heat-curing step after applying a heat-curing paint.
- a heating method conventionally known means such as hot air drying and infrared heating are used.
- the heating step is a step of curing the curable composition
- the temperature is 140 to 250 ° C.
- a method of curing a curable composition by heating, applying the curable composition to one or more substrates of a plurality of substrates, bonding the substrates together, and then applying the substrates to 140 to 250 The method of heating at °C and curing the curable composition is mentioned.
- the heating step is a heat curing step in which a coating applied to the composite is cured
- apply a primer, paint, sealer, potting material, coating material, etc. to heat and cure to a composite of multiple substrates bonded with a curable composition, and heat the paint by heating at 140-250 ° C.
- the method of hardening is mentioned.
- the application of the coating material to the composite may be performed after the curable composition is cured, but is performed before the curable composition is cured or when the surface is cured, and a heat curing process in which the coating material is heated and cured.
- the curable composition may be cured together. Examples of the coating method that cures by heating include baking coating and electrodeposition coating.
- 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.
- a polyoxypropylene polymer (Q-1) having an allyl group at the terminal site was obtained.
- this polymer (Q-1) 25 ⁇ l of platinum divinyldisiloxane complex solution was added, and 14.6 g of triethoxysilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted triethoxysilane was distilled off under reduced pressure to obtain 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 2.2 triethoxysilyl groups per molecule.
- Methanol was devolatilized from the obtained methanol solution to obtain polyoxypropylene (B-2) having a number average molecular weight of about 16400 having a trimethoxysilyl group at the terminal.
- the polymer (B-2) was found to have an average of 2.2 trimethoxysilyl groups per molecule.
- Example 1 IRGANOX245 (manufactured by BASF Japan Ltd., hindered phenol antioxidant), PPG3000 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name: Actcoal) with respect to 100 parts by weight of polymer (A-1) P-23) 50 parts by weight, Neolite SP (manufactured by Takehara Chemical Co., Ltd .: precipitated calcium carbonate) 160 parts by weight, LM2200 (manufactured by Maruo Calcium Co., Ltd .: heavy calcium carbonate), 54 parts by weight, A-1100 (Momentive) Product: 5 parts by weight of ⁇ -aminopropyltriethoxysilane) and 2 parts by weight of U-220H (manufactured by Nitto Kasei Co., Ltd .: dibutyltin bisacetylacetonate) are added and mixed well with a spatula. And uniformly deaerated.
- IRGANOX245 manufactured by BASF Japan
- the obtained curable composition is applied on an aluminum plate to a size of 20 mm ⁇ 120 mm ⁇ 2 mm (thickness). After curing the curable composition applied to aluminum in an environment of 23 ° C / 50% RH for 20 minutes, immediately cure it in a dryer adjusted to 100 ° C, 160 ° C, or 180 ° C, and immediately after curing is complete. The product was taken out and cooled for 10 minutes. The foamed state of the cured product after cooling was visually observed to confirm the presence or absence of foaming.
- Example 2 A cured product obtained in the same manner as in Example 1 except that 3 parts by weight of A-1100 and 4 parts by weight of ethylsilicate 48 (manufactured by Colcoat Co.) were used instead of 5 parts by weight of A-1100. The product was evaluated. The results are shown in Table 1.
- Example 3 A curable composition was prepared in the same manner as in Example 1. The obtained curable composition is applied to a size of 20 mm ⁇ 120 mm ⁇ 2 mm (thickness) on an aluminum plate. The curable composition applied to aluminum was cured for 20 minutes in an environment of 23 ° C./50% RH, and then an epoxy paint was applied on the curable composition. Immediately after the application of the epoxy-based paint, it was cured for 20 minutes in a dryer adjusted to 100 ° C. or 160 ° C., taken out immediately after the curing was completed, and cooled for 10 minutes. The foamed state of the cured product in the composite after cooling was visually observed to confirm the presence or absence of foaming.
- Example 1 The same as Example 1 except that the polymer (B-1) was used in place of the polymer (A-1), and A-1110 (manufactured by Momentive: ⁇ -aminopropyltrimethoxysilane) was used in place of A-1100. The cured product thus obtained was evaluated. The results are shown in Table 1.
- Example 2 The same operation as in Example 1 was performed except that the polymer (B-1) was used instead of the polymer (A-1). However, curing progressed during production, and a curable composition was not obtained. It was.
- Example 3 The same procedure as in Example 1 was carried out except that polymer (B-1) was used instead of polymer (A-1) and 1 part by weight of U-220H was used instead of 2 parts by weight of U-220H. The cured product thus obtained was evaluated. The results are shown in Table 1.
- Example 5 A curable composition was prepared in the same manner as in Comparative Example 1. Using the obtained curable composition, heating in a composite comprising a base material made of an aluminum plate, a cured product of the curable composition, and a coating film of a thermosetting paint was performed in the same manner as in Example 3. Later blisters were evaluated. As a result, it was evaluated as ⁇ when heated at 100 ° C, and there was no problem of blistering or foaming, but it was evaluated as ⁇ when heated at 160 ° C, and the coating film was affected by foaming in the cured product of the curable composition. Swelling also occurred on the surface. The x evaluation when heated at 160 ° C. is considered to be caused by blending the polymer (B-1) having a trimethoxy group into the curable composition.
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Abstract
Description
(1).基材と、硬化性組成物の硬化物と、加熱硬化型塗料の塗膜との複合体の製造方法であって、
硬化性組成物を基材に塗布した後、加熱硬化型塗料を塗布し、その後加熱を行うことを含み、
硬化性組成物が、加水分解性シリル基を有するポリオキシアルキレン系重合体(A)を含み、
加水分解性シリル基が、下記一般式(1):
-SiRa(OR1)3-a (1)
(Rはそれぞれ独立にヘテロ原子含有基またはハロゲン原子からなる置換基を有していてもよい炭素数1~10の炭化水素基を表し、R1はそれぞれ独立に炭素数2~10の炭化水素基を表し、aは0、1、2である。)
で表される、製造方法、
(2).加熱の温度が、140~250℃である(1)に記載の複合体の製造方法、
(3).加熱の温度が、150~250℃である(2)に記載の複合体の製造方法、
(4).硬化性組成物を基材に塗布した後、硬化性組成物が硬化する前に加熱を行う(1)~(3)のいずれか1つに記載の複合体の製造方法、
(5).R1がエチル基である(1)~(4)のいずれか1つに記載の複合体の製造方法、
(6).aが0である(1)~(5)のいずれか1つに記載の複合体の製造方法、
(7).硬化性組成物が、さらに加水分解性基がメトキシ基であるシランカップリング剤を含有し、シランカップリング剤の含有量が加水分解性シリル基を有するポリオキシアルキレン系重合体(A)100重量部に対して2重量部以下である(1)~(6)のいずれか1つに記載の複合体の製造方法、
(8).硬化性組成物が含有する加水分解性シリル基を有する化合物の加水分解性シリル基が一般式(1)に示す加水分解性シリル基のみである(1)~(6)のいずれか1つに記載の複合体の製造方法、
(9).加水分解性シリル基を有するポリオキシアルキレン系重合体(A)の一分子中に含まれるシリル基の数が、1.8~3.0個である(1)~(8)のいずれか1つに記載の複合体の製造方法、および、
(10).基材と、硬化性組成物の硬化物と、加熱硬化型塗料の塗膜との複合体であって、
硬化性組成物が、加水分解性シリル基を有するポリオキシアルキレン系重合体(A)を含み、
加水分解性シリル基が、下記一般式(1):
-SiRa(OR1)3-a (1)
(Rはそれぞれ独立にヘテロ原子含有基またはハロゲン原子からなる置換基を有していてもよい炭素数1~10の炭化水素基を表し、R1はそれぞれ独立に炭素数2~10の炭化水素基を表し、aは0、1、2である。)
で表される、複合体、
に関する。
当該製造方法は、硬化性組成物を基材に塗布した後、加熱硬化型塗料を塗布し、その後加熱を行うことを含む
複合体の製造に用いられる硬化性組成物は、加水分解性シリル基を有するポリオキシアルキレン系重合体(A)を含有する。
加水分解性シリル基は、下記一般式(1):
-SiRa(OR1)3-a (1)
(Rはそれぞれ独立にヘテロ原子含有基またはハロゲン原子からなる置換基を有していてもよい炭素数1~10の炭化水素基を表し、R1はそれぞれ独立に炭素数2~10の炭化水素基を表し、aは0、1、2である。)
で表される。
複合体の製造に用いる硬化性組成物は、下記一般式(1):
-SiRa(OR1)3-a (1)
(Rはそれぞれ独立にヘテロ原子含有基またはハロゲン原子からなる置換基を有していてもよい炭素数1~10の炭化水素基を表す。R1はそれぞれ独立に炭素数2~10の炭化水素基を表す。aは0、1、2である。)
で表される加水分解性シリル基を有するポリオキシアルキレン系重合体(A)を含有する。
一般式(1)のR1を炭素数2~10の炭化水素基にする事により、加熱したときに気化しやすい低分子量のメタノールが硬化時に発生しないため、硬化物表面に膨れやシワが発生しにくい。
以下、加水分解性シリル基を有するポリオキシアルキレン系重合体(A)について、(A)成分とも記す。
ポリオキシアルキレン系重合体(A)は下記一般式(1):
-SiRa(OR1)3-a (1)
(Rはそれぞれ独立にヘテロ原子含有基またはハロゲン原子からなる置換基を有していてもよい炭素数1~10の炭化水素基を表す。R1はそれぞれ独立に炭素数2~10の炭化水素基を表す。aは0、1、2である。)
で表される加水分解性シリル基を有する。
加水分解性シリル基を有するポリオキシアルキレン系重合体(A)の主鎖構造は、直鎖状であってもよいし、分岐鎖を有していてもよい。分岐構造の方が、発泡を抑制できるため好ましい。
硬化性組成物には、加水分解性シリル基を有するポリオキシアルキレン系重合体(A)の他に添加剤として、加水分解性シリル基を有するポリオキシアルキレン系以外の重合体、シラノール縮合触媒、充填剤、接着性付与剤、可塑剤、溶剤、希釈剤、タレ防止剤、酸化防止剤、光安定剤、紫外線吸収剤、物性調整剤、粘着付与樹脂、エポキシ基を含有する化合物、光硬化性物質、酸素硬化性物質、表面性改良剤、エポキシ樹脂、その他の樹脂、難燃剤を添加してもよい。また、硬化性組成物には、硬化性組成物または硬化物の諸物性の調整を目的として、必要に応じて各種添加剤を添加してもよい。このような添加物の例としては、例えば、硬化性調整剤、ラジカル禁止剤、金属不活性化剤、オゾン劣化防止剤、リン系過酸化物分解剤、滑剤、顔料、防かび剤などが挙げられる。
また、硬化性組成物が前述の(A)成分を含むため、耐熱性の高いポリマーを硬化性組成物に添加しなくても、複合体における硬化性組成物の硬化物の膨れを抑制しやすい。このため、硬化性組成物において、耐熱性の高いエポキシ樹脂、粘着付与樹脂などは少量添加されるか、添加されなくてもよい。耐熱性の高いエポキシ樹脂や粘着付与剤の添加量は(A)成分100重量部に対して1重量部未満であることが好ましく、実質的に添加しないことがより好ましい。
-SiRa(OR1)3-a (1)
(Rはそれぞれ独立にヘテロ原子含有基またはハロゲン原子からなる置換基を有していてもよい炭素数1~10の炭化水素基を表し、R1はそれぞれ独立に炭素数2~10の炭化水素基を表し、aは0、1、2である。)
で表される加水分解性シリル基のみであるのが、硬化時に膨れの原因となるメタノールが発生しないので、好ましい。
硬化性組成物は、下記一般式(2):
-SiR3 b(OR4)3-b (2)
(R3はそれぞれ独立にヘテロ原子含有基またはハロゲン原子からなる置換基を有していてもよい炭素数1~10の炭化水素基を表す。R4はそれぞれ独立に炭素数1~10の炭化水素基を表す。bは0、1、2である。)。
で表される加水分解性シリル基を有する、ポリオキシアルキレン系以外の重合体を含んでいてもよい。
硬化性組成物には、加水分解性シリル基を有するポリオキシアルキレン系重合体(A)の加水分解性シリル基を加水分解・縮合させる反応を促進し、重合体を鎖延長または架橋させる目的で、シラノール縮合触媒を配合してもよい。
硬化性組成物には、種々の充填剤を配合することができる。充填剤としては、ヒュームドシリカ、沈降性シリカ、結晶性シリカ、溶融シリカ、ドロマイト、無水ケイ酸、含水ケイ酸、およびカーボンブラックのような補強性充填剤;重質炭酸カルシウム、膠質炭酸カルシウム、炭酸マグネシウム、ケイソウ土、焼成クレー、クレー、タルク、酸化チタン、ベントナイト、有機ベントナイト、酸化第二鉄、アルミニウム微粉末、フリント粉末、酸化亜鉛、活性亜鉛華、PVC粉末、PMMA粉末など樹脂粉末のような充填剤;石綿、ガラス繊維およびフィラメントのような繊維状充填剤などが挙げられる。
本発明の組成物には、接着性付与剤を添加することができる。
-SiRa(OR1)3-a (1)
(Rはそれぞれ独立にヘテロ原子含有基またはハロゲン原子からなる置換基を有していてもよい炭素数1~10の炭化水素基を表し、R1はそれぞれ独立に炭素数2~10の炭化水素基を表し、aは0、1、2である。)
であるシランカップリング剤である事が好ましい。
具体的には、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルトリス(2-プロポキシ)シラン、γ-アミノプロピルメチルジエトキシシラン、N-β-アミノエチル-γ-アミノプロピルトリエトキシシラン、N-β-アミノエチル-γ-アミノプロピルメチルジエトキシシラン、N-β-アミノエチル-γ-アミノプロピルトリイソプロポキシシラン、γ-ウレイドプロピルトリエトキシシラン、N-ビニルベンジル-γ-アミノプロピルトリエトキシシラン、N-シクロヘキシルアミノメチルトリエトキシシラン、などのアミノ基含有シラン類;γ-イソシアネートプロピルトリエトキシシラン、γ-イソシアネートプロピルメチルジエトキシシラン、などのイソシアネート基含有シラン類;γ-メルカプトプロピルトリエトキシシラン、などのメルカプト基含有シラン類;γ-グリシドキシプロピルトリエトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリエトキシシランなどのエポキシ基含有シラン類;β-カルボキシエチルトリエトキシシラン、などのカルボキシシラン類;ビニルトリエトキシシラン、γ-アクリロイルオキシプロピルメチルトリエトキシシランなどのビニル型不飽和基含有シラン類などが挙げられる。
硬化性組成物には、可塑剤を添加することができる。可塑剤の添加により、組成物の粘度やスランプ性および硬化性組成物を硬化して得られる硬化物の硬度、引張り強度、伸びなどの機械特性が調整できる。可塑剤の具体例としては、ジブチルフタレート、ジイソノニルフタレート(DINP)、ジヘプチルフタレート、ジ(2-エチルヘキシル)フタレート、ジイソデシルフタレート(DIDP)、ブチルベンジルフタレートなどのフタル酸エステル化合物;ビス(2-エチルヘキシル)-1,4-ベンゼンジカルボキシレートなどのテレフタル酸エステル化合物(具体的には、商品名:EASTMAN168(EASTMAN CHEMICAL製));1,2-シクロヘキサンジカルボン酸ジイソノニルエステルなどの非フタル酸エステル化合物(具体的には、商品名:Hexamoll DINCH(BASF製));アジピン酸ジオクチル、セバシン酸ジオクチル、セバシン酸ジブチル、コハク酸ジイソデシル、アセチルクエン酸トリブチルなどの脂肪族多価カルボン酸エステル化合物;オレイン酸ブチル、アセチルリシノール酸メチルなどの不飽和脂肪酸エステル化合物;アルキルスルホン酸フェニルエステル(具体的には、商品名:Mesamoll(LANXESS製));トリクレジルホスフェート、トリブチルホスフェートなどのリン酸エステル化合物;トリメリット酸エステル化合物;塩素化パラフィン;アルキルジフェニル、部分水添ターフェニルなどの炭化水素系油;プロセスオイル;エポキシ化大豆油、エポキシステアリン酸ベンジルなどのエポキシ可塑剤、などを挙げることができる。
高分子可塑剤の具体例としては、ビニル系重合体、エステル化合物、ポリエステル系可塑剤、ポリエーテルポリオール、ポリエーテルポリオール誘導体、ポリスチレン系可塑剤などをあげることができる。
ビニル系重合体は、種々のビニル系モノマーを種々の方法で重合して得られる重合体である。ビニル系重合体は、単一の単量体の単独重合体であってもよく、二種以上の単量体の共重合体であってもよい。
エステル化合物としては、例えば、ジエチレングリコールジベンゾエート、トリエチレングリコールジベンゾエート、ペンタエリスリトールエステルなどの、2以上のアルコール性水酸基を有する脂肪族アルコールのエステル化合物が挙げられる。
ポリエステル系可塑剤としては、例えば2塩基酸と2価アルコールとから得られるポリエステル系可塑剤が挙げられる。2塩基酸としては、例えば、セバシン酸、アジピン酸、アゼライン酸、フタル酸などが挙げられる。2価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコールなどが挙げられる。
ポリエーテルポリオールとしては、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどが挙げられる。ポリエーテルポリオールの数平均分子量は500以上が好ましく1000以上がより好ましい。
ポリエーテルポリオール誘導体としては、これらポリエーテルポリオールのヒドロキシ基をエステル基、エーテル基などに変換した誘導体が挙げられる。
ポリスチレン系可塑剤としては、例えば、ポリスチレン、ポリ-α-メチルスチレンなどが挙げられる。
さらに、ポリブタジエン、ポリブテン、ポリイソブチレン、ブタジエン-アクリロニトリル、ポリクロロプレンなどが挙げられる。
また、各種重合体には反応性基含有モノマーを共重合して物性を付与させることもできる。例えば、マレイン酸をグラフトさせたポリブタジエンを使用することで接着性向上効果や弾性回復率が向上することが知られている。
硬化性組成物には溶剤または希釈剤を添加することができる。溶剤および希釈剤としては、特に限定されないが、脂肪族炭化水素、芳香族炭化水素、脂環族炭化水素、ハロゲン化炭化水素、アルコール、エステル、ケトン、エーテルなどを使用することができる。溶剤または希釈剤を使用する場合、組成物を屋内で使用した時の空気への汚染の問題から、溶剤の沸点は、150℃以上が好ましく、200℃以上がより好ましく、250℃以上が特に好ましい。上記溶剤または希釈剤は単独で用いてもよく、2種以上併用してもよい。
硬化性組成物には、必要に応じてタレを防止し、作業性を良くするためにタレ防止剤を添加してもよい。また、タレ防止剤としては特に限定されないが、例えば、ポリアミドワックス類;水添ヒマシ油誘導体類;ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸バリウムなどの金属石鹸類などが挙げられる。また、特開平11-349916号公報に記載されているような粒子径10~500μmのゴム粉末や、特開2003-155389号公報に記載されているような有機質繊維を用いると、チクソ性が高く作業性の良好な組成物が得られる。これらタレ防止剤は単独で用いてもよく、2種以上併用してもよい。
硬化性組成物には、酸化防止剤(老化防止剤)を使用することができる。酸化防止剤を使用すると硬化物の耐候性を高めることができる。酸化防止剤としてはヒンダードフェノール系、モノフェノール系、ビスフェノール系、ポリフェノール系が例示できるが、特にヒンダードフェノール系が好ましい。同様に、チヌビン622LD,チヌビン144;CHIMASSORB944LD,CHIMASSORB119FL(以上いずれもチバ・ジャパン株式会社製);アデカスタブLA-57,アデカスタブLA-62,アデカスタブLA-67,アデカスタブLA-63,アデカスタブLA-68(以上いずれも株式会社ADEKA製);サノールLS-770,サノールLS-765,サノールLS-292,サノールLS-2626,サノールLS-1114,サノールLS-744(以上いずれも三共ライフテック株式会社製)に示されたヒンダードアミン系光安定剤を使用することもできる。酸化防止剤の具体例は特開平4-283259号公報や特開平9-194731号公報にも記載されている。
硬化性組成物には、光安定剤を使用することができる。光安定剤を使用すると硬化物の光酸化劣化を防止できる。光安定剤としてベンゾトリアゾール系、ヒンダードアミン系、ベンゾエート系化合物などが例示できるが、特にヒンダードアミン系が好ましい。
硬化性組成物には、紫外線吸収剤を使用することができる。紫外線吸収剤を使用すると硬化物の表面耐候性を高めることができる。紫外線吸収剤としてはベンゾフェノン系、ベンゾトリアゾール系、サリチレート系、置換トリル系および金属キレート系化合物などが例示できるが、特にベンゾトリアゾール系が好ましく、市販名チヌビンP、チヌビン213、チヌビン234、チヌビン326、チヌビン327、チヌビン328、チヌビン329、チヌビン571(以上、BASF製)が挙げられる。2-(2H-1,2,3-ベンゾトリアゾール-2-イル)-フェノール系化合物が特に好ましい。さらに、フェノール系やヒンダードフェノール系酸化防止剤とヒンダードアミン系光安定剤とベンゾトリアゾール系紫外線吸収剤を併用して使用するのが好ましい。
硬化性組成物には、生成する硬化物の引張特性を調整する物性調整剤を、必要に応じて添加してもよい。物性調整剤としては特に限定されないが、例えば、フェノキシトリメチルシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、n-プロピルトリメトキシシランなどのアルキルアルコキシシラン類;ジフェニルジメトキシシラン、フェニルトリメトキシシランなどのアリールアルコキシシラン類;ジメチルジイソプロペノキシシラン、メチルトリイソプロペノキシシラン、γ-グリシドキシプロピルメチルジイソプロペノキシシランなどのアルキルイソプロペノキシシラン;トリス(トリメチルシリル)ボレート、トリス(トリエチルシリル)ボレートなどのトリアルキルシリルボレート類;シリコーンワニス類;ポリシロキサン類などが挙げられる。前記物性調整剤を用いることにより、硬化性組成物の硬化物の硬度を上げたり、逆に硬度を下げ、破断伸びを出したりし得る。上記物性調整剤は単独で用いてもよく、2種以上併用してもよい。
硬化性組成物には、基材への接着性や密着性を高める目的、あるいはその他必要に応じて粘着付与樹脂を添加できる。粘着付与樹脂としては、特に制限はなく通常使用されているものを使うことが出来る。
また、硬化性組成物が前述の(A)成分を含むため、耐熱性の高いポリマーを硬化性組成物に添加しなくても、複合体における硬化性組成物の硬化物の膨れを抑制しやすい。このため、硬化性組成物において、耐熱性の高い粘着付与樹脂は、少量添加されるか、添加されなくてもよい。耐熱性の高い粘着付与樹脂の添加量は(A)成分100重量部に対して1重量部未満であることが好ましく、実質的に添加しないことがより好ましい。
硬化性組成物においてはエポキシ基を含有する化合物を使用できる。エポキシ基を有する化合物を使用すると硬化物の復元性を高めることができる。エポキシ基を有する化合物としてはエポキシ化不飽和油脂類、エポキシ化不飽和脂肪酸エステル類、脂環族エポキシ化合物類、エピクロルヒドリン誘導体に示す化合物およびそれらの混合物などが例示できる。具体的には、エポキシ化大豆油、エポキシ化あまに油、ビス(2-エチルヘキシル)-4,5-エポキシシクロヘキサン-1,2-ジカーボキシレート(E-PS)、エポキシオクチルステアレ-ト、エポキシブチルステアレ-トなどが挙げられる。これらのなかではE-PSが特に好ましい。エポキシ化合物は加水分解性シリル基を有するポリオキシアルキレン系重合体(A)100重量部に対して0.5~50重量部の範囲で使用するのがよい。
硬化性組成物には光硬化性物質を使用できる。光硬化性物資を使用すると硬化物表面に光硬化性物質の皮膜が形成され、硬化物のべたつきや硬化物の耐候性を改善できる。光硬化性物質とは、光の作用によってかなり短時間に分子構造が化学変化をおこし硬化などの物性的変化を生ずるものである。この種の化合物には有機単量体、オリゴマー、樹脂あるいはそれらを含む組成物など多くのものが知られており、市販の任意のものを採用し得る。代表的なものとしては、不飽和アクリル系化合物、ポリケイ皮酸ビニル類あるいはアジド化樹脂などが使用できる。
硬化性組成物には酸素硬化性物質を使用することができる。酸素硬化性物質としては空気中の酸素と反応し得る不飽和化合物を例示できる。酸素硬化性物質は、空気中の酸素と反応して硬化物の表面付近に硬化皮膜を形成し表面のべたつきや硬化物表面へのゴミやホコリの付着を防止するなどの作用をもたらす。酸素硬化性物質の具体例には、キリ油、アマニ油などで代表される乾性油や、該化合物を変性してえられる各種アルキッド樹脂;乾性油により変性されたアクリル系重合体、エポキシ系樹脂、シリコン樹脂;ブタジエン、クロロプレン、イソプレン、1,3-ペンタジエンなどのジエン系化合物を重合または共重合させてえられる1,2-ポリブタジエン、1,4-ポリブタジエン、C5~C8ジエンの重合体などの液状重合体や、これらジエン系化合物と共重合性を有するアクリロニトリル、スチレンなどの単量体とをジエン系化合物が主体となるように共重合させてえられるNBR、SBRなどの液状共重合体や、さらにはそれらの各種変性物(マレイン化変性物、ボイル油変性物など)などが挙げられる。これらは単独で用いてもよく、2種以上併用してもよい。これらのうちではキリ油や液状ジエン系重合体がとくに好ましい。又、酸化硬化反応を促進する触媒や金属ドライヤーを併用すると効果が高められる場合がある。これらの触媒や金属ドライヤーとしては、ナフテン酸コバルト、ナフテン酸鉛、ナフテン酸ジルコニウム、オクチル酸コバルト、オクチル酸ジルコニウムなどの金属塩や、アミン化合物などが例示される。
硬化性組成物には、表面性改良剤を添加することができる。表面性改良材としては、ラウリルアミンなどの長鎖アルキルアミン、リン酸2,2‘-メチレンビス(4,6-ジ-t-ブチルフェニル)ナトリウム、トリス(2,4-ジ-t-ブチルフェニル)ホスファイトなどのリン化合物、オキサゾリジン化合物などが挙げられる。
硬化性組成物にはエポキシ樹脂を併用することができる。
なお、ここで、エポキシ樹脂とは、未硬化の状態のエポキシ基を有する化合物として定義される。エポキシ樹脂が添加された硬化性組成物は、基材との関係において、接着剤、殊に外壁タイル用接着剤として好ましく作用する。エポキシ樹脂としてはエピクロルヒドリン-ビスフェノールA型エポキシ樹脂、エピクロルヒドリン-ビスフェノールF型エポキシ樹脂、テトラブロモビスフェノールAのグリシジルエーテルなどの難燃型エポキシ樹脂、ノボラック型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールAプロピレンオキシド付加物のグリシジルエーテル型エポキシ樹脂、p-オキシ安息香酸グリシジルエーテルエステル型エポキシ樹脂、m-アミノフェノール系エポキシ樹脂、ジアミノジフェニルメタン系エポキシ樹脂、ウレタン変性エポキシ樹脂、各種脂環式エポキシ樹脂、N,N-ジグリシジルアニリン、N,N-ジグリシジル-o-トルイジン、トリグリシジルイソシアヌレート、ポリアルキレングリコールジグリシジルエーテル、グリセリンなどのごとき多価アルコールのグリシジルエーテル、ヒダントイン型エポキシ樹脂、石油樹脂などのごとき不飽和重合体のエポキシ化物などが例示される。エポキシ樹脂は、これらに限定されるものではなく、一般に使用されているエポキシ樹脂が使用されうる。エポキシ基を少なくとも分子中に2個含有するものが、硬化に際し反応性が高く、また硬化物が3次元的網目をつくりやすいなどの点から好ましい。さらに好ましいものとしてはビスフェノールA型エポキシ樹脂類またはノボラック型エポキシ樹脂などが挙げられる。
硬化性組成物には、ポリリン酸アンモニウムやトリクレジルホスフェートなどのリン系化合物、水酸化アルミニウム、水酸化マグネシウム、および、熱膨張性黒鉛などの難燃剤を添加することができる。上記難燃剤は単独で用いてもよく、2種以上併用してもよい。
硬化性組成物は、すべての配合成分を予め配合密封保存し、施工後空気中の湿気により硬化する1成分型として調製することも可能であり、硬化剤として別途硬化触媒、充填材、可塑剤、水などの成分を配合しておき、該配合材と有機重合体組成物を使用前に混合する2成分型として調製することもできる。作業性の点からは、1成分型が好ましい。
-SiRa(OR1)3-a (1)
(Rはそれぞれ独立にヘテロ原子含有基またはハロゲン原子からなる置換基を有していてもよい炭素数1~10の炭化水素基を表す。R1はそれぞれ独立に炭素数2~10の炭化水素基を表す。aは0、1、2である。)
で表される加水分解性記を有するシランカップリング剤を用いるのが好ましい。具体的には、n-プロピルトリエトキシシラン、ビニルトリエトキシシラン、γ-メルカプトプロピルトリエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、エチルシリケートが挙げられる。
本発明では、加水分解性シリル基を有するポリオキシアルキレン系重合体(A)を含有する硬化性組成物を基材に塗布した後、加熱硬化型塗料を塗布し、その後に加熱を行って複合体を製造する。
以上説明した方法により製造され得る複合体の用途としては、自動車の車体・部品、トラック、バスなどの大型車両の車体・部品、列車の車両・部品、航空機用部品、船舶用部品、コンテナ、電機・電子部品、家電製品、各種機械部品、サッシなどの建材などが挙げられる。
カラム:東ソー製TSK-GEL Hタイプ
溶媒:THF
分子量:ポリスチレン換算
測定温度:40℃
実施例中の末端基換算分子量は、水酸基価をJIS K 1557の測定方法により、ヨウ素価をJIS K 0070の測定方法により求め、有機重合体の構造(使用した重合開始剤によって定まる分岐度)を考慮して求めた分子量である。
数平均分子量が約3,000のポリオキシプロピレントリオールを開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキサイドの重合を行い、末端に水酸基を有する数平均分子量16400(末端基換算分子量12200)、分子量分布Mw/Mn=1.31のポリオキシプロピレン(P-1)を得た。得られた水酸基末端ポリオキシプロピレン(P-1)の水酸基に対して1.2モル当量のナトリウムメトキシドを28%メタノール溶液として添加した。真空脱揮によりメタノールを留去した後、重合体(P-1)の水酸基に対して、さらに1.5モル当量の塩化アリルを添加して末端の水酸基をアリル基に変換した。未反応の塩化アリルを減圧脱揮により除去した。得られた未精製のアリル基末端ポリオキシプロピレン100重量部に対し、n-ヘキサン300重量部と、水300重量部を混合撹拌した後、遠心分離により水を除去し、得られたヘキサン溶液にさらに水300重量部を混合撹拌し、再度遠心分離により水を除去した後、ヘキサンを減圧脱揮により除去した。以上により、末端部位にアリル基を有するポリオキシプロピレン重合体(Q-1)を得た。この重合体(Q-1)500gに対して白金ジビニルジシロキサン錯体溶液25μlを加え、撹拌しながら、トリエトキシシラン14.6gをゆっくりと滴下した。90℃で2時間反応させた後、未反応のトリエトキシシランを減圧下留去する事により、末端にトリエトキシシリル基を有する数平均分子量約16400のポリオキシプロピレン(A-1)を得た。重合体(A-1)はトリエトキシシリル基を1分子中に平均2.2個有することが分かった。
合成例1で得られた末端部位にアリル基を有するポリオキシプロピレン重合体(Q-1)500gに対して白金ジビニルジシロキサン錯体溶液25μlを加え、撹拌しながら、ジメトキシメチルシラン8.9gをゆっくりと滴下した。100℃で2時間反応させた後、未反応のジメトキシメチルシランを減圧下留去する事により、末端にジメトキシメチルシリル基を有する数平均分子量約16400のポリオキシプロピレン(B-1)を得た。重合体(B-1)はジメトキシメチルシリル基を1分子中に平均2.1個有することが分かった。
合成例1で得られたトリエトキシシリル基を有するポリオキシプロピレン(A-1)100重量部、メタノール15重量部、35wt%の塩酸水溶液18ppmを加えて70℃で1時間反応させた。その後、エポキシ化大豆油(新日本理化(株)製サンソサイザーE-2000H)を900ppm添加し、90℃で1時間撹拌した。得られたメタノール溶液からメタノールを減圧脱揮し、末端にトリメトキシシリル基を有する数平均分子量約16400のポリオキシプロピレン(B-2)を得た。重合体(B-2)はトリメトキシシリル基を1分子中に平均2.2個有することが分かった。
重合体(A-1)100重量部に対して、IRGANOX245(BASF・ジャパン(株)製、ヒンダードフェノール系酸化防止剤)3重量部、PPG3000(武田薬品(株)製、商品名:アクトコールP-23)50重量部、ネオライトSP(竹原化学工業(株)製:沈降炭酸カルシウム)160重量部、LM2200(丸尾カルシウム(株)製:重質炭酸カルシウム)54重量部、A-1100(Momentive製:γ-アミノプロピルトリエトキシシラン)5重量部、U-220H(日東化成(株)製:ジブチル錫ビスアセチルアセトナート)2重量部添加し、スパチュラで十分混合した後、自転公転ミキサーを用いて均一に混合脱泡した。
A-1100 5重量部の代わりに、A-1100を3重量部、エチルシリケート48(コルコート(株)製)4重量部を使用した以外は実施例1と同様の操作を行い、得られた硬化物の評価を行った。結果を表1に示す。
実施例1と同様にして硬化性組成物を調製した。得られた硬化性組成物をアルミ板の上に20mm×120mm×2mm(厚み)のサイズに施工する。アルミに施工した硬化性組成物を23℃/50%RHの環境下で20分養生したのち、エポキシ系の塗料を硬化性組成物上に塗布した。エポキシ系塗料の塗布後、直ちに100℃、または160℃に調整した乾燥機内で20分間養生し、養生完了後直ちに取り出し10分間冷却した。冷却後の複合体における硬化物の発泡状態を目視にて観察し、発泡の有無を確認した。複合体における硬化した塗膜について、硬化性組成物の硬化物の発泡に起因する膨れが無く、硬化性組成物の硬化物の内部に細かい気泡も無い状態を○、硬化性組成物の硬化物の内部に細かい気泡があるが硬化した塗膜の表面にシワや膨れがない場合を△、硬化した塗膜の表面にシワや膨れがある状態を×、とした。
その結果、100℃での加熱でも、160での加熱でも、アルミ板からなる基材と、トリエトキシシリル基を加水分解性基として有する(A)成分を含有する硬化性組成物の硬化物と、加熱硬化型塗料の塗膜とからなる複合体では、上記評価は○であり、膨れや発泡の問題が無かった。
重合体(A-1)の代わりに重合体(B-1)を、A-1100の代わりにA-1110(Momentive製:γ-アミノプロピルトリメトキシシラン)を使用した以外は実施例1と同様の操作を行い、得られた硬化物の評価を行った。結果を表1に示す。
重合体(A-1)の代わりに重合体(B-1)を使用した以外は実施例1と同様の操作を行ったが、作製中に硬化が進行し、硬化性組成物が得られなかった。
重合体(A-1)の代わりに重合体(B-1)を、U-220H 2重量部の代わりにU-220H 1重量部を使用した以外は実施例1と同様の操作を行い、得られた硬化物の評価を行った。結果を表1に示す。
重合体(A-1)の代わりに重合体(B-2)を、A-1100の代わりにA-1110(Momentive製:γ-アミノプロピルトリメトキシシラン)、U-220H 2重量部の代わりにU-100(日東化成(株)製:ジブチル錫ジラウレート) 0.2重量部を使用した以外は実施例1と同様の操作を行い、得られた硬化物の評価を行った。結果を表1に示す。
比較例1と同様にして硬化性組成物を調製した。得られた硬化性組成物を用いて、実施例3と同様にして、アルミ板からなる基材と、硬化性組成物の硬化物と、加熱硬化型塗料の塗膜とからなる複合体における加熱後の膨れについて評価した。
その結果、100℃での加熱では○評価であり、膨れや発泡の問題が無かったものの、160℃での加熱では×評価であり、硬化性組成物の硬化物における発泡の影響で、塗膜表面にも膨れが生じた。
160℃で加熱する場合の×評価は、トリメトキシ基を有している重合体(B-1)を硬化性組成物に配合したことに起因すると考えられる。
Claims (10)
- 基材と、硬化性組成物の硬化物と、加熱硬化型塗料の塗膜との複合体の製造方法であって、
前記硬化性組成物を基材に塗布した後、加熱硬化型塗料を塗布し、その後加熱を行うことを含み、
前記硬化性組成物が、加水分解性シリル基を有するポリオキシアルキレン系重合体(A)を含み、
前記加水分解性シリル基が、下記一般式(1):
-SiRa(OR1)3-a (1)
(Rはそれぞれ独立にヘテロ原子含有基またはハロゲン原子からなる置換基を有していてもよい炭素数1~10の炭化水素基を表し、R1はそれぞれ独立に炭素数2~10の炭化水素基を表し、aは0、1、2である。)
で表される、製造方法。 - 前記加熱の温度が、140~250℃である請求項1に記載の複合体の製造方法。
- 前記加熱の温度が、150~250℃である請求項2に記載の複合体の製造方法。
- 前記硬化性組成物を前記基材に塗布した後、前記硬化性組成物が硬化する前に前記加熱を行う請求項1~3のいずれか1項に記載の複合体の製造方法。
- 前記R1がエチル基である請求項1~4のいずれか1項に記載の複合体の製造方法。
- 前記aが0である請求項1~5のいずれか1項に記載の複合体の製造方法。
- 前記硬化性組成物が、さらに加水分解性基がメトキシ基であるシランカップリング剤を含有し、前記シランカップリング剤の含有量が、前記加水分解性シリル基を有するポリオキシアルキレン系重合体(A)100重量部に対して2重量部以下である請求項1~6のいずれか1項に記載の複合体の製造方法。
- 硬化性組成物が含有する加水分解性シリル基を有する化合物の加水分解性シリル基が一般式(1)に示す加水分解性シリル基のみである請求項1~6のいずれか1項に記載の複合体の製造方法。
- 前記加水分解性シリル基を有するポリオキシアルキレン系重合体(A)の一分子中に含まれるシリル基の数が、1.8~3.0個である請求項1~8のいずれか1項に記載の複合体の製造方法。
- 基材と、硬化性組成物の硬化物と、加熱硬化型塗料の塗膜との複合体であって、
前記硬化性組成物が、加水分解性シリル基を有するポリオキシアルキレン系重合体(A)を含み、
前記加水分解性シリル基が、下記一般式(1):
-SiRa(OR1)3-a (1)
(Rはそれぞれ独立にヘテロ原子含有基またはハロゲン原子からなる置換基を有していてもよい炭素数1~10の炭化水素基を表し、R1はそれぞれ独立に炭素数2~10の炭化水素基を表し、aは0、1、2である。)
で表される、複合体。
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