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WO2020129671A1 - Composition de résine d'uréthane, agent de traitement de surface et article - Google Patents

Composition de résine d'uréthane, agent de traitement de surface et article Download PDF

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Publication number
WO2020129671A1
WO2020129671A1 PCT/JP2019/047588 JP2019047588W WO2020129671A1 WO 2020129671 A1 WO2020129671 A1 WO 2020129671A1 JP 2019047588 W JP2019047588 W JP 2019047588W WO 2020129671 A1 WO2020129671 A1 WO 2020129671A1
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WO
WIPO (PCT)
Prior art keywords
mass
urethane resin
parts
resin composition
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/047588
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English (en)
Japanese (ja)
Inventor
竹村　潔
宏之 千々和
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2020561292A priority Critical patent/JP7342884B2/ja
Priority to CN201980084408.2A priority patent/CN113195615B/zh
Publication of WO2020129671A1 publication Critical patent/WO2020129671A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08K3/01—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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • 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

Definitions

  • the present invention relates to a urethane resin composition, a surface treatment agent, and an article having a layer of the surface treatment agent.
  • the surface is finished with a surface treatment agent in order to impart chemical resistance and design.
  • the material used for the conventional surface treatment agent was a solvent-based resin composition containing an organic solvent was the mainstream, but with the recent increase in environmental regulations, an aqueous surface treatment agent that does not substantially contain an organic solvent. Development is in progress.
  • the problem to be solved by the present invention is to provide a urethane resin composition containing water, which has an excellent effect of suppressing cissing on a substrate and is excellent in scratch resistance against nails and the like. Is.
  • the present invention provides a urethane resin (A), water (B), and a trisiloxane compound (C) having a structure represented by the following formula (1) and having no structure represented by the following formula (2).
  • the present invention provides a urethane resin composition comprising:
  • the present invention also provides a surface treatment agent containing the urethane resin composition, and an article having a layer formed by the surface treatment agent.
  • the urethane resin composition of the present invention has an effect of suppressing cissing on various base materials and is excellent in scratch resistance by nails and the like (hereinafter abbreviated as “nail scratch resistance”).
  • the urethane resin composition of the present invention contains water and is an environment-friendly material.
  • the urethane resin composition of the present invention contains a urethane resin (A), water (B), and a trisiloxane compound (C) having a specific structure.
  • the urethane resin (A) is dispersible in water (B), for example, a urethane resin having a hydrophilic group such as an anionic group, a cationic group or a nonionic group; A urethane resin dispersed in B) can be used.
  • urethane resins (A) may be used alone or in combination of two or more kinds.
  • Examples of the method for obtaining the urethane resin having an anionic group include a method using as a raw material one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group.
  • Examples of the compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, and 2,2- Herb acid and the like can be used. These compounds may be used alone or in combination of two or more.
  • Examples of the compound having a sulfonyl group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N-(2-aminoethyl)- 2-Aminoethylsulfonic acid or the like can be used. These compounds may be used alone or in combination of two or more.
  • the carboxyl group and sulfonyl group may be partially or entirely neutralized with a basic compound in the resin composition.
  • the basic compound include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; metal base compounds including sodium, potassium, lithium, calcium, and the like. You can
  • a method of obtaining the urethane resin having a cationic group for example, a method of using one or more compounds having an amino group as a raw material can be mentioned.
  • Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-methyl.
  • a compound having a tertiary amino group such as N-alkyldiaminoalkylamine such as diaminoethylamine and N-ethyldiaminoethylamine can be used. These compounds may be used alone or in combination of two or more.
  • a method for obtaining the urethane resin having a nonionic group for example, a method of using one or more compounds having an oxyethylene structure as a raw material can be mentioned.
  • a polyether polyol having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol can be used. These compounds may be used alone or in combination of two or more.
  • urethane can be obtained from the viewpoint that further excellent chemical resistance, abrasion resistance, weather resistance, and hydrolysis resistance can be obtained.
  • the content in the raw material of the resin (A) is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, and further preferably 1.5 to 7% by mass.
  • Examples of the emulsifier that can be used in obtaining the urethane resin that is forcibly dispersed in water (B) include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, and polyoxy.
  • Nonionic emulsifiers such as ethylene sorbitol tetraoleate, polyoxyethylene/polyoxypropylene copolymers; fatty acid salts such as sodium oleate, alkyl sulfate salts, alkylbenzene sulfonates, alkylsulfosuccinates, naphthalene sulfonates, Anionic emulsifiers such as polyoxyethylene alkyl sulfate, alkane sulfonate sodium salt, alkyl diphenyl ether sulfonic acid sodium salt; cationic emulsifiers such as alkyl amine salt, alkyl trimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, etc. may be used. it can. These emulsifiers may be used alone or in combination of two or more kinds.
  • urethane resin (A) specifically, for example, raw materials used for producing the urethane resin having a hydrophilic group described above, polyisocyanate (a1), polyol (a2), and chain extender ( The reaction product of a3) can be used. Known urethanization reactions can be used for these reactions.
  • polyisocyanate (a1) examples include aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate and carbodiimidated diphenylmethane polyisocyanate; hexamethylene diisocyanate.
  • aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate and carbodiimidated diphenylmethane polyisocyanate; hexamethylene diisocyanate.
  • Aliphatic or alicyclic polyisocyanates such as lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, and the like can be used.
  • These polyisocyanates may be used alone or in combination of two or more.
  • the polyisocyanate (a1) it is preferable to use an alicyclic polyisocyanate from the viewpoint that further excellent chemical resistance, abrasion resistance, and weather resistance can be obtained, and at least the nitrogen atom of the isocyanate group is cyclohexane. It is more preferable to use a polyisocyanate having one or more structures directly linked to a ring, and it is further preferable to use isophorone diisocyanate and/or dicyclohexylmethane diisocyanate. Further, the amount of the alicyclic polyisocyanate used is preferably 30% by mass or more in the polyisocyanate (a1) from the viewpoint that further excellent chemical resistance, abrasion resistance, and weather resistance can be obtained. 40 mass% or more is more preferable, and 50 mass% or more is still more preferable.
  • the alicyclic polyisocyanate and aliphatic polyisocyanate are used as the polyisocyanate (a1). It is preferable to use together with an isocyanate, and it is preferable to use hexamethylene diisocyanate as the aliphatic polyisocyanate.
  • the content of the alicyclic polyisocyanate in the polyisocyanate (a1) at this time is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more.
  • the amount of the polyisocyanate (a1) used is in the range of 5 to 50% by mass in the raw material of the urethane resin (A) from the viewpoint that further excellent chemical resistance, abrasion resistance and weather resistance can be obtained. It is preferably present, more preferably in the range of 15 to 40% by mass, still more preferably in the range of 20 to 37% by mass.
  • polyether polyol for example, polyether polyol, polyester polyol, polyacryl polyol, polycarbonate polyol, polybutadiene polyol, etc.
  • polycarbonate polyol for example, polycarbonate polyol, polybutadiene polyol, etc.
  • polycarbonate polyol for example, polycarbonate polyol from the viewpoint that further excellent chemical resistance, abrasion resistance, and weather resistance can be obtained.
  • polycarbonate polyol for example, a reaction product of a carbonic acid ester and/or phosgene and a compound having two or more hydroxyl groups can be used.
  • carbonic acid ester for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. can be used. These compounds may be used alone or in combination of two or more.
  • Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol and 2-methyl.
  • 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6 are preferred because they are able to obtain further excellent chemical resistance, abrasion resistance and weather resistance. It is preferable to use at least one compound selected from the group consisting of -hexanediol, 1,4-cyclohexanedimethanol, 3-methylpentanediol, and 1,10-decanediol. More preferable.
  • the amount of the polycarbonate polyol used is preferably 85% by mass or more, and 90% by mass or more in the polyol (a2) from the viewpoint that further excellent chemical resistance, abrasion resistance, and weather resistance can be obtained. Is more preferable, and 95 mass% or more is still more preferable.
  • the number average molecular weight of the polycarbonate polyol is preferably in the range of 100 to 100,000, from the viewpoint of further excellent chemical resistance, mechanical strength, abrasion resistance and weather resistance. It is more preferably in the range of to 10,000, more preferably in the range of 200 to 2,500.
  • the number average molecular weight of the polycarbonate polyol is a value measured by a gel permeation column chromatography (GPC) method.
  • the number average molecular weight of the polyol (a2) other than the polycarbonate polyol is preferably in the range of 500 to 100,000, and more preferably in the range of 700 to 50,000, from the viewpoint of further excellent weather resistance.
  • the range of 800 to 10,000 is more preferable.
  • the number average molecular weight of the polyol (a2) is a value measured by the gel permeation column chromatography (GPC) method.
  • the amount of the polyol (a2) used is preferably in the range of 30 to 80% by mass in the raw material of the urethane resin (A), more preferably in the range of 40 to 75% by mass, and in the range of 50 to 70% by mass. Is more preferable.
  • the chain extender (a3) is, for example, one having a number average molecular weight in the range of 50 to 450 (excluding the polycarbonate polyol), and specifically, ethylenediamine, 1,2-propanediamine, 1, 6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4′-dicyclohexylmethanediamine, 3,
  • a chain extender having an amino group is used from the viewpoint that further excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance can be obtained.
  • piperazine and/or hydrazine are more preferable, and the total amount of piperazine and hydrazine is preferably 30% by mass or more, more preferably 50% by mass or more, and 60% by mass in the chain extender (a3).
  • the above is more preferable, and 80% by mass or more is particularly preferable.
  • the chain extender (a3) preferably has an average number of functional groups of less than 3, and more preferably less than 2.5. Also,
  • the chain extender (a3) is used in an amount of 0.5 in the raw material of the urethane resin (A) from the viewpoint of further excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance. It is preferably in the range of to 10% by mass, more preferably in the range of 0.7 to 5% by mass, still more preferably in the range of 0.9 to 2.3.
  • the method for producing the urethane resin (A) for example, by reacting the polyisocyanate (a1), the polyol (a2), and the raw material used for producing the urethane resin having the hydrophilic group, an isocyanate group is obtained.
  • a method for producing a urethane prepolymer having ##STR3## and then reacting the urethane prepolymer with the chain extender (a3); the polyisocyanate (a1), the polyol (a2), and a hydrophilic group examples of the raw material used for producing the urethane resin having ##STR3## and a method of charging the chain extender (a3) at once and reacting. These reactions can be carried out, for example, at 50 to 100° C. for 3 to 10 hours.
  • the molar ratio [(isocyanate group)/(hydroxyl group and amino group)] with the isocyanate group of (a1) is preferably in the range of 0.8 to 1.2, and 0.9 to 1.1. The range is more preferable.
  • the urethane resin (A) When producing the urethane resin (A), it is preferable to deactivate the isocyanate group remaining in the urethane resin (A). When deactivating the isocyanate group, it is preferable to use an alcohol having one hydroxyl group such as methanol. The amount of the alcohol used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A).
  • An organic solvent may be used when producing the urethane resin (A).
  • the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetic ester compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; dimethylformamide, N-methylpyrrolidone and the like.
  • An amide compound or the like can be used.
  • These organic solvents may be used alone or in combination of two or more. It is preferable that the organic solvent is finally removed by a distillation method or the like.
  • the content of the urethane bond of the urethane resin (A) is preferably in the range of 980 to 4,000 mmol/kg from the viewpoint of obtaining further excellent chemical resistance, abrasion resistance and weather resistance.
  • the range of 3,000 to 3,500 mmol/kg is more preferable, the range of 1,100 to 3,000 mmol/kg is further preferable, and the range of 1,150 to 2,500 mmol/kg is further preferable.
  • the content of the urethane bond of the urethane resin (A) is the polyisocyanate (a1), the polyol (a2), the raw material used for producing the urethane resin having a hydrophilic group, and the chain extender (a3). ) Indicates the value calculated from the charged amount.
  • the content of the urea bond of the urethane resin (A) is preferably in the range of 315 to 850 mmol/kg, from the viewpoint of further excellent chemical resistance, abrasion resistance, and weather resistance.
  • the range of 350 to 830 mmol/kg is more preferable, the range of 400 to 800 mmol/kg is further preferable, and the range of 410 to 770 mmol/kg is further preferable.
  • the content of the urea bond of the urethane resin (A) is the polyisocyanate (a1), the polyol (a2), a raw material used for producing a urethane resin having a hydrophilic group, and a chain extender. The value calculated from the charged amount of (a3) is shown.
  • the content of the alicyclic structure of the urethane resin (A) is in the range of 500 to 3,000 mmol/kg from the viewpoint that further excellent chemical resistance, abrasion resistance and weather resistance can be obtained. Is preferable, the range of 600 to 2,900 mmol/kg is more preferable, and the range of 700 to 2,700 mmol/kg is further preferable.
  • the content of the alicyclic structure of the urethane resin (A) is the polyisocyanate (a1), the polyol (a2), the raw material used for producing the urethane resin having a hydrophilic group, and the chain extension. The value calculated from the charged amount of the agent (a3) is shown.
  • the content of the urethane resin (A) is preferably in the range of 3 to 50% by mass in the urethane resin composition from the viewpoint of coatability, workability and storage stability, and is preferably 5 to 30% by mass. A range is more preferable.
  • the water (B) ion exchanged water, distilled water or the like can be used.
  • the content of the water (B) is preferably in the range of 30 to 95% by mass in the urethane resin composition, from the viewpoint of coatability, workability and storage stability of the urethane resin composition, and 50 to 50% by weight.
  • the range of 90 mass% is more preferable.
  • the trisiloxane compound (C) is an essential component for obtaining an excellent repelling effect and scratch resistance by nails (hereinafter abbreviated as “nail scratch resistance”).
  • the trisiloxane compound (C) has a structure represented by the following formula (1) and does not have a structure represented by the following formula (2).
  • the oxygen atom in the above formula (1) may be directly linked to the Si atom in the trisiloxane compound (C), or may be linked to the Si atom via an alkylene group, an alkenyl group or the like. Further, the end not linked to the Si atom may be an alkyl group or a hydrogen atom linked to an oxygen atom.
  • the trisiloxane compound (C) may have other organic groups introduced therein.
  • the organic group for example, an alkyl group, a hydroxyl group, an amino group, a (meth)acryloyl group, a carboxyl group, a carbonyl group, an epoxy group or the like can be used. These organic groups may be used alone or in combination of two or more. Among these, an alkyl group is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable, from the viewpoint of obtaining even more excellent water dispersion stability.
  • the trisiloxane compound (C) 7 are alkyl groups out of 8 substituents that can be substituted on the Si atom in the trisiloxane compound (C) from the viewpoint of further excellent water dispersion stability.
  • the structure represented by the above formula (1) is substituted at the 3-position, and the alkyl group is substituted at the 1,1,1,3,5,5,5-position, that is, 3- It is preferable to use (polyoxyethylene)heptaalkyltrisiloxane and/or 3-(polyoxyethylene)alkylheptaalkyltrisiloxane, and more preferably 3-(polyoxyethylene)heptaalkyltrisiloxane.
  • the (polyoxyethylene) has the structure represented by the formula (1).
  • the (polyoxyethylene)alkyl has the structure represented by the formula (3).
  • R 1 represents an alkylene group having 1 to 5 carbon atoms, and n represents an integer of 1 to 30.
  • the molecular weight of the trisiloxane compound (C) is preferably in the range of 300 to 10,000, from the viewpoint of further excellent water dispersion stability, cissing suppression effect, and nail scratch resistance.
  • the range of 300 to 5,000 is more preferable, and the range of 500 to 3,000 is further preferable.
  • the molecular weight of the trisiloxane compound (C) indicates the chemical formula weight if it can be calculated from the chemical formula, and if it cannot be calculated, the number average molecular weight measured by gel permeation column chromatography (GPC) method. Show.
  • the content of the trisiloxane compound (C) in the urethane resin composition is in the range of 0.01 to 20% by mass from the viewpoint of further excellent crater suppressing effect and nail scratch resistance.
  • the range of 0.05 to 10% by mass is more preferable, the range of 0.1 to 8% by mass is more preferable, the range of 0.3 to 5% by mass is further preferable, and 0.4 to 2.5.
  • a mass% range is particularly preferred.
  • the range of parts is more preferable, the range of 1-27 parts by mass is further preferable, and the range of 3-25 parts by mass is particularly preferable.
  • the urethane resin composition of the present invention contains the urethane resin (A), water (B), and compound (C) as essential components, but other additives may be used if necessary.
  • Examples of the other additives include a filler (D), a crosslinking agent (E), an emulsifier, an antifoaming agent, a leveling agent, a thickener, a viscoelasticity adjusting agent, an antifoaming agent, a wetting agent, a dispersant, and an antiseptic agent.
  • Agents, plasticizers, penetrants, fragrances, bactericides, acaricides, fungicides, UV absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments (eg titanium white, red iron oxide, phthalocyanine, carbon) Black, permanent yellow, etc.) can be used.
  • These additives may be used alone or in combination of two or more.
  • a filler (D) for imparting a matte feeling to the coating film, and mechanical properties of the coating film is preferable to contain a crosslinking agent (E) in order to improve the strength.
  • Examples of the filler (D) include silica particles, organic beads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, and alumina silicate. Can be used. These fillers may be used alone or in combination of two or more.
  • silica particles for example, dry silica, wet silica and the like can be used. Among these, dry silica is preferable because it has a high scattering effect and a wide adjustment range of the gloss value.
  • the average particle diameter of these silica particles is preferably in the range of 2 to 14 ⁇ m, more preferably in the range of 3 to 12 ⁇ m.
  • the average particle size of the silica particles indicates the particle size when the integrated amount accounts for 50% in the integrated particle amount curve of the particle size distribution measurement results (the particle size at D50 in the particle size distribution).
  • organic beads for example, acrylic beads, urethane beads, silicon beads, olefin beads, etc. can be used.
  • the amount of the filler (D) used can be appropriately determined according to the matte feel to be imparted, but for example, it is in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the urethane resin (A). It is preferably in the range of 3 to 10 parts by mass.
  • crosslinking agent (E) for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a carbodiimide crosslinking agent, an oxazolidine crosslinking agent, an oxazoline crosslinking agent, a melamine crosslinking agent, etc. can be used. These crosslinking agents may be used alone or in combination of two or more kinds.
  • the amount of the cross-linking agent (E) used is, for example, preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the urethane resin (A). ..
  • the urethane resin composition of the present invention can provide a film having an excellent crater suppressing effect on various base materials and a nail scratch resistance. Therefore, the urethane resin composition of the present invention is suitably used as a surface treatment agent for various articles such as synthetic leather, polyvinyl chloride (PVC) leather, thermoplastic olefin resin (TPO) leather, dashboard, instrument panel and the like. be able to.
  • various articles such as synthetic leather, polyvinyl chloride (PVC) leather, thermoplastic olefin resin (TPO) leather, dashboard, instrument panel and the like. be able to.
  • the article of the present invention has a layer formed by the surface treatment agent.
  • the article include, for example, synthetic leather, artificial leather, natural leather, interior sheet of automobile using polyvinyl chloride (PVC) leather, sports shoes, clothing, furniture, thermoplastic olefin (TPO) leather, dashboard. , Instrument panels and the like.
  • PVC polyvinyl chloride
  • TPO thermoplastic olefin
  • the layer thickness of the surface treatment agent is, for example, in the range of 0.1 to 100 ⁇ m.
  • urethane resin (A-1) aqueous dispersion having a nonvolatile content of 30% by mass.
  • the urethane bond content of the obtained urethane resin (A-1) was 2,052 mmol/kg, the urea bond content was 698 mmol/kg, and the alicyclic structure content was 715 mmol/kg.
  • a methyl ethyl ketone solution of urethane prepolymer was obtained.
  • 4.5 parts by mass of piperazine and 9 parts by mass of triethylamine were mixed with a methyl ethyl ketone solution of this urethane prepolymer, and then 880 parts by mass of ion-exchanged water was added thereto to emulsify the urethane resin (A-2) in water.
  • a liquid was obtained.
  • methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added to obtain a urethane resin (A-2) aqueous dispersion having a nonvolatile content of 32% by mass.
  • the urethane bond content of the obtained urethane resin (A-2) was 1,278 mmol/kg, the urea bond content was 435 mmol/kg, and the alicyclic structure content was 1,713 mmol/kg.
  • urethane resin (A-3) aqueous dispersion having a nonvolatile content of 30% by mass.
  • the urethane bond content of the obtained urethane resin (A-3) was 1,747 mmol/kg, the urea bond content was 576 mmol/kg, and the alicyclic structure content was 2,341 mmol/kg.
  • Example 1 35 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide cross-linking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.), and a filler (manufactured by Evonik Degussa) ACEMATT TS 100", silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, 3-(polyoxyethylene)heptamethyltrisiloxane (molecular weight: 600, hereinafter abbreviated as "C1") 0
  • a urethane resin composition was obtained by mixing 1 part by weight and 59.9 parts by weight of water.
  • Example 2 35 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide cross-linking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.), and a filler (manufactured by Evonik Degussa) ACEMATT TS 100", silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, 0.5 parts by mass of C1 and 59.5 parts by mass of water are mixed to obtain a urethane resin composition. It was
  • Example 3 35 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide cross-linking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.), and a filler (manufactured by Evonik Degussa) ACEMATT TS 100", silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, C1 1 part by mass, and water 59 parts by mass were mixed to obtain a urethane resin composition.
  • a carbodiimide cross-linking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.)
  • a filler manufactured by Evonik Degussa) ACEMATT TS 100"
  • Example 4 35 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, 3 parts by mass of carbodiimide crosslinking agent "Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd., filler ("ACEMATT” manufactured by Evonik Degussa) TS 100", silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, C1 2 parts by mass, and water 58 parts by mass were mixed to obtain a urethane resin composition.
  • carbodiimide crosslinking agent "Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.
  • filler (“ACEMATT” manufactured by Evonik Degussa) TS 100”
  • silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, C1 2 parts by mass, and water 58 parts by mass were mixed to obtain a
  • Example 5 35 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, 3 parts by mass of carbodiimide crosslinking agent "Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd., filler ("ACEMATT” manufactured by Evonik Degussa) TS 100", silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, C1 3 parts by mass, and water 57 parts by mass were mixed to obtain a urethane resin composition.
  • carbodiimide crosslinking agent "Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.
  • filler (“ACEMATT” manufactured by Evonik Degussa) TS 100”
  • silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, C1 3 parts by mass, and water 57 parts by mass were mixed to obtain a
  • Example 6 35 parts by mass of the urethane resin (A-2) aqueous dispersion obtained in Synthesis Example 2, 3 parts by mass of carbodiimide crosslinking agent "Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd., filler ("ACEMATT” manufactured by Evonik Degussa) TS 100", silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, C1 1 part by mass, and water 59 parts by mass were mixed to obtain a urethane resin composition.
  • carbodiimide crosslinking agent "Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.
  • filler (“ACEMATT” manufactured by Evonik Degussa) TS 100”
  • silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, C1 1 part by mass, and water 59 parts by mass were mixed to obtain a
  • Example 7 35 parts by mass of the urethane resin (A-3) aqueous dispersion obtained in Synthesis Example 3, 3 parts by mass of carbodiimide crosslinking agent "Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd., filler ("ACEMATT” manufactured by Evonik Degussa) TS 100", silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, 3-(polyoxyethylene)heptamethyltrisiloxane (molecular weight: 800, hereinafter abbreviated as "C2”) 1
  • a urethane resin composition was obtained by mixing 50 parts by mass of water and 59 parts by mass of water.
  • a carbodiimide cross-linking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.)
  • a filler manufactured by Evonik Degussa) ACEMATT TS 100"
  • [Comparative example 2] 35 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide cross-linking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.), and a filler (manufactured by Evonik Degussa) ACEMATT TS 100", silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, 3-(polyoxyethylene polyoxypropylene) heptamethyltrisiloxane (structure (EO) shown in the above formula (1)) Ratio [EO/PO] 40/60, molecular weight; 600, hereinafter abbreviated as "EOPO".) 1 part by mass of water A urethane resin composition was obtained by mixing 59 parts by mass.
  • a carbodiimide cross-linking agent (“Carbodilite V-02-L2” manufactured by Niss
  • the number average molecular weight of the polyol used in the synthesis example is a value obtained by measurement by the gel permeation column chromatography (GPC) method under the following conditions.
  • Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSK gel G4000” (7.8 mm ID x 30 cm) x 1 "TSK gel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (differential refractometer) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL/min Injection volume: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • the urethane resin composition of the present invention has an excellent crater suppressing effect and nail scratch resistance.
  • Comparative Example 2 is an embodiment using a trisiloxane compound having a structure represented by the formula (2), but cissing was generated on the base material.

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

Abstract

La présente invention concerne une composition de résine d'uréthane caractérisée en ce qu'elle contient une résine d'uréthane (A), de l'eau (B) et un composé trisiloxane (C) ayant une structure représentée par la formule (1) mais n'ayant pas une structure représentée par la formule (2). La présente invention concerne également un agent de traitement de surface caractérisé en ce qu'il contient la composition de résine d'uréthane. La présente invention concerne en outre un article caractérisé en ce qu'il comprend une couche formée par l'agent de traitement de surface. Le composé trisiloxane (C) comprend de préférence sept groupes alkyle, et est plus préférentiellement le 3-(polyoxy-éthylène)hepta-alkyl-trisiloxane et/ou le 3-(polyoxy-éthylène)alkyl-hepta-alkyl-trisiloxane.
PCT/JP2019/047588 2018-12-21 2019-12-05 Composition de résine d'uréthane, agent de traitement de surface et article Ceased WO2020129671A1 (fr)

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Citations (8)

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JPH10216657A (ja) * 1997-02-13 1998-08-18 Ito Kogaku Kogyo Kk 有機光学要素の積層塗膜除去方法
WO2002002676A1 (fr) * 2000-07-05 2002-01-10 Nippon Arc Co., Ltd. Lamine transparent, lentille plastique pour monture de lunette et composition d'amorçage
JP2008519868A (ja) * 2004-11-09 2008-06-12 イーストマン コダック カンパニー ミクロゲル粒子を含むインクジェット組成物
JP2009545517A (ja) * 2006-05-15 2009-12-24 オーエムエス・インヴェストメンツ・インコーポレイティッド シリコーン界面活性剤系農業製剤及びその使用方法
JP2013510769A (ja) * 2009-11-12 2013-03-28 ダウ コーニング コーポレーション 被コーティング織物製品
JP2013510768A (ja) * 2009-11-12 2013-03-28 ダウ コーニング コーポレーション 被覆ファブリック製品
JP2018044052A (ja) * 2016-09-13 2018-03-22 トーヨーポリマー株式会社 防曇コーティング組成物および防曇皮膜

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Publication number Priority date Publication date Assignee Title
DE102009053224A1 (de) * 2009-11-06 2011-07-14 Bayer MaterialScience AG, 51373 Verfahren zur Herstellung eines Polyurethanschaums und hieraus erhältlicher Polyurethanschaum
BR112018011157A2 (pt) * 2015-11-30 2019-05-21 Kumiai Chemical Industry Co. Ltd composição agroquímica de suspensão aquosa.

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09291227A (ja) * 1996-02-26 1997-11-11 Ito Kogaku Kogyo Kk 光学要素用プライマー塗料
JPH10216657A (ja) * 1997-02-13 1998-08-18 Ito Kogaku Kogyo Kk 有機光学要素の積層塗膜除去方法
WO2002002676A1 (fr) * 2000-07-05 2002-01-10 Nippon Arc Co., Ltd. Lamine transparent, lentille plastique pour monture de lunette et composition d'amorçage
JP2008519868A (ja) * 2004-11-09 2008-06-12 イーストマン コダック カンパニー ミクロゲル粒子を含むインクジェット組成物
JP2009545517A (ja) * 2006-05-15 2009-12-24 オーエムエス・インヴェストメンツ・インコーポレイティッド シリコーン界面活性剤系農業製剤及びその使用方法
JP2013510769A (ja) * 2009-11-12 2013-03-28 ダウ コーニング コーポレーション 被コーティング織物製品
JP2013510768A (ja) * 2009-11-12 2013-03-28 ダウ コーニング コーポレーション 被覆ファブリック製品
JP2018044052A (ja) * 2016-09-13 2018-03-22 トーヨーポリマー株式会社 防曇コーティング組成物および防曇皮膜

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