WO2011070865A1 - Composition de résine d'uréthane, matériau de revêtement, adhésif, produit durci obtenu en utilisant la composition, et procédé de production d'un produit durci - Google Patents

Composition de résine d'uréthane, matériau de revêtement, adhésif, produit durci obtenu en utilisant la composition, et procédé de production d'un produit durci Download PDF

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Publication number
WO2011070865A1
WO2011070865A1 PCT/JP2010/068892 JP2010068892W WO2011070865A1 WO 2011070865 A1 WO2011070865 A1 WO 2011070865A1 JP 2010068892 W JP2010068892 W JP 2010068892W WO 2011070865 A1 WO2011070865 A1 WO 2011070865A1
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WIPO (PCT)
Prior art keywords
urethane resin
group
alcohol
resin composition
hydrolyzable silyl
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PCT/JP2010/068892
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English (en)
Japanese (ja)
Inventor
武志 岩尾
直孝 後藤
邦彦 小松崎
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Dic株式会社
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Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to KR1020117017656A priority Critical patent/KR101766735B1/ko
Priority to US13/501,124 priority patent/US8420725B2/en
Priority to EP10835787.2A priority patent/EP2457951B1/fr
Priority to CN201080014216.3A priority patent/CN102365333B/zh
Priority to JP2011505051A priority patent/JP4784715B2/ja
Publication of WO2011070865A1 publication Critical patent/WO2011070865A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4261—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups prepared by oxyalkylation of polyesterpolyols
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • 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
    • C08G18/83—Chemically modified polymers
    • 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
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the present invention relates to a urethane resin composition that can be used in various applications including the production of coating agents, adhesives, and various molded products.
  • urethane resin compositions solvent-based, water-based, and solvent-free ones are conventionally known, and they are used in various applications including molding materials such as films and sheets, adhesives, and coating agents. Yes.
  • solvent-based urethane resin compositions are still widely used because they can generally form a film having excellent durability and water resistance as compared with water-based urethane resin compositions.
  • urethane resin compositions using alcohol as a solvent which has a lower environmental impact than dimethylformamide
  • the molecular terminal or side obtained by a specific production method can be used.
  • An alcohol-soluble urethane resin composition containing a polyurethane resin having a hydrolyzable silyl group in the chain and an alcohol having 1 to 7 carbon atoms is known (for example, see Patent Document 1).
  • the urethane resin composition By the way, as the uses of the urethane resin composition are further expanded, for example, in the fields of automobile members, household appliance members, electronic materials, etc., it is a case where it is placed in a high temperature environment of approximately 200 ° C. or higher, preferably 260 ° C. or higher.
  • a urethane resin composition capable of forming a film having very excellent heat resistance that does not cause deformation or mass loss.
  • a method for improving the heat resistance a method is known in which a large number of functional groups that can become crosslinking points are introduced into a urethane resin.
  • a coating resin, an adhesive, and the like are generally urethane resin compositions into which a large number of the above-mentioned crosslinking points have been introduced, while excellent storage stability that does not cause gelation even when left at room temperature is required. It was difficult to say that it had practically sufficient storage stability and coating workability.
  • the problem to be solved by the present invention is a urethane resin composition capable of forming a cured product such as a film having excellent storage stability and coating workability without causing gelation with time and excellent heat resistance. Is to provide.
  • the resin composition containing inorganic particles having a functional group capable of crosslinking with the alcohol-soluble urethane resin While the inventors proceeded with the study based on the alcohol-soluble urethane resin composition described in Patent Document 1, the resin composition containing inorganic particles having a functional group capable of crosslinking with the alcohol-soluble urethane resin.
  • the product can maintain good storage stability, coating workability and handleability without increasing the viscosity in the presence of alcohol, and the resin composition is coated on the surface of the substrate, and the alcohol is volatilized.
  • cured materials, such as a film provided with the outstanding heat resistance, can be formed.
  • the present invention is a urethane resin composition containing an alcohol-soluble urethane resin (A) having a hydrolyzable silyl group, inorganic particles (B), and alcohol (C), wherein the inorganic particles (B ) Has a functional group [Y] capable of reacting with the functional group [X] generated from the hydrolyzable silyl group of the urethane resin (A), and a urethane resin composition,
  • the present invention relates to a coating material and an adhesive agent, and a cured product obtained using the urethane resin composition.
  • the present invention applies the composition obtained by mixing the urethane resin composition and water or an acid catalyst, if necessary, onto a substrate surface, and the alcohol (C) contained in the coating layer ),
  • the present invention relates to a method for producing a cured product characterized by reacting with [Y] to form a bond.
  • the urethane resin composition of the present invention has excellent storage stability and coating workability without causing gelation over time even when left at room temperature for a long time, and has excellent heat resistance for a long time. Since a film that can be maintained over a wide range can be formed, it can be used, for example, as a surface coating for automobile parts, electronic parts, etc., and as a coating agent or adhesive used for bonding them. In addition, the urethane resin composition of the present invention can be used as a molding material for cured products that require a very high level of heat resistance, such as medical materials, automobile parts, home appliance parts, and electronic materials. is there.
  • the present invention is a urethane resin composition containing a hydrolyzable silyl group-containing alcohol-soluble urethane resin (A), inorganic particles (B), alcohol (C), and other additives as necessary.
  • the inorganic particles (B) have a functional group [Y] that can react with the functional group [X] generated from the hydrolyzable silyl group of the urethane resin (A). It is a urethane resin composition.
  • the urethane resin composition is obtained by dissolving or dispersing the alcohol-soluble urethane resin (A) and the inorganic particles (B) in the alcohol (C) using the alcohol (C) as a solvent.
  • the alcohol-soluble urethane resin (A) and the inorganic particles (B) often react independently in the alcohol (C) as a solvent to form a bond and exist independently. This is because the hydrolyzable silyl group of the urethane resin (A) does not hydrolyze in the alcohol (C), and therefore does not form a silanol group corresponding to the functional group [X].
  • the urethane resin (A) having a functional group [X] such as a silanol group is used in advance
  • the silanol group is Since a hydrolyzable silyl group, specifically an alkoxysilyl group, is formed reversibly, it is difficult to form a bond with the functional group [Y] of the inorganic particles (B) in the presence of the alcohol (C).
  • the urethane resin composition of the present invention can maintain good storage stability and coating workability for a long period of time without causing an increase in viscosity over time.
  • the urethane resin composition of this invention is a range which does not impair the said favorable storage stability etc., the said alcohol soluble type urethane resin (A) and the said inorganic particle (B) will couple
  • the urethane resin composition of the present invention preferably has a viscosity in the range of 500 to 10,000 mmPa ⁇ s from the viewpoint of good coating workability and the like.
  • the urethane resin composition of the present invention when the urethane resin composition of the present invention is applied to the surfaces of various substrates, dried, and the alcohol (C) contained in the coating layer is volatilized and removed, the alcohol-soluble urethane resin (A) is hydrolyzed.
  • the functional silyl group is hydrolyzed by moisture (water) in the atmosphere, intentionally added water or the like to form a functional group [X] such as a silanol group.
  • a functional group [X] such as a silanol group rapidly forms a bond with the functional group [Y] of the inorganic particles (B) through a rapid hydrolysis condensation reaction.
  • the urethane resin composition of this invention can form hardened
  • the urethane resin composition of the present invention preferably contains 10 to 400 parts by mass of the inorganic particles (B) with respect to 100 parts by mass of the alcohol-soluble urethane resin (A).
  • the urethane resin composition of the present invention is excellent in storage because the alcohol (C) is used in the range of 50 to 300 parts by mass with respect to 100 parts by mass of the alcohol-soluble urethane resin (A). It is preferable for imparting stability, coating workability, and the like, and more preferably used in the range of 50 to 200 parts by mass.
  • the alcohol-soluble urethane resin (A) used in the present invention has a hydrolyzable silyl group in the presence of alcohol (C).
  • the hydrolyzable silyl group is cured to form a cured product such as a film, it reacts with moisture (water) in the atmosphere to form a functional group [X] such as a silanol group.
  • the said functional group [X] reacts with the functional group [Y] which the inorganic particle (B) mentioned later has, and forms a strong chemical bond (covalent bond).
  • the heat resistance of the obtained cured product can be remarkably improved.
  • the hydrolyzable silyl group of the alcohol-soluble urethane resin (A) is a functional group in which the hydrolyzable group is directly bonded to a silicon atom, and is represented by, for example, the following general formula (I). Functional group.
  • R 1 is a monovalent organic group such as an alkyl group, aryl group or aralkyl group
  • R 2 is a halogen atom, alkoxy group, acyloxy group, phenoxy group, aryloxy group, mercapto group, amino group, amide A group, an aminooxy group, an iminooxy group or an alkenyloxy group, and x is an integer of 0 to 2.
  • alkyl group examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, hexyl, and isohexyl groups. It is done.
  • Examples of the aryl group include a phenyl group, a naphthyl group, and a 2-methylphenyl group.
  • Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.
  • Examples of the acyloxy group include acetoxy, propanoyloxy, butanoyloxy, phenylacetoxy, acetoacetoxy, and the like.
  • Examples of the aryloxy group include phenyloxy, naphthyloxy, and the like.
  • Examples of the group include allyloxy group, 1-propenyloxy group, isopropenyloxy group and the like.
  • R 2 is preferably independently an alkoxy group, since it is easy to remove a leaving component such as the general formula R 2 OH that can be generated by hydrolysis.
  • the alcohol-soluble urethane resin (A) since the alcohol-soluble urethane resin (A) is usually difficult to hydrolyze in the presence of the alcohol (C), it does not form a functional group [X] such as a silanol group, and does not form a functional group such as an alkoxysilyl group. Although it has a decomposable silyl group, a very small part thereof may be present in the urethane resin (A) in a silanol group state.
  • the hydrolyzable silyl group is present in the range of 0.5 to 60% by mass relative to the mass of the alcohol-soluble urethane resin (A) in order to improve the heat resistance of the resulting cured product. More preferably, it is present in the range of 0.5 to 30% by mass, particularly preferably in the range of 1 to 20% by mass.
  • the alcohol-soluble urethane resin (A) it is preferable to use a resin having a number average molecular weight in the range of 1,000 to 300,000 from the viewpoint of improving ease of dissolution in the alcohol (C) described later.
  • the range of 1500 to 100,000 is more preferred, and 1500 to 50000 is particularly preferred.
  • the alcohol-soluble urethane resin (A) having a number average molecular weight of more than 10,000 is preferably produced by the (Method 1) described later from the viewpoint of improving production efficiency.
  • the alcohol-soluble urethane resin has a relatively low molecular weight in the range of generally 1000 to 30000, preferably 1000 to 10,000. It is preferable for maintaining good solubility in alcohol (C).
  • the alcohol-soluble urethane resin (A) is obtained, for example, by reacting a polyisocyanate (a1) and a polyol (a2) containing at least one selected from the group consisting of polyether polyol, polyester polyol and polycarbonate polyol.
  • a coupling agent (a4) comprising at least one selected from the group consisting of a urethane prepolymer (a3) having an isocyanate group or a hydroxyl group in the obtained molecule, an amino group-containing silane coupling agent and an isocyanate group-containing silane coupling agent.
  • the chain extender (a5) is necessary, if necessary, the chain extender (a5).
  • the alcohol-soluble urethane resin (A) includes, for example, a step of producing a urethane prepolymer (a3) having an isocyanate group or a hydroxyl group in the molecule (first step), and the urethane prepolymer.
  • Alcohol-soluble urethane that can be dissolved in the alcohol (C) by reacting (a3) with the coupling agent (a4) and the chain extender (a5) or only the coupling agent (a4). It can manufacture by the process (2nd process) which manufactures resin (A).
  • the polyisocyanate (a1) is reacted with a polyol (a2) containing one or more selected from the group consisting of a polyester polyol, a polyether polyol, and a polycarbonate polyol in the absence of a solvent.
  • a polyol (a2) containing one or more selected from the group consisting of a polyester polyol, a polyether polyol, and a polycarbonate polyol in the absence of a solvent.
  • This is a step for producing a urethane prepolymer (a3) having an isocyanate group or a hydroxyl group in the molecule.
  • the reaction between the polyisocyanate (a1) and the polyol (a2) is carried out by the equivalent ratio of the isocyanate group of the polyisocyanate (a1) and the hydroxyl group of the polyol (a2) [having the polyisocyanate (a1).
  • Isocyanate group / hydroxyl group of polyol (a2)] is preferably in the range of 0.8 to 10.0, more preferably in the range of 1.0 to 5.0, and preferably 1.1 to 2.0. It is particularly preferable to carry out within the range.
  • the reaction is performed in a range where the mass ratio exceeds 1.0. Preferably it is done.
  • a relatively low molecular weight urethane resin (A) in order to increase the solubility in alcohol (C) it is preferable to carry out the reaction in a range where the mass ratio is less than 1.0.
  • the reaction when the polyisocyanate (a1) and the polyol (a2) are reacted in the absence of a solvent is preferably in the range of 50 ° C. to 120 ° C.
  • a reaction temperature of 80 ° C. to 100 ° C. the polyisocyanate (a1) and the polyol (a2) are sequentially mixed, or one of them is successively supplied to the other by a method such as dropping to about 1 to The reaction can be carried out for about 15 hours.
  • the second step is a step comprising any one of the following (Method 1) to (Method 4), which is carried out following the first step of producing the urethane prepolymer (a3).
  • This step comprises reacting the urethane prepolymer (a3), the coupling agent (a4), and, if necessary, a chain extender (a5), thereby producing an alcohol-soluble urethane having a hydrolyzable silyl group.
  • This is a process for producing an alcohol (C) solution of resin (A).
  • the (Method 1) will be described.
  • the coupling agent (a4), the alcohol (C), and a mixture containing a chain extender (a5) as necessary, and the urethane prepolymer (a3) are mixed and reacted.
  • numerator can be manufactured.
  • the hydrolyzable silyl group is obtained as an alcohol-soluble type. It introduce
  • the diamine silane coupling agent mentioned later, a diisocyanate group containing silane coupling agent, etc. are used as the said coupling agent (a4), the said hydrolyzable silyl group is an alcohol-soluble urethane resin (A ) Introduced in the molecular side chain.
  • the mixture containing the coupling agent (a4), the alcohol (C) and, if necessary, the chain extender (a5) comprises the coupling agent (a4) the alcohol (C) and, optionally, the chain extender (a5).
  • a normal temperature specifically about 10 to 50 ° C., or in a batch, one of them is sequentially fed, mixed and stirred.
  • the coupling agent (a4) is in the presence of the alcohol (C), it does not substantially cause a hydrolysis condensation reaction between hydrolyzable silyl groups of the coupling agent (a4). .
  • the monoamine silane coupling agent is used as the coupling agent (a4), and an aliphatic cyclic structure-containing diamine or an aliphatic diamine is used in combination as the chain extender (a5). It is preferable for achieving both good solubility of the urethane resin (A) in the alcohol (C) and excellent heat resistance of the resulting cured product.
  • the urethane prepolymer obtained in the first step and the coupling agent (a4) prepared in advance or a mixture of the coupling agent (a4) and the chain extender (a5) are prepared.
  • Polymer (a3) is mixed and the urethane prepolymer (a3) has an isocyanate group or a hydroxyl group, and the coupling agent (a4) or the chain extender (a5) has a functional group such as an amino group or an isocyanate group.
  • the alcohol-soluble urethane resin having hydrolyzable silyl groups and / or silanol groups introduced into the molecule.
  • the obtained alcohol-soluble urethane resin and alcohol (C) are mixed and stirred to obtain the alcohol (C) solution of the alcohol-soluble urethane resin (A).
  • the silanol groups present in the urethane resin (A) form hydrolyzable silyl groups in the presence of the alcohol (C).
  • the coupling agent (a4) and the chain extender (a5) are used at room temperature, specifically about 10 to 50 ° C. It is preferable to mix under the following conditions.
  • the coupling agent (a4) alone or a mixture containing the coupling agent (a4) and the chain extender (a5) and the urethane prepolymer (a3) is preferably mixed at 10 to 50 ° C. More preferably, the reaction can be performed under a temperature condition of 10 to 30 ° C.
  • the mixture of the coupling agent (a4) and the chain extender (a5) and the urethane prepolymer (a3) may be mixed in a batch, or one of them may be dropped onto the other. May be carried out by a method of sequentially feeding and mixing.
  • the number average molecular weight of the urethane resin is approximately 1000 to It is preferable to adjust so as to obtain a relatively low molecular weight of about 10,000, preferably about 1000 to 5,000.
  • the mixing of the alcohol-soluble urethane resin (A) and the alcohol (C) obtained by the above method is preferably performed under a temperature condition of 10 to 50 ° C.
  • the alcohol-soluble urethane resin (A) and the alcohol (B) can also be mixed by a method of mixing them all together or a method of sequentially supplying and mixing one of them to the other by dropping or the like. it can.
  • a mixture prepared by dissolving the urethane prepolymer (a3) obtained in the first step in an alcohol (C) is prepared in advance, and the mixture, the coupling agent (a4), and a chain extender ( and a functional group such as an amino group or an isocyanate group included in the coupling agent (a4) or the chain extender (a5) and an isocyanate group or a hydroxyl group included in the urethane prepolymer (a3).
  • the alcohol (C) solution of the alcohol-soluble urethane resin (A) can be obtained.
  • the mixing of the urethane prepolymer (a3) and the alcohol (C) is from the viewpoint of preventing the reaction between the isocyanate group of the urethane prepolymer (a3) and the hydroxyl group of the alcohol (C). It is important to carry out the reaction at room temperature or relatively low temperature, preferably 10 to 50 ° C., more preferably 10 to 30 ° C.
  • the mixing of the urethane prepolymer (a3) and the alcohol (C) may be performed by a method of mixing them all at once, or a method of sequentially supplying and mixing one of them to the other by dropping or the like.
  • the mixture of the urethane prepolymer (a3) and the alcohol (C) and the coupling agent (a4) and the chain extender (a5) were mixed and stirred together.
  • any of the components may be sequentially supplied to other components by a method such as dropping.
  • a mixture of the urethane prepolymer (a3) and the alcohol (C) was produced from the viewpoint of preventing the reaction between the isocyanate group of the urethane prepolymer (a3) and the hydroxyl group of the alcohol (C).
  • the coupling agent (a4) and the chain extender (a5) as soon as possible, specifically, preferably at a temperature of 10 to 50 ° C. within about 2 hours after the preparation of the mixture.
  • the reaction is preferably carried out at about 10 to 50 ° C.
  • the monoamine silane coupling agent is used as the coupling agent (a4), and an aliphatic cyclic structure-containing diamine or an aliphatic diamine is used in combination as the chain extender (a5). It is preferable for achieving both good solubility of the urethane resin (A) in the alcohol (C) and excellent heat resistance of the resulting cured product.
  • the (Method 4) is an alcohol-soluble urethane resin (A) having a hydrolyzable silyl group and / or silanol group by mixing and reacting the coupling agent (a4) and the urethane prepolymer (a3). Then, the alcohol-soluble urethane resin (A) having a hydrolyzable silyl group and / or silanol group is obtained by mixing the alcohol-soluble urethane resin (A) and the alcohol (B). This is a method for producing an alcohol (C) solution.
  • the coupling agent (a4) and the urethane prepolymer (a3) obtained in the first step are mixed, and the functional group such as isocyanate group or amino group which the coupling agent (a4) has.
  • the above-mentioned alcohol-soluble urethane resin (A) by reacting the isocyanate group or hydroxyl group of the urethane prepolymer (a3) with the resulting alcohol-soluble urethane resin (A)
  • the alcohol (B) solution of the alcohol-soluble urethane resin (A) can be obtained by mixing and stirring the alcohol (C). At that time, most of the silanol groups present in the urethane resin (A) form hydrolyzable silyl groups in the presence of the alcohol (C).
  • the mixing of the coupling agent (a4) and the urethane prepolymer (a3) is preferably a method of mixing them together under a condition of preferably 10 to 50 ° C., more preferably 10 to 30 ° C., Any one of the methods of supplying and mixing one by one like dropping or the like may be used.
  • the alcohol-soluble urethane resin (A) and the alcohol (B) may be mixed by, for example, a method in which they are mixed together under a condition of 10 to 50 ° C. or one of them is dropped. Any one of the methods of sequentially supplying to and mixing them may be used.
  • the monoamine silane coupling agent can be preferably used as the coupling agent (a4).
  • the polyisocyanate (a1) and polyol (a2) or the said polyester polyol and polycarbonate polyol are used as said polyol (a2) Even so, it is possible to efficiently produce an alcohol-soluble urethane resin capable of forming a cured product having excellent durability such as heat resistance and chemical resistance.
  • the urethane resin has a number average molecular weight of about 1000 to 10,000, preferably about 1,000 to 5,000, from the viewpoint of maintaining good solubility in alcohol. It is preferable to adjust so that a low molecular weight thing may be obtained.
  • the alcohol-soluble urethane resin (A) obtained in the first step and the second step has excellent solubility in the alcohol (C) described later.
  • the solubility of the urethane resin (A) indicates that preferably 95% by mass or more of the urethane resin (A) can be dissolved in the alcohol (C), more preferably 99% by mass or more can be dissolved, and particularly preferable. Means that substantially 100% by mass is dissolved.
  • the solubility of the said urethane resin (A) points out the state which does not cause white turbidity when the urethane resin composition of this invention is visually observed but can maintain a transparent state.
  • Examples of the polyisocyanate (a1) that can be used in the production of the alcohol-soluble urethane resin (A) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidization.
  • Polyisocyanates containing aromatic cyclic structures such as diphenylmethane polyisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, water
  • Polyisocyanates containing aliphatic cyclic structures such as hydrogenated diphenylmethane diisocyanate and hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, Mer acid diisocyanate, an aliphatic polyisocyanate such as norbornene diisocyanate can be used.
  • the aliphatic cyclic It is preferable to use structure-containing polyisocyanates and aliphatic polyisocyanates, and it is particularly preferable to use isophorone diisocyanate.
  • aromatic cyclic structure containing polyisocyanate alone as said polyisocyanate (a1) it is preferable to perform the said method 2 and 4 as a 2nd process at the time of manufacturing a urethane resin (A). .
  • polystyrene resin As the polyol (a2) capable of reacting with the polyisocyanate (a1), one containing at least one selected from the group consisting of polyether polyol, polyester polyol and polycarbonate polyol can be used.
  • a polyether polyol is preferably used as the polyol (a2) when a urethane resin composition containing a relatively high molecular weight alcohol-soluble urethane resin (A) of about 10,000 to 300,000 is produced. .
  • A alcohol-soluble urethane resin
  • polycarbonate polyol or polyester polyol is used as the polyol (a2). Is preferably used in combination with the polyether polyol.
  • the alcohol-soluble urethane resin (A) has a molecular weight of about 1000. It is preferable to adjust the molecular weight to a relatively low molecular weight of about 10000, preferably about 1000 to 5000. Moreover, it is preferable to employ
  • polyol (a2) it is preferable to use a polyol having a number average molecular weight in the range of 800 to 5000 from the viewpoint of enhancing the solubility of the resulting alcohol-soluble urethane resin (A) in alcohol. It is more preferable to use those in the range of ⁇ 3000.
  • polyether polyol for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.
  • the initiator examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolethane, trimethylolpropane and the like can be used.
  • alkylene oxide for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or the like can be used.
  • polyether polyol specifically, polyethylene glycol, polypropylene glycol, or polytetramethylene glycol is used to maintain excellent solubility of the resulting urethane resin (A) in the alcohol (C). Particularly preferred.
  • polyester polyol examples include aliphatic polyester polyols and aromatic polyester polyols obtained by esterification of low molecular weight polyols and polycarboxylic acids, and cyclic ester compounds such as ⁇ -caprolactone and ⁇ -butyrolactone. Polyesters obtained by ring polymerization reaction, copolymerized polyesters thereof, and the like can be used.
  • the polyester polyol an aromatic cyclic structure-containing polyester polyol from the viewpoint of achieving both improvement in durability such as heat resistance and chemical resistance of the obtained cured product and high hardness and good solubility in alcohol. Is preferably used.
  • the aromatic cyclic structure-containing polyester polyol it is preferable to employ either method 2 or 4 as the second step in producing the alcohol-soluble urethane resin (A). .
  • low molecular weight polyol examples include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol.
  • 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and the like can be used alone or in combination of two or more.
  • polycarboxylic acid examples include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and these.
  • An anhydride or an ester-forming derivative can be used.
  • aromatic polycarboxylic acids such as a terephthalic acid, isophthalic acid, a phthalic acid, and a naphthalene dicarboxylic acid, as the said polycarboxylic acid.
  • polycarbonate polyol for example, those obtained by reacting a carbonic acid ester and a polyol, or those obtained by reacting phosgene with bisphenol A or the like can be used.
  • carbonate ester methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, or the like can be used.
  • polyol that can react with the carbonate ester examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-
  • polyol (a2) in addition to the polyether polyol, polyester polyol and polycarbonate polyol, other polyols may be used in combination as required.
  • Examples of the other polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, Hydrophilic group-containing polyols such as 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, dimethylolpropionic acid, etc., and acrylic polyols in which hydroxyl groups are introduced into an acrylic copolymer Polybutadiene polyol which is a copolymer of butadiene containing a hydroxyl group in the molecule, hydrogenated polybutadiene polyol, partially saponified product of ethylene-vinyl acetate copolymer, and the like can be appropriately used.
  • the coupling agent (a4) used for the production of the alcohol-soluble urethane resin (A) is used for introducing a hydrolyzable silyl group into the molecular terminal or molecular side chain of the urethane resin (A).
  • the coupling agent (a4) for example, an amino group-containing silane coupling agent or an isocyanate group-containing silane coupling agent can be used.
  • the amino group-containing silane coupling agent for example, a monoamine silane coupling agent or a diamine silane coupling agent can be used.
  • the monoamine silane coupling agent when the molecular end of the urethane prepolymer (a3) is an isocyanate group, the isocyanate group reacts with the amino group of the monoamine silane coupling agent. Thereby, the alcohol-soluble urethane resin (A) having a hydrolyzable silyl group at the molecular end can be obtained.
  • the molecular end of the urethane prepolymer (a3) is an isocyanate group
  • the isocyanate group reacts with the amino group of the diamine silane coupling agent.
  • Examples of the monoamine silane coupling agent include monoamine silane coupling agents such as ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -aminopropylmethyldiethoxysilane. Can be used alone or in combination of two or more.
  • diamine silane coupling agent for example, a diamine silane coupling agent such as N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane alone or Two or more types can be used in combination.
  • a diamine silane coupling agent such as N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane alone or Two or more types can be used in combination.
  • isocyanate group-containing silane coupling agent for example, a monoisocyanate group-containing silane coupling agent or a diisocyanate group-containing silane coupling agent can be used.
  • the hydroxyl group reacts with the isocyanate group of the monoisocyanate group-containing silane coupling agent.
  • the alcohol-soluble urethane resin (A) having a hydrolyzable silyl group at the molecular end can be obtained.
  • the molecular end of the urethane prepolymer (a3) is a hydroxyl group
  • the hydroxyl group reacts with the isocyanate group of the diisocyanate group-containing silane coupling agent.
  • ⁇ -isocyanatopropyltriethoxysilane for example, ⁇ -isocyanatopropyltrimethoxysilane, etc. can be used alone or in combination of two or more.
  • the monoamine silane coupling agent (a4) from the viewpoint of obtaining a cured product having excellent heat resistance, the monoamine silane coupling agent is preferably used, and ⁇ -aminopropyltriethoxysilane, ⁇ -isocyanatopropyltrimethyl is used. More preferably, ethoxysilane is used.
  • the coupling agent (a4) is used in such a range that the amino group has a ratio of 0.01 to 1.0 (equivalent ratio) with respect to 1.00 equivalent of the isocyanate group of the urethane prepolymer (a3). It is preferable to use at a ratio of 0.01 to 0.9 (equivalent ratio). Further, when the functional group is a hydroxyl group at the molecular end of the urethane prepolymer (a3), the isocyanate group of the coupling agent (a4) is 0.01 to 1. It is preferably used in the range of 0 (equivalent ratio), more preferably 0.01 to 0.9 (equivalent ratio).
  • the coupling agent (a4) is used in such a range that the amino group has a ratio of 0.01 to 1.0 (equivalent ratio) with respect to 1.00 equivalent of the isocyanate group of the urethane prepolymer (a3). It is preferable to use at a ratio of 0.01 to 0.1 (equivalent ratio).
  • the coupling agent (a4) preferably ⁇ -aminopropyltriethoxysilane or ⁇ -isocyanatopropyltriethoxysilane, within such an equivalence ratio, a cured product with even better heat resistance can be formed.
  • a urethane resin composition can be obtained.
  • the urethane resin (A) when the alcohol-soluble urethane resin (A) is produced, the urethane resin (A) has a high molecular weight, and for the purpose of improving the heat resistance of the resulting cured product, a chain is formed as necessary.
  • An extender (a5) can be used.
  • chain extender (a5) conventionally known diamines, alkanolamines, and the like can be used. Among them, the use of diamines maintains good storage stability of the resulting urethane resin composition. In addition, it is preferable.
  • the said diamine silane coupling agent and diisocyanate group containing silane coupling agent as said coupling agent (a4) can also be used as a chain extender, when using them, the said chain
  • the extender (a5) is not necessarily used.
  • the alcohol-soluble urethane resin (A) has a high molecular weight and is excellent.
  • the chain extender (a5) it is preferable to use the chain extender (a5).
  • diamine examples include dicyclohexylmethanediamine, isophoronediamine, 4,4′-diphenylmethanediamine, diaminoethane, 1,2- or 1,3-diaminopropane, 1,2- or 1,3- or 1,4- Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N, N′-bis- (2-aminoethyl) piperazine, bis- (4-aminocyclohexyl) methane, bis- (4-amino -3-Butylcyclohexyl) methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, norbornenediamine, hydrazine, dihydrazine adipate and the like can be used alone or in combination.
  • the alcohol-soluble urethane resin (A) excellent in solubility in the alcohol (C) it is preferable to use an aliphatic cyclic structure-containing diamine or an aliphatic diamine, and dicyclohexylmethane. More preferably, diamine or isophoronediamine is used.
  • chain extenders in addition to the diamine, other chain extenders may be used in combination as necessary.
  • the diamine is preferably used in a range where the amino group is in a ratio of 0.50 to 1.00 (equivalent ratio) with respect to 1.00 equivalent of the isocyanate group of the urethane prepolymer (a3). It is more preferable to use at a ratio of .60 to 0.90 in order to impart excellent heat resistance to the resulting cured product.
  • the inorganic particles (B) used in the present invention hardly react with the hydrolyzable silyl group or the like of the urethane resin (A) in the presence of the alcohol (C).
  • the alcohol resin (C) is removed by applying the urethane resin composition of the present invention to a substrate surface, for example, and drying, the hydrolyzable silyl group of the alcohol-soluble urethane resin (A) is in the atmosphere. It has a functional group [Y] capable of forming a bond by reacting with a functional group [X] such as a silanol group formed by hydrolysis by moisture (water).
  • the functional group [Y] of the inorganic particle (B) can react with a functional group [X] such as a silanol group generated from the hydrolyzable silyl group.
  • a functional group [X] such as a silanol group generated from the hydrolyzable silyl group.
  • Examples include hydrophilic groups such as silyl groups and silanol groups.
  • the functional group [Y] is preferably present in an amount of 2 or more per 1 nm 2 of the surface area of the inorganic particles (B), more preferably in the range of 3 or more and 20 or less, and 3 or more and 10 or less. It is particularly preferable to exist within the range in order to improve the heat resistance of the resulting cured product and the ease of dispersion of the inorganic particles (B) in the urethane resin (A).
  • metal oxides generally known as silica, alumina, titania, zirconia, etc., hydrolysis condensates thereof, and the like can be used. More specifically, oxides of one or more metals selected from the group consisting of silicon, zirconium, iron, silver, aluminum, titanium, zinc, indium, copper, germanium, tin, cerium, tungsten and magnesium, and their Hydrolysis condensates can be used.
  • any of the inorganic particles (B) can be used, but from the viewpoint of imparting further excellent heat resistance, chemical resistance, and high hardness, silicon, aluminum, titanium, zirconium, zinc It is preferable to use one or more metal oxides selected from the group consisting of tin and their hydrolysis condensates. Among these, it is more preferable to use a silicon compound having a hydroxyl group, a silanol group or the like, which is generally referred to as hydrophilic silica, and a hydrolysis condensate thereof.
  • the alkoxy group and hydroxyl group directly bonded to the silicon atom are specifically the same as the hydrolyzable silyl group of the alcohol-soluble urethane resin (A) and the silanol group formed by hydrolysis thereof. It is preferable that.
  • the hydrophilic silica may be, for example, a product name manufactured by Nissan Chemical Industries, Ltd .: methanol silica sol, MEK-ST, MIBK-ST. IPA-ST, IPA-ST-UP, IPA-ST-L, IPA-ST-ZL, NPC-ST-30, XBA-ST, EG-ST, DMAC-ST, Nippon Aerosil Co., Ltd.
  • the average particle diameter is generally in the order of micrometers or nanometers, preferably nanometers. It can be used those.
  • Examples of the inorganic particles (B) that are aluminum oxides or hydrolyzed condensates thereof include, for example, product names: Alumina Sol-100, Alumina Sol-200, Alumina Sol-520 manufactured by Nissan Chemical Industries, Ltd. Can be used. Further, as the inorganic particles that are zirconium oxide or its hydrolyzed condensate, for example, trade name ZSL10T manufactured by Daiichi Rare Element Co., Ltd. can be used.
  • inorganic particles (B) in addition to those described above, powders of titanium oxide, indium oxide, tin oxide and zinc oxide, and those in which they are dispersed in a solvent can be used.
  • the inorganic particles (B) those having an average particle diameter of approximately 10 nm to 10,000 nm (10 ⁇ m) are preferably used, those having an average particle diameter of 10 nm to 90 nm are preferably used, and those having an average particle diameter of 10 nm to 80 nm are used. It is more preferable to obtain a cured product excellent in heat resistance and flexibility (elongation). In order to further improve the flexibility (elongation) of the obtained cured product, it is preferable to use inorganic particles having an average particle size of preferably about 40 nm to 90 nm, more preferably about 50 nm to 90 nm.
  • the inorganic particles (B) and the urethane resin (A) are mixed using a stirring device such as a homomixer as necessary to uniformly disperse the inorganic particles in the urethane resin composition. Is preferred.
  • the average particle diameter of the inorganic particle (B) as used in the field of this invention points out the value measured by the dynamic scattering method.
  • the inorganic particles (B) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indeterminate shape, preferably a spherical shape or a hollow shape.
  • the specific surface area of the inorganic particles (B) (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m 2 / g, more preferably 50 to 100 m 2 / g.
  • the inorganic particles (B) powdery ones can be used, but when the urethane resin composition of the present invention is produced, the alcohol-soluble urethane resin (A) and its alcohol (C ) From the viewpoint of ease of mixing with the solution, it is preferable to use the inorganic particles (B) previously dispersed in a solvent such as ethanol or isopropyl alcohol.
  • the inorganic particles (B) have a particle surface having alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, Esters such as ethyl lactate, ⁇ -butyrolactone, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; It may be modified with amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.
  • ketones such as acetone, methyl ethyl ketone, methyl isobuty
  • the alcohol (C) used in the present invention will be described.
  • the alcohol (C) is used as a solvent for the alcohol-soluble urethane resin (A) and the inorganic particles (B).
  • the alcohol (C) may have any structure such as a straight chain structure, a branched structure, and a cyclic structure, but from the viewpoint of enhancing the ease of dissolution of the urethane resin (A), methyl alcohol, ethyl alcohol, It is preferable to use an alcohol having 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms, such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, More preferably, methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol are used alone or in combination of two or more.
  • the alcohol (C) is classified as a weak solvent.
  • the urethane resin composition of the present invention is applied to the surface of an adherend. Even in this case, dissolution or deterioration of the adherend surface is not caused.
  • the adherend is a porous body, the pores constituting the porous body are not broken, and the flexibility derived from the porous body is not impaired.
  • the hydrolysis condensation reaction does not proceed substantially. Therefore, in the urethane resin composition of the present invention, it is important to use the alcohol (C) as a solvent.
  • the urethane resin composition of the present invention may contain a solvent other than the alcohol (C) as a solvent.
  • a solvent other than the alcohol (C) for example, it does not exclude the presence of a strong solvent such as dimethylformamide or toluene, but the amount used is preferably as small as possible from the viewpoint of reducing environmental burden.
  • the mass ratio of the alcohol (C) to the total mass of the solvent contained in the composition is preferably 95 to 100% by mass, and 98 to 100 More preferably, it is 100 mass%, and it is especially preferable that it is 100 mass%.
  • the urethane resin composition of the present invention supplies the alcohol (C) solution of the alcohol-soluble urethane resin (A) obtained by the above-described method and the inorganic particles (B) all together, or one to the other. It can be manufactured by sequentially feeding, mixing and stirring. At this time, as the inorganic particles (B), the inorganic particles (B) dispersed in a solvent such as ethanol or isopropyl alcohol in advance can be dispersed relatively uniformly. In addition, it is also preferable for improving the production efficiency of the urethane resin composition of the present invention.
  • Mixing of the alcohol (C) solution of the urethane resin (A) and the inorganic particles (B) can be performed, for example, with a stirring rod or the like under a temperature condition of about 10 to 50 ° C., or a homomixer or the like. It can also carry out using the stirring apparatus of.
  • a stirring device such as a homomixer from the viewpoint of uniformly dispersing the inorganic particles (B).
  • the urethane resin composition of the present invention includes, for example, a crosslinking agent, a catalyst, a film forming aid, a filler, a thixotropy imparting agent, a tackifier, a surfactant, a pigment, a resin for blending, and the like, if necessary.
  • a crosslinking agent for example, a crosslinking agent, a catalyst, a film forming aid, a filler, a thixotropy imparting agent, a tackifier, a surfactant, a pigment, a resin for blending, and the like, if necessary.
  • an isocyanate-based crosslinking agent for example, an isocyanate-based crosslinking agent can be used. Specifically, tolylene diisocyanate, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, trimethylolpropane modified tolylene diisocyanate, and the like. Can be used.
  • said catalyst it is anhydrous from a viewpoint which advances hydrolytic condensation reaction of the hydrolyzable silyl group and silanol group which the said urethane resin (A) has, and the hydroxyl group which the said inorganic particle (B) has, for example.
  • Acid catalysts such as maleic acid and phosphoric acid can be used.
  • the film forming aid is not particularly limited, and examples thereof include anionic surfactants (such as dioctyl sulfosuccinate soda salt), hydrophobic nonionic surfactants (such as sorbitan monooleate), and silicone oil. It is done.
  • anionic surfactants such as dioctyl sulfosuccinate soda salt
  • hydrophobic nonionic surfactants such as sorbitan monooleate
  • silicone oil silicone oil
  • Examples of the filler include carbonates (eg, calcium salts, calcium / magnesium salts, magnesium salts), silicic acid, silicates (eg, aluminum salts, magnesium salts, calcium salts), water, other than the inorganic particles (B).
  • Oxides eg, aluminum salts, magnesium salts, calcium salts, etc.
  • sulfates eg, barium salts, calcium salts, magnesium salts, etc.
  • borates eg, aluminum salts, zinc salts, calcium salts, etc.
  • titanates eg, Potassium salts, etc.
  • metal oxides eg, zinc, titanium, magnesium, calcium, aluminum, etc.
  • thixotropy-imparting agent examples include fatty acid, fatty acid metal salt, fatty acid ester, paraffin, resin acid, surfactant, polyacrylic acid and the like surface-treated filler, polyvinyl chloride powder, hydrogenated castor oil, Fine powder silica, organic bentonite, sepiolite and the like can be mentioned.
  • the tackifier is not particularly limited, and examples thereof include tackifiers such as rosin resin, terpene resin, and phenol resin.
  • additives include, for example, reaction accelerators (metal, metal salt, amine, etc.), stabilizers (ultraviolet absorbers, antioxidants, heat stabilizers, etc.), moisture removal agents (4- Various additions such as paratoluenesulfonyl isocyanate, adsorbents (quick lime, slaked lime, zeolite, molecular sieves, etc.), adhesion promoters (coupling agents, organometallic coupling agents, etc.), antifoaming agents, leveling agents, etc. Agents.
  • reaction accelerators metal, metal salt, amine, etc.
  • stabilizers ultraviolet absorbers, antioxidants, heat stabilizers, etc.
  • moisture removal agents 4- Various additions such as paratoluenesulfonyl isocyanate, adsorbents (quick lime, slaked lime, zeolite, molecular sieves, etc.), adhesion promoters (coupling agents,
  • the urethane resin composition of the present invention is less likely to cause gelation and the like, has excellent dispersion stability, and can form a cured product having excellent heat resistance when cured. Moreover, since alcohol is used as a solvent, it does not cause dissolution or deterioration of the substrate surface.
  • the urethane resin composition of the present invention can be used, for example, as a coating agent used for surface coating of a member requiring heat resistance, or an adhesive thereof. Specifically, it is more preferable to use it as a top layer forming coating agent or a primer layer forming coating agent.
  • a plated steel plate such as a galvanized steel plate or an aluminum-zinc alloy steel plate, an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate, or the like can be used.
  • plastic substrate examples include a polycarbonate substrate, a polyester substrate, an acrylonitrile-butadiene-styrene substrate, a polyacryl substrate, a polystyrene substrate, a polyurethane substrate, an epoxy resin substrate, a polyvinyl chloride substrate, and the like.
  • a polyamide-based substrate or the like can be used.
  • Examples of the method for applying the coating agent or adhesive onto the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.
  • the urethane resin composition of the present invention can be used for the production of cured products that require a very high level of heat resistance, such as automobile parts, home appliance parts, electronic materials, and the like.
  • the urethane resin composition of the present invention can achieve both excellent heat resistance and good elongation (flexibility) by optimizing the average particle size and the amount of the inorganic particles (B), for example, It can be used for the production of coating agents, adhesives and various parts in the fields of automobile parts and electronic materials that are repeatedly used in an environment where the temperature changes rapidly.
  • the urethane resin composition is applied to the surface of the substrate by the above-described method and dried to dry the alcohol in the coating layer.
  • the method include a step of removing (C) and a step of hydrolytic condensation reaction of the urethane resin (A) and the inorganic particles (B).
  • the step of removing the alcohol (C) is preferably performed, for example, by leaving it at room temperature or leaving it at about 30 to 80 ° C.
  • the reaction step can be rapidly advanced by, for example, heating to about 80 to 150 ° C.
  • the hydrolysis condensation reaction can be rapidly advanced by using the acid catalyst or adding water as necessary.
  • the above (Method 2) or (Method 4) is employed and the urethane resin (A) is produced using polycarbonate polyol or polyester polyol, the hydrolyzability of the urethane resin (A). Since the mass ratio of the silyl group and the silanol group increases, it is preferable to add water when curing the urethane resin composition of the present invention to promote the hydrolysis condensation reaction.
  • the water is preferably used in the range of 0.1 to 10% by mass with respect to the total mass of the urethane resin (A) and the inorganic particles (B).
  • a cured product such as a coating obtained by such a method does not cause deformation or mass loss even when placed in an environment of approximately 200 ° C. or higher, and has very excellent heat resistance.
  • coating agents and adhesives containing the urethane resin composition of the present invention include, for example, mobile phones, home appliances, OA equipment, automobile parts such as automobile interior and exterior materials, parts of various household appliances, electronic It can be used in various applications including production of materials, building material products, medical materials such as artificial bones and artificial teeth, and surface coating and adhesion thereof.
  • Example 1 As a first step, 167 g of isophorone diisocyanate and 300 g of polytetramethylene glycol (molecular weight 1000) are charged into a reactor having a stirrer, a thermometer, and a nitrogen gas introduction tube, and stirred at 90 ° C. in a solvent-free and nitrogen stream. By reacting for a time, a urethane prepolymer (a3-1) was synthesized.
  • urethane prepolymer (a3-1) 85 g of dicyclohexylmethanediamine, 5.4 g of ⁇ -aminopropyltriethoxysilane, and 1300 g of isopropyl alcohol are mixed in advance in an environment at 25 ° C. while stirring the above-mentioned mixture.
  • urethane prepolymer (a3-1) By adding 558 g of urethane prepolymer (a3-1) and reacting at approximately 30 to 40 ° C. for 3 hours, urethane resin (A-1) having a hydrolyzable silyl group (number average molecular weight 20000) is converted to isopropyl alcohol.
  • a dissolved resin solution (I-1) was obtained.
  • the resin solution (I-1) and nano silica (trade name “IPA-ST-L”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 45 nm and isopropyl alcohol, non-volatile content of 30% by mass Are mixed and stirred so that the mass ratio of the nonvolatile content of the urethane resin (A-1) and the hydroxyl group-containing silica [urethane resin (A-1) / hydroxyl group-containing silica] is 100/100.
  • the urethane resin composition (I) of the present invention was obtained.
  • Example 2 As a first step, 76 g of isophorone diisocyanate and 174 g of polytetramethylene glycol (molecular weight 1000) are charged into a reactor having a stirrer, a thermometer, and a nitrogen gas introduction tube, and stirred at 90 ° C. in a solvent-free and nitrogen stream. By reacting for a time, a urethane prepolymer (a3-2) was synthesized.
  • urethane prepolymer (a3-2) By adding 250 g of urethane prepolymer (a3-2) and reacting at approximately 30 to 40 ° C. for 3 hours, urethane resin (A-2) having a hydrolyzable silyl group (number average molecular weight 20000) is converted to isopropyl alcohol. A dissolved resin solution (I-2) was obtained.
  • the resin solution (I-2) and nano silica (trade name “IPA-ST-ZL”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle diameter of 85 nm and isopropyl alcohol, nonvolatile content of 30% by mass Are mixed and stirred so that the mass ratio of the nonvolatile content of the urethane resin (A-2) and the hydroxyl group-containing silica [urethane resin (A-2) / hydroxyl group-containing silica] is 100/100.
  • the urethane resin composition (II) of the present invention was obtained.
  • Example 3 As a first step, 167 g of isophorone diisocyanate and 300 g of polytetramethylene glycol (molecular weight 1000) are charged into a reactor having a stirrer, a thermometer, and a nitrogen gas introduction tube, and stirred at 90 ° C. in a solvent-free and nitrogen stream. By reacting for a time, a urethane prepolymer (a3-3) was synthesized.
  • urethane prepolymer (a3-3) 85 g of dicyclohexylmethanediamine, 5.4 g of ⁇ -aminopropyltriethoxysilane, and 1300 g of isopropyl alcohol are mixed in advance in an environment at 25 ° C. while stirring the above-mentioned mixture.
  • urethane prepolymer (a3-3) 558 g of urethane prepolymer (a3-3) and reacting at approximately 30 to 40 ° C. for 3 hours, urethane resin (A-3) having a hydrolyzable silyl group (number average molecular weight 20000) is converted to isopropyl alcohol.
  • a dissolved resin solution (I-3) was obtained.
  • the resin solution (I-3) and nano silica (trade name “IPA-ST-UP”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 12 nm and isopropyl alcohol, nonvolatile content of 15% by mass Is mixed and stirred so that the mass ratio of the nonvolatile content of the urethane resin (A-3) and the hydroxyl group-containing silica [urethane resin (A-3) / hydroxyl group-containing silica] is 100/100.
  • the urethane resin composition (III) of the present invention was obtained.
  • Example 4 As a first step, 167 g of isophorone diisocyanate and 300 g of polytetramethylene glycol (molecular weight 1000) are charged into a reactor having a stirrer, a thermometer, and a nitrogen gas introduction tube, and stirred at 90 ° C. in a solvent-free and nitrogen stream. By reacting for a time, a urethane prepolymer (a3-4) was synthesized.
  • urethane prepolymer (a3-4) 85 g of dicyclohexylmethanediamine, 5.4 g of ⁇ -aminopropyltriethoxysilane, and 1300 g of isopropyl alcohol are mixed in advance in an environment at 25 ° C. while stirring the above-mentioned mixture.
  • urethane prepolymer (a3-4) By adding 558 g of urethane prepolymer (a3-4) and reacting at approximately 30 to 40 ° C. for 3 hours, urethane resin (A-4) having a hydrolyzable silyl group (number average molecular weight 20000) is converted to isopropyl alcohol.
  • a dissolved resin solution (I-4) was obtained.
  • the resin solution (I-4) and nano silica (trade name “IPA-ST”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 13 nm and isopropyl alcohol, nonvolatile content of 30% by mass) Is mixed and stirred so that the mass ratio of the nonvolatile content of the urethane resin (A-4) and the hydroxyl group-containing silica [urethane resin (A-4) / hydroxyl group-containing silica] is 100/100.
  • the urethane resin composition (IV) of the present invention was obtained.
  • Example 5 As a first step, 166 g of isophorone diisocyanate and 300 g of polytetramethylene glycol (molecular weight 1000) are charged into a reactor having a stirrer, a thermometer, and a nitrogen gas introduction tube, and stirred at 90 ° C. in a solvent-free and nitrogen stream. By reacting for a period of time, a urethane prepolymer (a3-5) having an isocyanate group at the molecular end was synthesized.
  • a urethane prepolymer (a3-5) having an isocyanate group at the molecular end was synthesized.
  • urethane prepolymer (a3-5), 56 g of dicyclohexylmethanediamine and 6 g of ⁇ -aminopropyltriethoxysilane were mixed, and then reacted at 90 ° C. for 6 hours in the absence of solvent and in a nitrogen stream, thereby hydrolyzable silyl.
  • a urethane resin (a-5) having a group and / or a silanol group was obtained.
  • the urethane resin (A-5) (number average molecular weight 2000) having a hydrolyzable silyl group is mixed with isopropyl alcohol by mixing the urethane resin (a-5) and 353 g of isopropyl alcohol in an environment of 25 ° C.
  • a resin solution (I-5) dissolved in 1 was obtained.
  • the resin solution (I-5) and nano silica (trade name “IPA-ST-L”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 45 nm and isopropyl alcohol, nonvolatile content of 30% by mass Are mixed and stirred so that the mass ratio of the nonvolatile content of the urethane resin (A-5) and the hydroxyl group-containing silica [urethane resin (A-5) / hydroxyl group-containing silica] is 100/100.
  • the urethane resin composition (V) of the present invention was obtained.
  • Example 6 As a first step, 166 g of isophorone diisocyanate and 300 g of polytetramethylene glycol (molecular weight 1000) are charged into a reactor having a stirrer, a thermometer, and a nitrogen gas introduction tube, and stirred at 90 ° C. in a solvent-free and nitrogen stream. By reacting for 6 hours, a urethane prepolymer (a3-6) having an isocyanate group at the molecular end was synthesized.
  • a urethane prepolymer (a3-6) having an isocyanate group at the molecular end was synthesized.
  • urethane prepolymer (a3-6), 56 g of dicyclohexylmethanediamine and 6 g of ⁇ -aminopropyltriethoxysilane were mixed, and then reacted at 90 ° C. for 6 hours in the absence of solvent and in a nitrogen stream, thereby producing a hydrolyzable silyl group.
  • a urethane resin (a-6) having a group and / or a silanol group was obtained.
  • the urethane resin (A-6) (number average molecular weight 2000) having the hydrolyzable silyl group is obtained by mixing the urethane resin (a-6) and 353 g of isopropyl alcohol under an environment of 25 ° C. A resin solution (I-6) dissolved in alcohol was obtained.
  • the resin solution (I-6) and nano silica (trade name “IPA-ST”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 13 nm and isopropyl alcohol, nonvolatile content: 15% by mass) are mixed and stirred so that the mass ratio [urethane resin (A-6) / hydroxyl group-containing silica] of the nonvolatile content of the urethane resin (A-6) and the hydroxyl group-containing silica is 100/100,
  • the urethane resin composition (VI) of the present invention was obtained.
  • Example 7 As a first step, 167 g of isophorone diisocyanate and 300 g of polytetramethylene glycol (molecular weight 1000) are charged into a reactor having a stirrer, a thermometer, and a nitrogen gas introduction tube, and stirred at 90 ° C. in a solvent-free and nitrogen stream.
  • the urethane prepolymer (a3-7) was synthesized by reacting for 6 hours.
  • the resin solution (I-7) and nano silica (trade name “IPA-ST-L”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 45 nm and isopropyl alcohol, nonvolatile content of 30% by mass Are mixed and stirred so that the mass ratio of the nonvolatile content of the urethane resin (A-7) and the hydroxyl group-containing silica [urethane resin (A-7) / hydroxyl group-containing silica] is 100/100.
  • the urethane resin composition (VII) of the present invention was obtained.
  • Example 8 As a first step, 167 g of isophorone diisocyanate and 300 g of polytetramethylene glycol (molecular weight 1000) are charged into a reactor having a stirrer, a thermometer, and a nitrogen gas introduction tube, and stirred at 90 ° C. in a solvent-free and nitrogen stream. By reacting for 6 hours, a urethane prepolymer (a3-8) was synthesized.
  • a second step 85 g of dicyclohexylmethanediamine and ⁇ -aminopropyltriethoxy were added to a mixture obtained by previously mixing the urethane prepolymer (a3-8) and 1300 g of isopropyl alcohol in an environment of 25 ° C.
  • a resin solution (I ⁇ ) in which a urethane resin (A-8) having a hydrolyzable silyl group (number average molecular weight 20000) is dissolved in isopropyl alcohol. 8) was obtained.
  • the resin solution (I-8) and nano silica (trade name “IPA-ST”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 13 nm and isopropyl alcohol, nonvolatile content of 30% by mass) Is mixed and stirred so that the mass ratio of the urethane resin (A-8) and the hydroxyl group-containing silica [urethane resin (A-8) / hydroxyl group-containing silica] is 100/100.
  • a urethane resin composition (VIII) was obtained.
  • Example 9 As a first step, 66 g of isophorone diisocyanate and 600 g of T-5651 (manufactured by Asahi Kasei Chemicals Co., Ltd., polycarbonate diol, molecular weight 1000) are charged into a reactor having a stirrer, a thermometer and a nitrogen gas introduction tube. A urethane prepolymer (a3-9) having a hydroxyl group at the molecular end was synthesized by reacting for 6 hours while stirring at 90 ° C. in an air stream.
  • urethane prepolymer (a3-9) and 138 g of ⁇ -monoisocyanatepropyltriethoxysilane were mixed at 90 ° C. and reacted for 6 hours at 90 ° C. in the absence of a solvent and in a nitrogen stream, whereby hydrolyzable silyl groups and / or Alternatively, a urethane resin (a-9) having a silanol group (number average molecular weight 2000) was obtained.
  • the urethane resin (a-9) and 89 g of isopropyl alcohol are mixed at 80 ° C. or lower, whereby the urethane resin (A-9) having a hydrolyzable silyl group is dissolved in isopropyl alcohol (I -9) was obtained.
  • the resin solution (I-9) and nano silica (trade name “IPA-ST-L”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 45 nm and isopropyl alcohol, nonvolatile content of 30% by mass Are mixed so that the mass ratio [urethane resin (A-9) / hydroxyl group-containing silica] of the non-volatile content of the urethane resin (A-9) and the hydroxyl group-containing silica is 100/100.
  • the urethane resin composition (IX) of the present invention was obtained by mixing and stirring 0.5 g of List ML (an acid catalyst manufactured by DIC Corporation) and 1 g of water.
  • Example 10 As the first step, 66 g of isophorone diisocyanate and 600 g of polyester diol (molecular weight 1000) obtained by reacting 3-methylpentanediol and adipic acid are charged into a reaction apparatus having a stirrer, a thermometer and a nitrogen gas introduction tube. A urethane prepolymer (a3-10) having a hydroxyl group at the molecular end was synthesized by reacting for 6 hours with stirring at 90 ° C. in a solvent-free and nitrogen stream.
  • urethane prepolymer (a3-10) and 138 g of ⁇ -monoisocyanatepropyltriethoxysilane are mixed and reacted for 6 hours at 90 ° C. in the absence of a solvent and in a nitrogen stream, whereby hydrolyzable silyl groups and / or silanols are reacted.
  • a urethane resin (a-10) having a group was obtained.
  • the urethane resin (A-10) (number average molecular weight 2000) having the hydrolyzable silyl group is mixed with isopropyl alcohol by mixing the urethane resin (a-10) and 89 g of isopropyl alcohol in an environment of 25 ° C.
  • a resin solution (I-10) dissolved in alcohol was obtained.
  • the resin solution (I-10) and nano silica (trade name “IPA-ST-L”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 45 nm and isopropyl alcohol, nonvolatile content of 30% by mass )
  • the urethane resin (A-10) and the hydroxyl group-containing silica are mixed so that the mass ratio [urethane resin (A-10) / hydroxyl group-containing silica] is 100/100.
  • a urethane resin composition (X) of the present invention was obtained by mixing and stirring 0.5 g of List ML (DIC acid catalyst) and 1 g of water.
  • Example 11 As a first step, 78 g of 2,4-tolylene diisocyanate and 500 g of polytetramethylene glycol (molecular weight 1000) are charged into a reactor having a stirrer, a thermometer, and a nitrogen gas introduction tube, and are used in a solventless and nitrogen stream. By reacting at 6 ° C. for 6 hours with stirring, a urethane prepolymer (a3-11) having a hydroxyl group in the molecule was synthesized.
  • the urethane prepolymer (a3-11) and ⁇ -isocyanatopropyltriethoxysilane (0.85 g) are mixed and reacted for 6 hours at 90 ° C. in the absence of a solvent and under a nitrogen stream, whereby hydrolyzable silyl groups and / or A urethane resin (a-11) having a silanol group was obtained.
  • the urethane resin (a-11) and 559 g of isopropyl alcohol are mixed in an environment at 25 ° C., whereby the resin solution (I) in which the urethane resin (A-11) (number average molecular weight 2000) is dissolved in isopropyl alcohol. -11) was obtained.
  • the resin solution (I-11) and nano silica (trade name “IPA-ST-L”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 45 nm and isopropyl alcohol, nonvolatile content of 30% by mass ),
  • the mass ratio [urethane resin (A-11) / hydroxyl group-containing silica] of the nonvolatile content of the hydrolyzable silyl group-containing urethane resin (A-11) and the hydroxyl group-containing silica is 100/300.
  • 1 g of water was further mixed and stirred to obtain the urethane resin composition (XI) of the present invention.
  • Example 12 As a first step, 167 g of isophorone diisocyanate and 300 g of polytetramethylene glycol (molecular weight 1000) are charged into a reactor having a stirrer, a thermometer, and a nitrogen gas introduction tube, and stirred at 90 ° C. in a solvent-free and nitrogen stream. By reacting for a time, a urethane prepolymer (a3-12) was synthesized.
  • urethane prepolymer (a3-1) 85 g of dicyclohexylmethanediamine, 5.4 g of ⁇ -aminopropyltriethoxysilane, and 1300 g of isopropyl alcohol are mixed in advance in an environment at 25 ° C. while stirring the above-mentioned mixture.
  • urethane prepolymer (a3-1) By adding 558 g of urethane prepolymer (a3-1) and reacting at approximately 30 to 40 ° C. for 3 hours, urethane resin (A-12) having a hydrolyzable silyl group (number average molecular weight 20000) is converted to isopropyl alcohol.
  • a dissolved resin solution (I-12) was obtained.
  • the resin solution (I-12) and fine particle titanium oxide (trade name “TTO-W-5”, manufactured by Ishihara Sangyo Co., Ltd., an aqueous sol of hydroxyl group-containing fine particle titanium oxide having an average particle size of 15 nm, nonvolatile content 30 mass %) Is mixed and stirred so that the mass ratio [urethane resin (A-12) / titanium oxide] of the nonvolatile content of the urethane resin (A-12) and the hydroxyl group-containing fine particle titanium oxide is 100/100.
  • the urethane resin composition (XII) of the present invention was obtained.
  • urethane prepolymer (a3′-1) 85 g of dicyclohexylmethanediamine, 5.4 g of ⁇ -aminopropyltriethoxysilane, and 1300 g of isopropyl alcohol are mixed in advance in an environment at 25 ° C. while stirring the above-mentioned mixture.
  • urethane prepolymer (a3′-1) By adding 558 g of urethane prepolymer (a3′-1) and reacting at 25 ° C. for 3 hours, urethane resin (A′-1) having a hydrolyzable silyl group (number average molecular weight 20000) is dissolved in isopropyl alcohol.
  • the obtained resin solution (I′-1) was obtained.
  • the resin solution (I′-1) and hydrophobic silica (trade name “R972”, manufactured by Degussa Co., Ltd., average particle diameter of 16 nm, a mixture of silica having no functional group [Y] and isopropyl alcohol. ) Is a mass ratio of the urethane resin (A′-1) and the silica having no functional group [Y] [urethane resin (A′-1) / silica having no functional group [Y]]. Was mixed and stirred so as to be 100/100 to obtain a urethane resin composition (I ′) of the present invention.
  • urethane prepolymer (a3′-2) is stirred into a mixture obtained by previously mixing 85 g of dicyclohexylmethanediamine and 1300 g of isopropyl alcohol in an environment of 25 ° C.
  • the resultant was added and reacted at approximately 30 to 40 ° C. for 3 hours to obtain a resin solution (I′-2) in which the urethane resin (A′-2) (number average molecular weight 20000) was dissolved in isopropyl alcohol.
  • the resin solution (I′-2) and nano silica (trade name “IPA-ST-L”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 45 nm and isopropyl alcohol, nonvolatile content of 45 mass %) Is mixed so that the mass ratio [urethane resin (A′-2) / hydroxyl group-containing silica] of the nonvolatile content of the urethane resin (A′-2) and the hydroxyl group-containing silica is 100/100, By stirring, the urethane resin composition (II ′) of the present invention was obtained.
  • a second step 85 g of dicyclohexylmethanediamine, 5.4 g of ⁇ -aminopropyltriethoxysilane, and 1300 g of dimethylformamide (DMF) are mixed in advance in an environment of 25 ° C. and stirred. While adding 558 g of the urethane prepolymer (a3′-3) and reacting at approximately 30 to 40 ° C. for 3 hours, the urethane resin (A′-3) having a hydrolyzable silyl group and / or silanol group Got.
  • DMF dimethylformamide
  • the urethane resin (A′-3) (number average molecular weight 20000) is dissolved in dimethylformamide by mixing the urethane resin (A′-3) and dimethylformamide in an environment of 25 ° C. (I'-3) was obtained.
  • the resin solution (I′-3) and nano silica (trade name “IPA-ST-L”, manufactured by Nissan Chemical Industries, Ltd., a mixture of hydroxyl group-containing silica having an average particle size of 45 nm and isopropyl alcohol, nonvolatile content of 45 mass %) Is mixed so that the mass ratio [urethane resin (A′-3) / hydroxyl group-containing silica] of the nonvolatile content of the urethane resin (A′-3) and the hydroxyl group-containing silica is 100/100, By stirring, the urethane resin composition (III ′) of the present invention was obtained.
  • the viscosity of the urethane resin composition was put in a glass bottle and immersed for 2 hours in a constant temperature bath set at a water temperature of 25 ° C., and the viscosity was measured in the same manner as described above.
  • the ratio of the viscosity after immersion for 2 hours to the initial viscosity [viscosity after immersion for 2 hours / initial viscosity] is less than 1.2, ⁇ , 1.2 to less than 1.5
  • a value of 1.5 or more and less than 2.0 was evaluated as ⁇ , and a value of 2.0 or more was evaluated as ⁇ .
  • the evaluation of storage stability was “x”, the following “heat resistance”, “transparency” and “flexibility” could not be evaluated. It showed in.
  • the heat resistance of the cured product obtained by curing the urethane resin composition of the present invention is based on “flow start temperature”, “dimensional stability after heat test”, and “mass loss temperature (40 mass%)”. And evaluated.
  • urethane resin compositions obtained in Examples and Comparative Examples were coated on release paper so that the dry film thickness was 30 ⁇ m, and then dried at 60 ° C. for 2 minutes, so that isopropyl alcohol and dimethylformamide were obtained. Volatilized.
  • the flow start temperature of the test film was Shimadzu flow tester CFT500D-1 (manufactured by Shimadzu Corporation, temperature rising method, measurement start temperature: 80 ° C., die: 1 mm ⁇ 1 mmL, load: 98 N, hold time: 600 sec). Measured. Those having a flow start temperature of 260 ° C. or higher were evaluated as having excellent heat resistance.
  • the upper end in the longitudinal direction of the cut test film was fixed in a drier (manufactured by SATAKE), and a 5 g weight was fixed to the lower end of the test film.
  • the temperature of the dryer was adjusted to 120 ° C., the test film was heated, and the heating time required for the test film to break was measured.
  • the time required for the test film to break is 400 hours or more, ⁇ , 200 hours or more and less than 400 hours ⁇ , 100 hours or more and less than 200 hours ⁇ , and less than 100 hours ⁇ evaluated.
  • Method of measuring mass loss temperature (40% by mass) of test film (cured product) The test film was heated using a differential thermal-thermogravimetric simultaneous measurement apparatus (TG-DTA6200, manufactured by SII Nanotechnology Inc., temperature range: 30 ° C. to 550 ° C., heating rate: 10 ° C./min). Based on the mass of the test film before heating, the temperature at which 40% by mass of the test film was lost was measured, and the test film having a higher temperature was evaluated as having higher heat resistance.
  • TG-DTA6200 differential thermal-thermogravimetric simultaneous measurement apparatus

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Abstract

La présente invention concerne une composition de résine d'uréthane qui ne souffre pas de gélification même après l'écoulement du temps et qui présente donc une stabilité au stockage et une applicabilité excellentes et qui peut fournir un produit durci (tel qu'un film de revêtement) ayant une excellente résistance à la chaleur. L'invention concerne une composition de résine d'uréthane qui comprend (A) une résine d'uréthane soluble dans l'alcool ayant un groupe silyle hydrolysable, (B) des particules inorganiques, et (C) un alcool, caractérisée en ce que les particules inorganiques (B) ont des groupes fonctionnels (b) qui réagissent avec un groupe fonctionnel (a) formé à partir du groupe silyle hydrolysable de la résine d'uréthane (A) ; un matériau de revêtement et un adhésif qui contiennent la composition de résine d'uréthane; et un produit durci obtenu en utilisant la composition de résine d'uréthane.
PCT/JP2010/068892 2009-12-10 2010-10-26 Composition de résine d'uréthane, matériau de revêtement, adhésif, produit durci obtenu en utilisant la composition, et procédé de production d'un produit durci WO2011070865A1 (fr)

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KR1020117017656A KR101766735B1 (ko) 2009-12-10 2010-10-26 우레탄 수지 조성물, 코팅제 및 접착제, 및 그것을 사용하여 얻어지는 경화물 및 경화물의 제조 방법
US13/501,124 US8420725B2 (en) 2009-12-10 2010-10-26 Urethane resin composition, coating material, adhesive, cured product obtained using the same, and method for producing cured product
EP10835787.2A EP2457951B1 (fr) 2009-12-10 2010-10-26 Composition de résine d'uréthane, matériau de revêtement, adhésif, produit durci obtenu en utilisant la composition, et procédé de production d'un produit durci
CN201080014216.3A CN102365333B (zh) 2009-12-10 2010-10-26 聚氨酯树脂组合物、涂覆剂及粘接剂以及使用其获得的固化物及固化物的制造方法
JP2011505051A JP4784715B2 (ja) 2009-12-10 2010-10-26 ウレタン樹脂組成物、コーティング剤及び接着剤、ならびにそれを用いて得られる硬化物及び硬化物の製造方法

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