Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
  • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
  • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates

Definitions

• the present invention relates to a urethane curable composition containing a catalyst, a polyol, a polyisocyanate and silica particles.
• General-purpose plastics such as acrylic resin, polycarbonate resin, polystyrene resin and ABS resin are easy to mold, lightweight and excellent in impact resistance, and are used in various fields.
• moldings made of these resins are inferior in scratch resistance and abrasion resistance to the surface of glass, etc., so scratches or dents are caused by scratching with nails, contact with or contact with dust and pebbles.
• aesthetics and functions are easily impaired.
• a method of covering and protecting the surface of a resin molded body with a coating film having excellent scratch resistance is generally performed, and various curable compositions having such functions have been proposed. I came.
• the curable composition using the urethanization reaction between polyol and polyisocyanate is suitable for low-temperature thermal curing and short-time curing that does not cause thermal deformation of the resin molding, and various compositions are proposed. It has been.
• urethane curable compositions a coating film containing silica particles has high surface hardness and excellent scratch resistance, and therefore various compositions have been proposed (for example, JP-A-2002-327146). Gazette, JP-T 2009-539603, JP-A 2010-189477, JP-A 2012-21111.
• metal compounds such as dibutyltin dilaurate, tin octylate and lead naphthenate and salts thereof (F. Hosttler, EF Cox, Ind. Eng. Chem. , 52,609 (1960)), metal chelate compounds such as zirconium tetraacetylacetonate and titanium diisopropoxybis (ethylacetoacetate) and organic amines such as triethylenediamine, triethylamine and tri-n-butylamine (J. Burkus, J. Org. Chem., 26, 779 (1961)) and salts thereof (JP-A-60-240415).
• dialkyl tin compounds such as dibutyl tin dilaurate are particularly widely used because of their high catalytic activity.
• acidic substances such as silica particles having the same chemical structure as silica gel are known as catalyst deactivators in the urethanization reaction between hydroxyl groups and isocyanate groups or in the isocyanurate reaction between isocyanate groups (special characteristics).
• catalyst deactivators in the urethanization reaction between hydroxyl groups and isocyanate groups or in the isocyanurate reaction between isocyanate groups (special characteristics).
• Kaihei 08-027123 a urethane curable composition containing the same hardly undergoes the curing reaction.
• urethane curing catalysts As described above, these are typical urethane curing catalysts described in JP-A No. 2002-327146, JP-T 2009-539603, JP-A 2010-189477, and JP-A 2012-21111.
• a temperature at which the general-purpose plastic molded body does not undergo thermal deformation (for example, the thermal deformation temperature is an acrylic resin).
• the thermal deformation temperature is an acrylic resin.
• the curing reaction does not proceed sufficiently.
• an organic amine compound is used as a catalyst, it is adsorbed on silica particles that are acidic substances and aggregates them, so that it is practically difficult to use this curable composition.
• the present invention solves the above-mentioned problems, and the object thereof is a urethane curable composition containing silica particles, even under curing conditions at a low temperature below the heat distortion temperature of a general-purpose plastic molded body, It is providing the curable composition containing the catalyst which fully advances hardening reaction.
• catalyst (a) polyol (b) having two or more hydroxyl groups in one molecule, polyisocyanate (c) having two or more isocyanate groups in one molecule, and silica A urethane curable composition containing particles (d),
• the catalyst (a) is a carboxylic acid metal salt represented by the formula (1), M (OCOR) n (1)
• M is Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, or Pb
• R is saturated carbonization having 1 to 20 carbon atoms.
• the polyisocyanate (c) is blended such that the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate (c) to the hydroxyl group of the polyol (b) is 0.25 to 5.0
• the catalyst (a) is 0.1 to 2.0% by weight based on the silica particles (d).
• M is preferably Li, Na, K, Rb or Cs.
• a curing reaction can sufficiently proceed even under curing conditions in a short time of several tens of minutes below the heat distortion temperature of a general-purpose plastic molded body.
• M is an alkali metal, such as Li, Na, K, Rb, or Cs
• a urethane curable composition excellent in environmental safety and pot life of the curable composition is provided. be able to.
• the urethane curable composition of the present invention is a composition containing a catalyst (a), a polyol (b), a polyisocyanate (c), and silica particles (d).
• the catalyst used in the present invention is a component that promotes the urethanization reaction between a hydroxyl group and an isocyanate group, and compared with other urethanization catalysts in curing a urethane curable composition containing silica particles. It has a function capable of reacting at a low temperature for a short time, and also promotes the reaction between isocyanates.
• the catalyst used in the present invention is a carboxylic acid metal salt represented by the following formula (1).
• M is Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, or Pb, and R is saturated carbonization having 1 to 20 carbon atoms.
• R is saturated carbonization having 1 to 20 carbon atoms.
• the carboxylic acid metal salt includes a carboxylic acid having any one of a saturated hydrocarbon group, a chain unsaturated hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and Li, Na, K, Rb, Cs. , Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, and a carboxylic acid metal salt composed of a metal selected from Pb.
• Examples of the saturated hydrocarbon group include a straight chain saturated hydrocarbon group such as a methyl group and an ethyl group, and a branched chain saturated hydrocarbon group such as an isopropyl group and an isobutyl group.
• Examples of the chain unsaturated hydrocarbon group include alkenyl groups obtained by removing one hydrogen atom from any carbon atom of the saturated hydrocarbon group.
• Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as a cyclohexyl group.
• Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group and a benzyl group.
• the hydrocarbon group is a linear saturated hydrocarbon group having 1 to 11 carbon atoms such as a methyl group, a heptyl group, and an undecyl group, or a carbon atom, from the viewpoints of solubility in a urethane curable composition and catalyst efficiency.
• a chain unsaturated hydrocarbon group having an alkenyl group having a number of 2 to 17 is preferred.
• the metal is an alkali metal of Li, Na, K, Rb, or Cs, or a transition metal of Fe, Mn, Co, Ni, Cu, Zn, or Pb from the viewpoint of solubility in the curable composition or catalyst efficiency.
• alkali metals such as Li, Na, K, Rb, and Cs are more preferable.
• the metal carboxylate is sodium acetate, potassium acetate, potassium octoate, potassium oleate, Linear saturated fatty acid alkali metal salts such as rubidium acetate, cesium acetate and potassium laurate, or chain unsaturated fatty acid alkali metal salts such as sodium oleate and potassium oleate are preferred.
• the amount of the catalyst used in the present invention is 0.1 to 2.0% by weight, preferably 0.2 to 1.7% by weight, based on the amount of silica particles (d) described below. It is a range. If it is less than 0.1% by weight based on the silica particles, the curing reaction may not proceed sufficiently. On the other hand, if it exceeds 2.0% by weight based on the silica particles, the pot life is too short, workability and storage stability are deteriorated, and the performance of the composition after curing may be affected.
• polyol used in the present invention a known one can be used, which is a hydroxyl compound having two or more hydroxyl groups in one molecule.
• polyols include ethanediol, propanediol, 1,4-butanediol, 1,6-hexanediol, cyclohexyldimethanol, methylpropanediol, neopentylglycol, butylethylpropanediol, glycerin, trimethylolethane, trimethylolpropane.
• Low molecular polyols such as polycaprolactone triol, ditrimellirol propane, pentaerythritol, polycaprolactone tetraol, dipentaerythritol, sorbitol, mannitol; alkylene polyols such as ethylene glycol and propylene glycol, and alkylene oxides such as ethylene oxide and propylene oxide
• a polyether polyol obtained by reacting with A polyester polyol obtained by reacting a carboxylic acid with an alkylene polyol such as ethylene glycol or propylene glycol; an alkylene carbonate such as ethylene carbonate or trimethylene carbonate; and an alkylene polyol such as ethylene glycol or 1,3-propanediol; Polycarbonate diol obtained by reacting with a homopolymer of a hydroxyl group-containing acrylic monomer such as 2-hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acryl
• the blending amount of the polyol (b) in the present invention is 5 to 90% by weight, preferably 7 to 85% by weight, more preferably 10 to 75%, based on the total weight of the components (b) to (d). It is in the range of wt%. If it is such a compounding quantity, flexibility and hardness can be expressed in the hardened
• (C) Polyisocyanate As the polyisocyanate used in the present invention, a known one can be used, which is a bifunctional or higher functional isocyanate. Examples of the bifunctional isocyanate include hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1-3 bis (isocyanatomethyl) cyclohexane, 4,4-dicyclohexyl diisocyanate, and the like. These modified products, for example, synthesized from the above diisocyanates as starting materials, include burettes, trimethylolpropane adducts, isocyanurates, allophanates, and the like. Moreover, these block type isocyanates can also be used. These may be used alone or in combination of two or more.
• the polyisocyanate is blended and used so that the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyol is in the ratio of 0.25 to 5.0. Preferably it is in the range of 0.5 to 3.0, preferably 0.8 to 2.0. If it is such a compounding quantity, the crosslinked density of hardened
• the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate and the hydroxyl group of the polyol is the total number of NCO groups of the polyisocyanate and the total number of OH groups of the polyol contained in the curable composition. The ratio.
• silica particles used in the present invention have a primary particle size of 1 to 500 nm.
• the silica is fumed silica, colloidal silica or amorphous silica.
• Examples of commercially available silica particles include Aerosil R-972 and Aerosil R-200 manufactured by Degussa.
• silica particles (silica sol) dispersed in an organic solvent include methanol-dispersed silica sol (trade name: MA-ST), isopropyl alcohol-dispersed silica sol (trade name: IPA-ST), n- Butanol-dispersed silica sol (trade name: NBA-ST), ethylene glycol-dispersed silica sol (trade name: EG-ST), xylene / butanol-dispersed silica sol (trade name: XBA-ST), ethyl cellosolve-dispersed silica sol (trade name: ETC-ST) ), Butyl cellosolve dispersed silica sol (trade name: BTC-ST), dimethylformamide dispersed silica sol (trade name: DBF-ST), dimethylacetamide dispersed silica sol (trade name: DMAC-ST), methyl ethyl ketone dispersed silica sol (trade name: MEK-ST)
• the amount of the silica particles (d) is 5 to 85% by weight, preferably 10 to 80% by weight, based on the total weight of the components (b) to (d). If it is such a compounding quantity, the improvement of hardness can be provided to hardened
• this composition can be diluted with a diluent solvent in order to adjust the solid content of the curable composition.
• a diluent solvent for example, alcohol-based, carboxylic acid ester-based, ketone-based, amide-based, ether-based, aliphatic and aromatic hydrocarbon-based organic solvents are used.
• alcohol solvents include methanol, isopropyl alcohol, n-butanol, diacetone alcohol, 2-methoxyethanol (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), tertiary amyl Alcohol, etc .; carboxylate solvents such as ethyl acetate, n-propyl acetate, butyl acetate, butyl formate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexanone; amide solvents such as dimethyl Formamide, dimethylacetamide, etc .; ether solvents include diethyl ether, methoxytoluene, 1,2-dimethoxyethane, 1,2-dibutoxyethane, 1,1-dimethoxymethane Emissions, 1,1-dimethoxyethane, 1,4-
• the composition of the present invention is cured by heat treatment.
• the heat treatment temperature varies depending on the type and amount of the catalyst and the type and amount of the solvent, but is usually 40 ° C. or higher and 200 ° C. or lower, preferably 60 ° C. or higher and 150 ° C. or lower, more preferably 75 ° C. or higher and 130 ° C. or lower.
• the heat treatment is generally performed at a temperature equal to or lower than the heat deformation temperature.
• the temperature is usually 80 ° C. or lower for an acrylic resin and 130 ° C. or lower for a polycarbonate resin.
• the curable composition of the present invention can be produced by mixing the catalyst (a), polyol (b), polyisocyanate (c) and silica particles (d) so as to be uniform in an organic solvent.
• Various other additives commonly used in the chemical industry for example, UV absorbers, antioxidants, antifoaming agents, leveling agents, rheology control agents, viscosity modifiers, matting agents, light stability Agents, dyes, pigments and the like can be appropriately used in conventional amounts within a range that does not impair the effects of the present invention.
• the curable composition of the present invention can be used for adhesives, mold preparations, vibration-proof materials, vibration-damping materials, sound-proof materials, foam materials, paints, spray materials, and the like.
• composition of Examples 1-28 and Comparative Examples 1-21 The above components (a), (b) and (d) and the diluent solvent were blended in the proportions shown in Table 1, stirred sufficiently, and the solubility of the catalyst was visually evaluated according to the following method. Then, after adding the said (c) component in the ratio shown in Table 1, and stirring sufficiently, the consumption rate and catalytic ability of an isocyanate group were evaluated in accordance with the following method. The results of each test are listed in Table 2.
• each curable composition is applied onto a silicon wafer (2 cm ⁇ 2 cm, manufactured by Silicon Technology Co., Ltd.) and subjected to heat treatment under predetermined conditions (A: 115 ° C. ⁇ 20 minutes, B: 150 ° C. ⁇ 20 minutes).
• the infrared absorption spectra before and after were measured by the transmission method. Prior to heating, nitrogen was blown to volatilize the solvent so as not to be affected by the C—H stretching peak intensity of the solvent as much as possible.
• the isocyanate (NCO) group consumption rate was calculated based on the following formula (2) from the N ⁇ C ⁇ O reverse symmetrical stretching peak intensity present at 2270 cm ⁇ 1 and the CH stretching peak intensity present at 2952 cm ⁇ 1 . . Moreover, based on the obtained NCO group consumption rate, each catalytic ability was evaluated as follows. Evaluation of catalytic ability A: NCO consumption rate is 80% or more under A condition, B: 55% or more and less than 80% under A condition, C: other than those

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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)
• Polyurethanes Or Polyureas (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2013
  • 2013-03-25 JP JP2013062033A patent/JP5696735B2/ja active Active
• 2014
  • 2014-03-18 EP EP14774736.4A patent/EP2980112B1/en active Active
  • 2014-03-18 IN IN2572DEN2015 patent/IN2015DN02572A/en unknown
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  • 2014-03-18 WO PCT/JP2014/057261 patent/WO2014156810A1/ja not_active Ceased
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