CN114698377B - Polyurethane aqueous dispersion, inkjet ink composition, aqueous printing ink composition, and aqueous coating composition - Google Patents

Polyurethane aqueous dispersion, inkjet ink composition, aqueous printing ink composition, and aqueous coating composition Download PDF

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CN114698377B
CN114698377B CN202080077839.9A CN202080077839A CN114698377B CN 114698377 B CN114698377 B CN 114698377B CN 202080077839 A CN202080077839 A CN 202080077839A CN 114698377 B CN114698377 B CN 114698377B
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aqueous
polyolefin
acid
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CN114698377A (en
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饭室美纪
山根增美
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Sanyo Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/06—Oxidation
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Electrochemistry (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The purpose of the present invention is to provide an aqueous polyurethane dispersion which has excellent storage stability and exhibits excellent adhesion to a variety of substrates. The present invention relates to an aqueous polyurethane dispersion comprising water and a polyurethane resin (U) wherein the polyurethane resin (U) is obtained by reacting an active hydrogen group-containing compound component (W) with an isocyanate component (B), the active hydrogen group-containing compound component (W) comprises a polymer polyol (A) which is a polyol comprising a hydroxyl group-containing polyolefin (A1) and not comprising a polyester polyol (RA) having a structural unit represented by the following general formula (1), and the weight ratio of ethylene to an alpha-olefin having 3 to 8 carbon atoms [ ethylene/alpha-olefin ] as a constituent monomer of the hydroxyl group-containing polyolefin (A1)]From 5/95 to 65/35, the isotactic of the alpha-olefin portion of (A1)The regularity is 1-50%. [ chemical formula 1 ] ]

Description

Polyurethane aqueous dispersion, inkjet ink composition, aqueous printing ink composition, and aqueous coating composition
Technical Field
The present invention relates to an aqueous polyurethane dispersion, an inkjet ink composition, an aqueous printing ink composition, an aqueous coating composition, a paste for printing, an electrode binder for a nonaqueous electrolyte secondary battery, an electrode for a nonaqueous electrolyte secondary battery, and a nonaqueous electrolyte secondary battery.
Background
Conventionally, aqueous polyurethane resins have been used for paints, adhesives, fiber processing agents, paper processing agents, inks, and the like. The coated substrate is of various kinds such as iron, fiber, PET film, and olefin resin substrate, and recently, the use of olefin resin substrate such as PP (polypropylene) has been increasing particularly from the viewpoint of cost and recyclability. On the other hand, the olefin resin base material has no polar group in the molecule and is chemically inert, and therefore has a problem that it is difficult to apply and adhere.
In order to improve adhesion to an olefin-based substrate, an aqueous polyurethane resin composition using a chlorinated polyol has been proposed (for example, patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. H06-172637
Disclosure of Invention
Problems to be solved by the invention
However, even in the technique of patent document 1, the storage stability is not sufficiently satisfactory, and improvement is required. The purpose of the present invention is to provide a polyurethane aqueous dispersion which has excellent substrate adhesion and storage stability of a coating film.
Means for solving the problems
The present inventors have studied in order to achieve the above object and as a result, have completed the present invention.
Specifically, the present invention relates to an aqueous polyurethane dispersion comprising water and a polyurethane resin (U) wherein the polyurethane resin (U) is obtained by reacting an active hydrogen group-containing compound component (W) with an isocyanate component (B), the active hydrogen group-containing compound component (W) comprises a polymer polyol (a) which is a polyol containing a hydroxyl group-containing polyolefin (A1) and not containing a polyester polyol (RA) having a structural unit represented by the following general formula (1), and the weight ratio [ ethylene/α -olefin ] of ethylene to a c-number of 3 to 8, which is a constituent monomer of the hydroxyl group-containing polyolefin (A1), is 5/95 to 65/35, and the stereoregularity of the α -olefin portion of the hydroxyl group-containing polyolefin (A1) is 1 to 50%; an inkjet ink composition, an aqueous printing ink composition, an aqueous coating composition, a printing paste, and a nonaqueous electrolyte secondary battery electrode binder each using the above polyurethane aqueous dispersion; an electrode for a nonaqueous electrolyte secondary battery formed using an active material, a metal current collector, and the above-described nonaqueous electrolyte secondary battery electrode binder; the nonaqueous electrolyte secondary battery comprises an electrolyte, a separator and the electrode for nonaqueous electrolyte secondary battery.
[ chemical 1]
ADVANTAGEOUS EFFECTS OF INVENTION
The aqueous polyurethane dispersion of the present invention exhibits the following effects.
(1) The storage stability is excellent.
(2) The coating film has excellent adhesion to the substrate.
Detailed Description
< polyurethane resin (U) >)
The polyurethane resin (U) in the present invention is a polyurethane resin obtained by reacting an active hydrogen group-containing compound component (W) with an isocyanate component (B). The urethane resin (U) may have an ureido group, and in this case, the urethane resin (U) is a polyurethaneurea resin.
The active hydrogen group-containing compound component (W) contains a polymer polyol (a).
The polymer polyol (a) is a polyol which contains the polyolefin (A1) having a hydroxyl group and does not contain the polyester polyol (RA) having a structural unit represented by the following general formula (1).
[ chemical 2]
< polyolefin containing hydroxyl group (A1) >)
The hydroxyl group-containing polyolefin (A1) in the present invention can be obtained, for example, by reacting an amino alcohol (G) with an acid-modified polyolefin (X) obtained by modifying a polyolefin (a 01) having a carbon-carbon double bond, which will be described later, with an unsaturated (poly) carboxylic acid (anhydride) (E), or by reacting an acid-modified polyolefin (X) with an alkylene oxide (hereinafter referred to simply as AO).
The polyolefin (A01) contains ethylene and an alpha-olefin (having 3 to 8 carbon atoms) as constituent monomers.
The alpha-olefin (having 3 to 8 carbon atoms) is an alpha-olefin having 3 to 8 carbon atoms, and examples of the alpha-olefin having 3 to 8 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. In the present specification, "α -olefin" does not include ethylene unless specifically stated otherwise.
The alpha-olefin may be used in combination of 2 or more, but 1 is preferable.
Among the above-mentioned α -olefins, from the viewpoint of adhesion (substrate adhesion) between a coating film obtained from the polyurethane aqueous dispersion and a polyolefin-based substrate, a linear α -olefin (having 3 to 8 carbon atoms) is preferable, a linear α -olefin (having 3 to 6 carbon atoms) is more preferable, and propylene is particularly preferable.
The weight ratio [ ethylene/α -olefin ] of ethylene to α -olefin (having 3 to 8 carbon atoms) as a constituent monomer of the polyolefin (A01) is preferably 5/95 to 65/35, more preferably 10/90 to 60/40, still more preferably 15/85 to 40/60.
The weight ratio of ethylene to an alpha-olefin having 3 to 8 carbon atoms of the polyolefin (A01) is directly reflected in the weight ratio of ethylene to an alpha-olefin having 3 to 8 carbon atoms of the hydroxyl group-containing polyolefin (A1), and therefore, when the weight ratio [ ethylene/alpha-olefin ] is less than 5/95, the storage stability of the aqueous polyurethane dispersion is inferior; if the weight ratio [ ethylene/α -olefin ] exceeds 65/35, the adhesion of the base material is poor.
The above weight ratio [ ethylene/alpha-olefin ]]For example, by 1 H-NMR calculation. The weight ratio of ethylene to an α -olefin having 3 to 8 carbon atoms in the polyolefin (a 01) can be adjusted by the weight ratio of ethylene to an α -olefin having 3 to 8 carbon atoms in the high molecular weight polyolefin (a 00) to be described later.
In the polyolefin (a 01), other monomers may be used as the constituent monomers in addition to ethylene and α -olefin (having 3 to 8 carbon atoms). In this case, the weight of the other monomers is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less, based on the weight of all monomers constituting the polyolefin (a 01).
Examples of the other monomer include 2-butene, isobutylene, an α -olefin having 9 to 30 carbon atoms (e.g., 1-decene and 1-dodecene) and an unsaturated monomer other than the α -olefin having 4 to 30 carbon atoms (e.g., vinyl acetate).
The number average molecular weight (Mn) of the polyolefin (a 01) is preferably 800 to 5,800, more preferably 900 to 4,800, particularly preferably 1,000 to 3,800, from the viewpoints of adhesion to a substrate and storage stability.
The conditions for measuring Mn and weight average molecular weight (Mw) of the hydroxyl group-containing polyolefin (A1), polyolefin (a 01), high molecular weight polyolefin (a 00), acid-modified polyolefin (X) and polyurethane resin (U) based on GPC (gel chromatography) in the present invention are as follows.
The device comprises: high temperature gel permeation chromatography
[ "Alliance GPC V2000", manufactured by Waters Co., ltd ]
The detection device comprises: refractive index detector
Solvent: o-dichlorobenzene
Reference substance: polystyrene sample concentration: 3mg/ml
Column stationary phase: PLgel 10 μm, MIXED-B2 root tandem
[ Polymer Laboratories Co., ltd.)
Column temperature: 135 DEG C
The number of double bonds per 1,000 carbon atoms [ (the molecular terminal and/or the number of carbon-carbon double bonds in the molecular chain ] of the polyolefin (a 01) is preferably 1 to 30, more preferably 1.5 to 20, particularly preferably 2 to 15 from the viewpoints of reactivity with the (poly) carboxylic acid (anhydride) (E) described later and productivity.
Here, the double bond number may be determined by the polyolefin (A01) 1 The spectrum of H-NMR (nuclear magnetic resonance) spectroscopy was obtained. That is, the peaks in the spectrum are assigned, and the relative value of the number of double bonds of the polyolefin (A01) and the number of carbon atoms of the polyolefin (A01) is obtained from the integral value of double bonds at 4.5 to 6ppm from the polyolefin (A01) and the integral value from the polyolefin (A01), and the number of double bonds in the molecular terminal and/or molecular chain of the polyolefin (A01) per 1,000 carbon atoms is calculated. The number of double bonds in examples described below was calculated by this method.
The isotacticity of the α -olefin portion of the polyolefin (a 01) is preferably 1 to 50%, more preferably 5 to 45%, particularly preferably 10 to 40%, from the viewpoints of adhesion and storage stability.
The isotacticity of the α -olefin portion of the polyolefin (a 01) tends to be directly reflected in the isotacticity of the α -olefin portion of the acid-modified polyolefin (X) and the hydroxyl group-containing polyolefin (A1) described later. The isotacticity of the α -olefin portion of the polyolefin (a 01) tends to reflect the isotacticity of the α -olefin portion of the high-molecular weight polyolefin (a 00) to be described later as a raw material, and thus can be adjusted by the high-molecular weight polyolefin (a 00) of the raw material used.
The isotacticity mentioned above can be used, for example 13 C-NMR (nuclear magnetic resonance spectroscopy). It is well known that in general, a side chain methyl group is affected by a steric configuration (meso or racemic) to the extent of two adjacent methyl groups (triad ), two adjacent methyl groups (pentad ) to the triad, and further two adjacent methyl groups (heptad, heppad) to the pentad, peaks are observed at different chemical shifts. The evaluation of the stereoregularity is usually performed on the pentad, and the isotacticity in the present invention can be calculated based on the evaluation of the pentad.
That is, in the case where the α -olefin is propylene, the reaction proceeds by 13 When the carbon peak derived from the side chain methyl group in propylene obtained by C-NMR is (H) and the peak derived from methyl group in isotactic propylene formed by meso structure alone in the pentad is (Ha), the isotacticity is calculated by the following formula.
Isotacticity (%) = [ (Ha)/Σ (H) ]×100 (1)
Wherein Ha is the peak height of the isotactic (pentad is formed by meso structure only) signal and H is the peak height of pentad.
The isotacticity of the α -olefin portion of the polyolefin (a 01) or the acid-modified polyolefin (X) may be measured in the same manner as described above.
Examples of the method for producing the polyolefin (a 01) include a method of thermally degrading a polyolefin (a 00) having a high molecular weight (preferably Mn 60,000 ～ 400,000, more preferably Mn 80,000 ～ 250,000).
The thermal degradation method includes: a method of thermally degrading the above-mentioned high molecular weight polyolefin (A00) (1) in the absence of an organic peroxide, for example, at 300 to 450 ℃ for 0.5 to 10 hours; and (2) a method of thermally degrading for 0.5 to 10 hours in the presence of an organic peroxide [ e.g., 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane ], e.g., at 180 to 300 ℃; etc.
Among these, the method (1) is preferred in which a polyolefin having a larger number of double bonds at the molecular terminals and/or in the molecular chain is easily obtained from the industrial aspect and the modification characteristics aspect.
The weight ratio of ethylene to α -olefin [ ethylene/α -olefin ] as a monomer constituting the polyolefin (A01) tends to be constant with the weight ratio of the high molecular weight polyolefin (A00) [ ethylene/α -olefin ].
In addition, the higher the thermal degradation temperature and the longer the thermal degradation time, the greater the number of double bonds per 1000 carbon atoms tends to be.
Further, the smaller the Mn of the high molecular weight polyolefin (a 00), the higher the thermal degradation temperature and the longer the thermal degradation time, the smaller the Mn of the high molecular weight polyol (a) tends to be.
In addition, the greater the isotacticity of the high molecular weight polyolefin (A00), the greater the isotacticity of the polyolefin (A01) tends to be.
The unsaturated (poly) carboxylic acid (anhydride) (E) includes (poly) carboxylic acids (anhydrides) having 1 polymerizable unsaturated group and having 3 to 30 carbon atoms [ hereinafter, may be abbreviated as "C").
In the present invention, the unsaturated (poly) carboxylic acid (anhydride) means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and/or an unsaturated polycarboxylic acid anhydride.
Among the unsaturated (poly) carboxylic acids (anhydrides) (E), examples of the unsaturated monocarboxylic acids include aliphatic monocarboxylic acids (C3 to 24, for example, acrylic acid, methacrylic acid, α -ethacrylic acid, crotonic acid, isocrotonic acid), and alicyclic monocarboxylic acids (C6 to 24, for example, cyclohexene carboxylic acid); examples of the unsaturated polybasic (C2 to 3 or more) carboxylic acid (anhydride) include unsaturated dicarboxylic acid (anhydride) [ aliphatic dicarboxylic acid (anhydride) (C4 to 24, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and anhydrides thereof), alicyclic dicarboxylic acid (anhydride) (C8 to 24, for example, cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptene dicarboxylic acid, methyltetrahydrophthalic acid, and anhydrides thereof), and the like ]. The unsaturated (poly) carboxylic acid (anhydride) (E) may be used alone or in combination of 1 or more than 2.
Among the above-mentioned unsaturated (poly) carboxylic acids (anhydrides) (E), unsaturated dicarboxylic anhydrides are preferred, and maleic anhydride is more preferred from the viewpoints of reactivity, storage stability and mechanical strength of the polyolefin (a 01).
< acid-modified polyolefin (X) >)
The acid-modified polyolefin (X) of the present invention comprises the above-mentioned polyolefin (A01) having a carbon-carbon double bond and an unsaturated (poly) carboxylic acid (anhydride) (E) as structural units. The polyolefin (A01) is preferably reacted with an unsaturated (poly) carboxylic acid (anhydride) (E) in the absence or presence of a radical initiator.
From the viewpoint of balance between the substrate adhesion and the storage stability, the weight ratio of the polyolefin (a 01) to the unsaturated (poly) carboxylic acid (anhydride) (E) [ polyolefin (a 01)/unsaturated (poly) carboxylic acid (anhydride) (E) ] is preferably 80/20 to 99.5/0.5, more preferably 90/10 to 99/1.
The acid-modified polyolefin (X) can be preferably produced as follows: in the presence of a radical initiator (F), an appropriate organic solvent [ C3-18, for example, hydrocarbon (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbon (dichloroethane, trichloroethane or tetrachloroethane, dichlorobutane, etc.), ketone (acetone, methyl ethyl ketone, di-t-butyl ketone, etc.), ether (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc. ], and the like, are added to the polyolefin (A01) and the unsaturated (poly) carboxylic acid (anhydride) (E), if necessary, and reacted.
The radical initiator (F) may be a known radical initiator, for example, an azo initiator (azobisisobutyronitrile or the like) or a peroxide initiator (dicumyl peroxide or the like).
Among the above radical initiators (F), peroxide initiators are preferred.
The reaction temperature is preferably 100 to 270 ℃, more preferably 120 to 250 ℃, particularly preferably 130 to 240 ℃ in view of reactivity and productivity of the polyolefin (a 01) and the unsaturated (poly) carboxylic acid (anhydride) (E).
The acid value of the acid-modified polyolefin (X) is preferably 1 to 130mgKOH/g, more preferably 3 to 75mgKOH/g, particularly preferably 5 to 50mgKOH/g, from the viewpoint of adhesion to a substrate. The acid value here is in accordance with JIS K0070:1992 values measured according to the following steps (i) to (iii).
(i) 1g of the acid-modified polyolefin (X) was dissolved in 100g of xylene whose temperature was adjusted to 100 ℃.
(ii) At this temperature, phenolphthalein was used as an indicator and titrated with 0.1mol/L potassium hydroxide ethanol solution [ trade name "0.1mol/L ethanol potassium hydroxide solution", manufactured by Fuji photo-pure chemical Co., ltd.).
(iii) The amount of potassium hydroxide required for titration was converted to mg, and the acid value (unit: mgKOH/g) was calculated.
In the above measurement, the result was obtained that 1 acid anhydride group was equivalent to 1 carboxyl group.
The acid value can be appropriately adjusted by the number of double bonds of the polyolefin (a 01), the weight of the polyolefin (a 01), the type of the unsaturated (poly) carboxylic acid (anhydride) (E), and the weight of the unsaturated (poly) carboxylic acid (anhydride) (E).
The Mn of the acid-modified polyolefin (X) is preferably 900 to 5,900, more preferably 900 to 5,000, particularly preferably 900 to 4,000, from the viewpoints of solvent solubility and substrate adhesion.
The isotacticity of the α -olefin portion of the acid-modified polyolefin (X) is preferably 1 to 50%, more preferably 5 to 45%, particularly preferably 10 to 40%, from the viewpoints of solvent solubility and substrate adhesion.
The hydroxyl group-containing polyolefin (A1) in the aqueous polyurethane dispersion of the present invention can be obtained by a reaction of the acid-modified polyolefin (X) with the amino alcohol (G), a reaction of the acid-modified polyolefin (X) with AO, or the like.
Examples of the aminoalcohol (G) include linear alkanolamines, cycloalkanolamines, and alkylalkanolamines having 2 to 12 carbon atoms (for example, 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminocaprol, diethanolamine, di-n-propanolamine, isopropanolamine, 3-aminomethyl-3, 5-trimethylcyclohexanol, methylethanolamine, and ethylethanolamine), etc., and 2-aminoethanol is preferable from the viewpoint of adhesion to a substrate.
Examples of the AO include AO having 2 to 12 carbon atoms (such as ethylene oxide, 1, 2-propylene oxide, or 1, 3-propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, or 1, 3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, styrene oxide, and an alpha-olefin oxide), and AO having 2 to 4 carbon atoms is preferable from the viewpoint of adhesion to a substrate, and ethylene oxide and propylene oxide are more preferable. The AO may be used alone or in combination of 2 or more.
From the viewpoint of adhesion to a substrate, the addition mole number of AO is preferably 1 to 10 moles or more, more preferably 1 to 5 moles, and particularly preferably 1 mole per 1 carboxyl group of the acid-modified polyolefin (X).
The modification of the acid-modified polyolefin (X) with the amino alcohol (G) can be carried out by a known method. For example, the following methods may be mentioned: an excess (for example, 1.1 to 2 times mol or more) of the aminoalcohol (G) is added to the carboxyl group (carbonyl group in the case of an acid anhydride) of the acid-modified polyolefin (X) to react the same, and then unreacted aminoalcohol is removed by a distillation method or the like. The reaction may be carried out in the presence or absence of an organic solvent. The reaction temperature is preferably 100 to 220℃and more preferably 120 to 200℃in terms of reaction rate and reaction stability.
Modification of the acid-modified polyolefin (X) with AO is carried out by a known method. For example, the reaction temperature at the time of ring-opening addition polymerization of AO is preferably 40 to 200℃and more preferably 70 to 160℃in terms of reaction rate and reaction stability. The reaction pressure is preferably-0.1 to 0.5MPa. The reaction is carried out in the presence of a catalyst as required.
The hydroxyl group-containing polyolefin (A1) may be used alone or in combination of 2 or more.
The weight ratio of ethylene to an alpha-olefin (having 3 to 8 carbon atoms) [ ethylene/alpha-olefin ] as a constituent monomer of the hydroxyl group-containing polyolefin (A1) is 5/95 to 65/35, preferably 10/90 to 60/40, more preferably 15/85 to 40/60.
When the weight ratio [ ethylene/α -olefin ] is less than 5/95, the storage stability is poor; if the ratio exceeds 65/35, the substrate adhesion is poor.
The weight ratio of ethylene to the alpha-olefin having 3 to 8 carbon atoms as the constituent monomer of the hydroxyl group-containing polyolefin (A1) can be suitably adjusted by the ratio of ethylene to the alpha-olefin having 3 to 8 carbon atoms used for the high molecular weight polyolefin (A00).
The isotacticity of the alpha-olefin portion of the hydroxyl group-containing polyolefin (A1) is 1 to 50%, preferably 5 to 45%, more preferably 10 to 40%. If the isotacticity of the α -olefin portion of the hydroxyl group-containing polyolefin (A1) is less than 1%, the substrate adhesion is poor; if it exceeds 50%, the solvent solubility is poor.
The isotacticity of the α -olefin portion of the above-mentioned hydroxyl group-containing polyolefin (A1) can be appropriately adjusted by the isotacticity of the polyolefin (a 01).
The Mn of the hydroxyl group-containing polyolefin (A1) is preferably 500 or more, and from the viewpoints of adhesion to a substrate and storage stability, it is preferably 1,000 to 10,000, more preferably 1,100 to 7,500, and particularly preferably 1,400 to 5,500.
Mn of the hydroxyl group-containing polyolefin (A1) can be appropriately adjusted by controlling Mn of the polyolefin (A01), the kind and amount of the unsaturated (poly) carboxylic acid (anhydride) (E), and the reaction of the polyolefin (A01) with the unsaturated (poly) carboxylic acid (anhydride) (E).
The hydroxyl value (mgKOH/g) of the hydroxyl group-containing polyolefin (A1) is preferably 12 to 120, more preferably 15 to 110, particularly preferably 20 to 80, from the viewpoint of adhesion to a substrate.
The hydroxyl value of the hydroxyl group-containing polyolefin (A1) can be appropriately adjusted by the number of double bonds possessed by the polyolefin (A01), the amount of the polyolefin (A01), the kind and amount of the unsaturated (poly) carboxylic acid (anhydride) (E), and the kind and amount of the amino alcohol (G) or AO.
The acid value (mgKOH/g) of the hydroxyl group-containing polyolefin (A1) is preferably 0 to 50, more preferably 0 to 30, from the viewpoint of the water resistance of the coating film.
The hydroxyl value and the acid value of the hydroxyl group-containing polyolefin (A1) were measured in accordance with JIS K0070-1992.
In the present invention, the hydroxyl number of the hydroxyl group-containing polyolefin (A1) per 1 molecule is preferably 1.5 to 2.0, more preferably 1.6 to 2.0, from the viewpoint of adhesion to a substrate. The hydroxyl number of the polyolefin (A1) having hydroxyl groups per 1 molecule can be calculated by the following formula (1).
Hydroxyl number=mn of hydroxyl group per 1 molecule of the hydroxyl group-containing polyolefin (A1) A1 ×OHV/56100(1)
Mn A1 : mn of the hydroxyl group-containing polyolefin (A1)
OHV: hydroxyl value (mgKOH/g) of polyolefin having hydroxyl group (A1)
When a plurality of hydroxyl group-containing polyolefins (A1) are used as the polyurethane resin (U), the average value of the hydroxyl groups of all the hydroxyl group-containing polyolefins (A1) constituting the polyurethane resin (U) is preferably 1.5 to 2.0, more preferably 1.6 to 2.0, per 1 molecule of the hydroxyl group-containing polyolefin (A1), from the viewpoint of adhesion to the substrate of the polyurethane resin (U).
In the polyurethane resin (U) of the present invention, the polymer polyol (a) is a polyol which contains the polyolefin (A1) having a hydroxyl group as an essential constituent monomer and does not contain the polyester polyol (RA) having a structural unit represented by the following general formula (1).
The polyurethane resin (U) of the present invention is excellent in storage stability of an aqueous polyurethane dispersion by not containing a polyester polyol (RA) having a structural unit represented by the following general formula (1).
[ chemical 3]
As the polymer polyol (a) other than the hydroxyl group-containing polyolefin (A1), 1 or more of the condensed polyester polyol (A2), the polylactone polyol (A3), the polycarbonate polyol (A4), the polyether polyol (A5) and the poly (meth) acrylic polyol (A6) other than the polyester polyol (RA) having the structural unit represented by the general formula (1) can be used together. The polymer polyol (A) other than the hydroxyl group-containing polyolefin (A1) may be used alone in an amount of 1 or 2 or more. The above-mentioned (A2) to (A6) are also referred to as polymer polyols (A2) to (A6).
The Mn of the polymer polyol (a) other than the hydroxyl group-containing polyolefin (A1) is preferably 500 or more, more preferably 500 to 5000, and particularly preferably 1000 to 4000, from the viewpoint of the adhesion to the substrate.
Examples of the condensed polyester polyol (A2) other than the polyester polyol (RA) having the structural unit represented by the general formula (1) include a substance obtained by condensing a diol having Mn of less than 500 with a dicarboxylic acid other than terephthalic acid or an ester-forming derivative thereof [ an acid anhydride, a lower (c 1-4) alkyl ester, an acid halide, or the like ].
The diols having Mn of less than 500 include: aliphatic 2-alcohols having 2 to 8 carbon atoms [ straight-chain diols (ethylene glycol, diethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, etc.) and diols having branched alkyl chains (1, 2-propanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2-diethyl-1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 2, 3-butanediol, etc.) ]; alicyclic 2-alcohols having 6 to 10 carbon atoms [1, 4-bis (hydroxymethyl) cyclohexane, 2-bis (4-hydroxycyclohexyl) propane, etc. ]; an aromatic ring-containing 2-membered alcohol [ isophthalonitrile or terephthalonitrile, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene ] having 8 to 20 carbon atoms; AO adducts of bisphenols (bisphenol a, bisphenol S, bisphenol F, etc.), AO adducts of dihydroxynaphthalene, bis (2-hydroxyethyl) terephthalate, etc. ], and the like. The number of diols having Mn of less than 500 may be 1 alone or 2 or more.
Examples of dicarboxylic acids other than terephthalic acid or ester-forming derivatives thereof include aliphatic dicarboxylic acids having 2 to 15 carbon atoms [ oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc. ], aromatic dicarboxylic acids having 8 to 12 carbon atoms [ phthalic acid, isophthalic acid, etc. ], ester-forming derivatives thereof [ acid anhydrides, lower alkyl esters (dimethyl esters, diethyl esters, etc.), acid halides (acid chlorides, etc. ], and the like. The dicarboxylic acid may be used alone or in combination of 1 or more than 2.
Specific examples of the condensed polyester polyol (A2) include polyethylene adipate glycol, polybutylene adipate glycol, polyhexamethylene isophthalate glycol, polyhexamethylene adipate glycol, polyethylene glycol propylene adipate glycol, polyethylene glycol butylene adipate glycol, polybutylene adipate hexanediol, poly (polytetramethylene ether) adipate glycol, poly (3-methylpentanediol adipate) glycol, polyethylene azelate glycol, polyethylene sebacate glycol, polybutylene azelate glycol, and polybutylene sebacate glycol. The condensed polyester polyol (A2) may be used alone or in combination of 1 or more than 2.
The polylactone polyol (A3) may be obtained by ring-opening polymerization of a lactone monomer (such as gamma-butyrolactone, gamma-valerolactone, epsilon-caprolactone, or a mixture of 2 or more thereof) using the diol having Mn of less than 500 as an initiator. Specific examples of the polylactone polyol (A3) include polylactone diol, and polycaprolactone diol. The polylactone polyol (A3) may be used alone or in combination of 1 or more than 2.
The polycarbonate polyol (A4) is a polycarbonate diol produced by condensing a diol having an Mn of less than 500 with a low-molecular carbonate compound (for example, a dialkyl carbonate having an alkyl group and having 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group and having 2 to 6 carbon atoms, and a diaryl carbonate having an aryl group and having 6 to 9 carbon atoms) while dealcoholizing the diol. The polycarbonate polyol (A4) may be used alone or in combination of 1 or more than 2.
Specific examples of the polycarbonate polyol (A4) include polyhexamethylene carbonate glycol, polypentadiol carbonate glycol, polybutylene carbonate glycol and poly (butylene/hexylene glycol) carbonate glycol (for example, a glycol obtained by condensing 1, 4-butanediol and 1, 6-hexanediol with a dialkyl carbonate while dealcoholizing them), and the like.
The polyether polyol (A5) includes adducts of the AO having 2 to 12 carbon atoms with the diol having less than 500 Mn, and the like, and 1 kind of AO having 2 to 12 carbon atoms may be used alone, or 2 or more kinds may be subjected to block copolymerization or random copolymerization.
Among the polyether polyols (A5), from the viewpoint of resolubility, a substance having a branched alkyl chain is preferable, that is, a substance using a diol having a branched alkyl chain among diols having Mn of less than 500 as a raw material, a substance using 1, 2-propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, 1, 3-butylene oxide, 3-methyltetrahydrofuran or the like as AO in the AO adduct, and the like are more preferable, and an aliphatic polyether diol of a 2-polyol having a branched alkyl chain is particularly preferable, and polyoxypropylene glycol is particularly preferable. The polyether polyol (A5) may be used alone or in combination of 1 or more than 2.
The poly (meth) acrylic polyol (A6) is not particularly limited, and examples thereof include homopolymers and copolymers of (meth) acrylic esters having hydroxyl groups.
In addition to the (meth) acrylic acid ester having a hydroxyl group, the poly (meth) acrylic polyol (A6) may be obtained by copolymerizing a compound having a polymerizable unsaturated bond.
In the present invention, "(meth) acrylic acid" means "methacrylic acid and/or acrylic acid".
Examples of the hydroxyl group-containing (meth) acrylate include those having 1 (meth) acryloyl group include those having a hydroxyalkyl group having 2 to 20 carbon atoms { for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like (meth) acrylate }, and 3-membered (meth) acrylate monoesters { for example, (meth) acrylate monoesters of glycerin, and (meth) acrylate monoesters of trimethylolpropane and the like }, and the like.
Examples of the compound having a polymerizable unsaturated bond include compounds having 1 polymerizable unsaturated bond include: alkyl (meth) acrylates having 4 to 50 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, glycidyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; unsaturated carboxylic acids having 3 to 50 carbon atoms such as (meth) acrylic acid, maleic acid, itaconic acid, etc.; unsaturated amides having 3 to 50 carbon atoms such as (meth) acrylamide, N-methylol (meth) acrylamide and diacetone (meth) acrylamide; other polymerizable monomers such as styrene, vinyl toluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.
Examples of the polymerization method of the (meth) acrylate having a hydroxyl group and the compound having a polymerizable unsaturated bond include emulsion polymerization, suspension polymerization, dispersion polymerization, and solution polymerization. The emulsion polymerization may be carried out stepwise.
Specific examples of the commercially available poly (meth) acrylic polyol (A6) include "ARUFON UH-2000, UH-2041, UH-2190, UHE-2012" manufactured by Tokyo Synthesis Co., ltd., and "ACTFLOW UT-1001, UMM-1001" manufactured by UK Chemie Co., ltd.
Among the poly (meth) acrylic polyols (A6), from the viewpoint of compatibility with the hydroxyl group-containing polyolefin (A1), it is preferable to use at least one selected from the group consisting of n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate and 2-ethylhexyl (meth) acrylate as the above-mentioned compound having a polymerizable unsaturated bond, and it is more preferable to use a polyacrylic polyol of n-butyl (meth) acrylate and/or 2-ethylhexyl (meth) acrylate. The poly (meth) acrylic polyol (A6) may be used alone in an amount of 1 or 2 or more.
When the condensed polyester polyol (A2), the polylactone polyol (A3), the polycarbonate polyol (A4), the polyether polyol (A5) and/or the poly (meth) acrylic polyol (A6) are used together with the hydroxyl group-containing polyolefin (A1), the weight ratio [ (A1) weight) of the hydroxyl group-containing polyolefin (A1) to the total weight of the condensed polyester polyol (A2), the polylactone polyol (A3), the polycarbonate polyol (A4), the polyether polyol (A5) and the poly (meth) acrylic polyol (A6) is from the viewpoint of the adhesion to the substrate: the total weight of (A2) to (A6) is preferably 100:0 to 30: 70. further preferably 100:0 to 50:50.
the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer polyol (A) other than the hydroxyl group-containing polyolefin (A1) in the present invention can be measured by gel chromatography, for example, under the following conditions.
The device comprises: "Waters Alliance 2695" [ Waters Co., ltd.)
Column: "Guardcolumn Super H-L" (1 root), "1 root TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Co., ltd.)" each of which was connected "
Sample solution: 0.25% by weight tetrahydrofuran solution
Solution injection amount: 10 μl of
Flow rate: 0.6 ml/min
Measuring temperature: 40 DEG C
The detection device comprises: refractive index detector
Reference substance: standard polyethylene glycol
< isocyanate component (B) >)
Examples of the isocyanate component (B) in the present invention include compounds having 2 to 3 or more isocyanate groups, for example, aromatic polyisocyanates (B1) having 6 to 20 carbon atoms (except for carbon in the isocyanate groups, the same applies hereinafter), aliphatic polyisocyanates (B2) having 2 to 18 carbon atoms, alicyclic polyisocyanates (B3) having 4 to 15 carbon atoms, aromatic aliphatic polyisocyanates (B4) having 8 to 15 carbon atoms, and modified products (B5) of (B1) to (B4). The isocyanate component (B) may be used alone or in combination of 1 or more than 2.
Examples of the aromatic polyisocyanate (B1) having 6 to 20 carbon atoms include 1, 3-or 1, 4-phenylene diisocyanate, 2, 4-or 2, 6-Toluene Diisocyanate (TDI), 4' -diphenylmethane diisocyanate or 2,4' -diphenylmethane diisocyanate (MDI), 1, 5-naphthalene diisocyanate, 4',4 "-triphenylmethane triisocyanate, m-or p-isocyanatobenzenesulfonyl isocyanate, and crude MDI.
Examples of the aliphatic polyisocyanate (B2) having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene Diisocyanate (HDI), dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2-isocyanatoethyl-2, 6-diisocyanatohexanoate.
Examples of the alicyclic polyisocyanate (B3) having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), 4-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1, 2-dicarboxylate, 2, 5-norbornane diisocyanate, and 2, 6-norbornane diisocyanate.
Examples of the aromatic aliphatic polyisocyanate (B4) having 8 to 15 carbon atoms include m-xylylene diisocyanate, p-Xylylene Diisocyanate (XDI), and α, α, α ', α' -tetramethylxylylene diisocyanate (TMXDI).
Examples of the modified products (B5) of (B1) to (B4) include modified products of (B1) to (B4) having a urethane group, a carbodiimide group, an allophanate group, an urea group, a biuret group, a uretdione group, a uretonimine group, an isocyanurate group, or an oxazolidone group.
Among the isocyanate components (B), aliphatic polyisocyanates (B2) having 2 to 18 carbon atoms and alicyclic polyisocyanates (B3) having 4 to 15 carbon atoms are preferable, alicyclic polyisocyanates (B3) are more preferable, and IPDI and hydrogenated MDI are particularly preferable, from the viewpoints of mechanical strength and weather resistance.
< chain extender (C) >)
The polyurethane resin (U) may be further reacted with a chain extender (C) in addition to the polymer polyol (a) and the isocyanate component (B).
Examples of the chain extender (C) include a compound (C1) containing an ionic group and 2 active hydrogen atoms, a polyol (C2) having Mn or a chemical formula weight of less than 500, a polyalkylene polyamine (C3), hydrazine or a derivative thereof (C4), an amino alcohol (C5) having 2 to 10 carbon atoms, a polyepoxide compound (C6) having 2 to 30 carbon atoms, water, and the like.
The compound (c 1) containing an ionic group and 2 active hydrogen atoms is also used for introducing an ionic group into the polyurethane resin (U).
1 of the chain extenders (C), (C1) to (C6) and water may be used alone or in any combination.
< Compound (c 1) containing an ionic polar group and 2 active Hydrogen atoms >
The compound (c 1) containing an ionic polar group and 2 active hydrogen atoms includes a compound (c 11) containing an anionic group and an active hydrogen atom, and a compound (c 12) containing a cationic group and an active hydrogen atom. (c1) The number of the components may be 1 alone or 2 or more.
The anionic group in the compound (c 11) containing an anionic group and an active hydrogen atom means an acid group and a neutralized acid anionic group. Examples of the compound (c 11) containing an anionic group and an active hydrogen atom include: a compound having a carboxyl group as an anionic group and having 2 to 10 carbon atoms [ dihydroxyalkyl alkanoic acids (e.g., 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, 2-dimethylolheptanoic acid, and 2, 2-dimethyloloctanoic acid), tartaric acid, amino acids (e.g., glycine, alanine, and valine), and the like ]; a compound having a sulfonic acid group as an anionic group and having 2 to 16 carbon atoms [ e.g., 3- (2, 3-dihydroxypropoxy) -1-propanesulfonic acid and sulfoisophthalic acid bis (ethylene glycol) ester ]; a compound having a sulfamic acid group as an anionic group and having 2 to 10 carbon atoms [ N, N-bis (2-hydroxyethyl) sulfamic acid, etc. ]; and salts obtained by neutralizing these compounds with a neutralizing agent.
Examples of the neutralizing agent used in the salt of the compound (c 11) containing an anionic group and an active hydrogen atom include ammonia, an amine compound having 1 to 20 carbon atoms, and an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like).
Examples of the amine compound having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine and monoethanolamine; secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine, diisopropanolamine, methylpropanolamine, and the like; tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine and triethanolamine, and the like.
The neutralizing agent used in the salt of the compound (c 11) containing an anionic group and an active hydrogen atom is preferably a compound having a high vapor pressure at 25℃from the viewpoints of the drying property of the aqueous polyurethane dispersion to be produced and the water resistance of the coating film to be obtained. From this point of view, as the neutralizing agent used in the salt of the compound (c 11) containing an anionic group and an active hydrogen atom, ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine are preferable.
The amount of the neutralizing agent used in the salt of the compound (c 11) containing an anionic group and an active hydrogen atom is preferably 50 to 200%, more preferably 60 to 150% based on the amount of the acidic group contained in the polyurethane resin (U) in terms of water resistance and dispersion stability of the resin.
Among the compounds (c 11) containing an anionic group and an active hydrogen atom, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid and salts thereof are preferable from the viewpoints of resin properties of the obtained coating film and dispersion stability of the aqueous polyurethane dispersion, and the neutralized salts of 2, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid obtained using ammonia or an amine compound having 1 to 20 carbon atoms are more preferable.
The cationic group in the compound (c 12) containing a cationic group and an active hydrogen atom means a group to which a proton is added to a tertiary amino group, an unneutralized tertiary amino group, and a quaternary ammonium group.
Examples of the compound (c 12) containing a cationic group and an active hydrogen atom include: a salt obtained by neutralizing a compound having a tertiary amino group as a cationic group and a hydroxyl group as an active hydrogen atom, a tertiary amino group-containing diol [ N-alkyldialkanolamine (for example, N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and N-methyldipropanolamine) ] having 3 to 20 carbon atoms, and N, N-dialkylmonoalkanolamine (for example, N-dimethylethanolamine) with a neutralizing agent.
Examples of the neutralizing agent used for the compound (c 12) containing a cationic group and an active hydrogen atom include monocarboxylic acids having 1 to 10 carbon atoms (for example, formic acid, acetic acid, propionic acid, etc.), carbonic acid, dimethyl carbonate, dimethyl sulfate, methyl chloride, benzyl chloride, etc.
The neutralizing agent used for the compound (c 11) containing an anionic group and an active hydrogen atom and the compound (c 12) containing a cationic group and an active hydrogen atom may be added at any time before the urethanization reaction of the compound component (W) containing an active hydrogen group with the isocyanate component (B), during the urethanization reaction, after the urethanization reaction, before the water dispersion step, during the water dispersion step or after the water dispersion step, and is preferably added before the water dispersion step or during the water dispersion step in view of stability of the urethane resin and stability of the aqueous dispersion. The neutralizing agent that volatilizes when the solvent is removed may be added after the solvent is removed, and the type of neutralizing agent to be added may be freely selected from the neutralizing agents described above.
The polyol (c 2) having a Mn or formula weight of less than 500 may be: 2-membered alcohol having 2 to 20 carbon atoms [ aliphatic diol (ethylene glycol, propylene glycol, 1, 3-butanediol or 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 1, 2-decanediol or 1, 10-decanediol and 1, 2-dodecanediol or 1, 12-dodecanediol, etc.), alicyclic diol (1, 2-cyclohexanediol, 1, 3-cyclohexanediol or 1, 4-cyclohexanediol, etc.), aromatic aliphatic diol { 1-phenylethane-1, 2-diol, 1, 4-bis (hydroxyethyl) benzene, etc. }, ether group-containing diol { 3-butoxy-1, 2-propanediol, 3- (2-ethylhexyloxy) -1, 2-propanediol, 3-phenoxy-1, 2-propanediol, 3- (p-tert-butylphenoxy) -1, 2-propanediol, etc. }, halogen-containing diol (3-chloro-1, 2-propanediol, etc. ]; 3-alcohols having 3 to 20 carbon atoms [ aliphatic triols (glycerol, trimethylolpropane, etc. ] and 4 to 8-alcohols having 5 to 20 carbon atoms [ aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerol, dipentaerythritol, etc.) and saccharides (sucrose, glucose, mannose, fructose, methylglucoside, and derivatives thereof) ] and the like.
The polyalkylene polyamine (c 3) may be: aliphatic polyamines having 2 to 20 carbon atoms (ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.), alicyclic polyamines having 6 to 20 carbon atoms (diaminocyclohexane, dicyclohexylmethane diamine, isophoronediamine, etc.), aromatic polyamines having 2 to 20 carbon atoms (phenylenediamine, toluenediamine, diphenylmethane diamine, etc.), heterocyclic polyamines having 2 to 20 carbon atoms (piperazine, N-aminoethylpiperazine, etc.), etc.
The hydrazine or the derivative (c 4) thereof includes hydrazine (hydrazine, monoalkylhydrazine, etc.), dihydrazide (succinic dihydrazide, adipic dihydrazide, etc.), and the like.
Examples of the amino alcohol (c 5) having 2 to 10 carbon atoms include ethanolamine, diethanolamine, 2-amino-2-methylpropanol, and triethanolamine.
Examples of the polyepoxide compound (c 6) having 2 to 30 carbon atoms include AO, glycidyl, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, p-t-butylphenyl glycidyl ether, 1, 2-epoxydecane, 1, 2-epoxydodecane, epoxycyclohexane, styrene oxide, epichlorohydrin, 1, 6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether and the like having 2 to 4 carbon atoms.
When the compound (c 1) containing an ionic polar group and 2 active hydrogen atoms has a carboxyl group, the polyepoxide (c 6) having 2 to 30 carbon atoms is used as a chain extender together with the compound (c 1) containing an ionic polar group and 2 active hydrogen atoms, and the epoxy group reacts with the carboxyl group, whereby the chain extension reaction proceeds.
Among the chain extenders (C), the compound (C1) containing an ionic polar group and 2 active hydrogen atoms, the polyol (C2), the polyalkylene polyamine (C3), the aminoalcohol (C5) and water are preferable, and the compound (C1) containing an ionic polar group and 2 active hydrogen atoms, the 2-polyol, the 3-polyol, the aliphatic polyamine, the alicyclic polyamine, the aminoalcohol (C5) and water are more preferable from the viewpoint of adhesion to the substrate.
The amount of the compound (c 1) containing an ionic polar group and 2 active hydrogen atoms is adjusted so that: the content of the ionic polar group in the urethane resin (U) is preferably 0.5 to 5.0 wt%, more preferably 0.5 to 4.8 wt%, and particularly preferably 0.5 to 4.5 wt%, based on the weight of the urethane resin (U).
The content of the ionic polar group in the present invention means the weight of the non-neutralized cationic group or anionic group excluding the weight of the counter ion. For example, the content of the ionic polar group in the compound (c 11) containing an anionic group and an active hydrogen atom means the weight% of the carboxyl group (-COOH) in the case of the triethylamine salt of 2, 2-dimethylolpropionic acid and the sulfo group (-SO) in the case of the triethylamine salt of 3- (2, 3-dihydroxypropoxy) -1-propanesulfonic acid 3 H) Is defined as weight percent. The content of the ionic polar group in the compound (c 12) containing a cationic group and an active hydrogen atom means weight% of only nitrogen atoms in the tertiary amino group.
The polyurethane resin (U) of the present invention may use a reaction terminator as needed. Examples of the reaction terminator include: a monohydric alcohol having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolve, carbitol, etc.) and a monoamine having 1 to 10 carbon atoms (a monoalkylamine or dialkylamine such as monomethylamine, monoethylamine, monobutylamine, dibutylamine, shan Xinan, etc., a monoalkanolamine or dialkanolamine such as monoethanolamine, diethanolamine, diisopropanolamine, etc.). The reaction terminator may be used alone or in combination of 2 or more.
The polyurethane resin (U) of the present invention may contain additives such as antioxidants, coloring agents, weather stabilizers, plasticizers, and mold release agents, if necessary. The amount of these additives is preferably as small as possible in the range capable of exhibiting the effect of the additives, based on the weight of the polyurethane resin (U), and is preferably 10% by weight or less, more preferably 3% by weight or less, and particularly preferably 1% by weight or less.
The urethane group content in the urethane resin (U) in the present invention is preferably 0.5 to 3.0mmol/g, more preferably 0.7 to 2.5mmol/g, particularly preferably 0.9 to 2.0mmol/g, from the viewpoint of the substrate adhesion of the obtained coating film.
The urethane group content of the urethane resin (U) can be set to a desired range by appropriately adjusting the types and proportions of the polyolefin (A1) containing hydroxyl groups, the polymer polyol (a) of the above (A2) to (A6) used as needed, the isocyanate component (B), and the chain extender (C) as needed.
The urethane group content can be determined from the N atom content quantified by a nitrogen analyzer and the utilization 1 The ratio of urethane groups to urea groups and the allophanate groups to biuret groups were determined by H-NMR and calculated.
The urea group content in the polyurethane resin (U) is preferably 1.5mmol/g or less, more preferably 1.2mmol/g or less, particularly preferably 1.0mmol/g or less, and most preferably 0.8mmol/g or less, based on the weight of the polyurethane resin (U), from the viewpoint of adhesion to a substrate.
In order to adjust the urea group content in the polyurethane resin (U) to a desired range, the amino group content, the moisture content, and the isocyanate group content in the raw material of the polyurethane resin (U) may be appropriately adjusted.
The urea group content can be quantified by the N atom content by a nitrogen analyzer and by 1 The ratio of urethane groups to urea groups and the allophanate and biuret group contents were determined by H-NMR.
< polyurethane aqueous Dispersion >
The aqueous polyurethane dispersion of the present invention comprises water and the polyurethane resin (U).
The aqueous polyurethane dispersion can be produced by any one of the following methods (1) to (4), for example.
(1) A solution (for example, a solution of a solvent to be described later) of a polyurethane prepolymer (P) having an isocyanate group at the end thereof, which contains a polymer polyol (A) containing a hydroxyl group-containing polyolefin (A1) and an isocyanate component (B) as constituent monomers, is prepared.
Then, water, if necessary, a solvent, a chain extender (C) and a neutralizing agent are added to carry out phase inversion emulsification, and if necessary, the solvent is distilled off to obtain an aqueous polyurethane dispersion.
(2) A solution (for example, a solution of an organic solvent described later) of a polyurethane prepolymer (P) having an isocyanate group at the end thereof, which contains a polymer polyol (A) containing a hydroxyl group-containing polyolefin (A1) and an isocyanate component (B) as constituent monomers, is prepared.
Then, water, if necessary, a solvent, a neutralizing agent, and a chain extender (C) are added, and the mixture is dispersed by a known dispersing machine, and if necessary, the solvent is distilled off to obtain an aqueous polyurethane dispersion.
(3) A solution (for example, a solution of a solvent to be described later) of a polyurethane prepolymer (P) having an isocyanate group at the end thereof, which contains a polymer polyol (A) containing a hydroxyl group-containing polyolefin (A1) and an isocyanate component (B) as constituent monomers, is prepared.
Next, a mixture of water and a solution containing the polyurethane prepolymer (P) is dispersed by a known dispersing machine, and then a neutralizing agent and a reaction terminator are added as needed, and the solvent is distilled off as needed to obtain an aqueous polyurethane dispersion.
(4) A solvent solution of a polyurethane resin (U) containing a polymer polyol (A) containing a hydroxyl group-containing polyolefin (A1) and an isocyanate component (B) as constituent monomers is prepared.
Then, water is added, for example, by dispersing with a dispersing machine, and the solvent is distilled off as needed to obtain an aqueous polyurethane dispersion.
In the step of obtaining the aqueous polyurethane dispersion, a known anionic surfactant, cationic surfactant, amphoteric surfactant, or nonionic surfactant may be used as needed in addition to the polyurethane prepolymer (P), the solvent, the neutralizing agent, the chain extender (C), water, and the reaction terminator.
Examples of the solvent include organic solvents such as ketone solvents (e.g., acetone and methyl ethyl ketone), ester solvents [ e.g., ethyl acetate and dibasic acid ester (DBE) ], ether solvents (e.g., tetrahydrofuran), amide solvents (e.g., N-dimethylformamide and N-methylpyrrolidone), alcohol solvents (e.g., ethanol and isopropanol), and aromatic hydrocarbon solvents (e.g., toluene).
The aqueous polyurethane dispersion may contain the solvent.
The solid content concentration (the content of the component other than the volatile component) of the aqueous polyurethane dispersion is preferably 20 to 65% by weight, more preferably 25 to 55% by weight, from the viewpoint of ease of handling the aqueous polyurethane dispersion. The solid content concentration can be calculated as follows: after accurately weighing about 1g of the polyurethane aqueous dispersion, the dispersion was thinly spread on a petri dish, heated at 130℃for 45 minutes using a circulating constant temperature dryer, and the heated weight was accurately weighed, and the ratio (percentage) of the residual weight after heating to the weight before heating was calculated, whereby the solid content concentration was calculated.
In addition, from the viewpoint of handleability, the viscosity of the aqueous polyurethane dispersion at 25℃is preferably 10 to 100,000 mPas, more preferably 10 to 5,000 mPas. The viscosity can be measured using a BL-type viscometer at a constant temperature of 25 ℃.
The pH of the aqueous polyurethane dispersion is preferably 2 to 12, more preferably 4 to 10, from the viewpoint of compounding stability. The pH can be measured at 25℃using a pH Meter M-12 manufactured by horiba, inc.
The volume average particle diameter (Dv) of the particles of the polyurethane resin (U) in the aqueous polyurethane dispersion of the present invention is preferably 0.01 to 1 μm, more preferably 0.02 to 0.7 μm, and particularly preferably 0.03 to 0.4 μm, from the viewpoint of dispersion stability. When the volume average particle diameter (Dv) is 0.01 μm or more, the viscosity is appropriate and the handleability is good; when the volume average particle diameter (Dv) is 1 μm or less, the dispersion stability is good.
The volume average particle diameter (Dv) can be controlled by the amount of ionic polar groups in the polyurethane resin (U) and the type and operating conditions of the dispersing machine used in the dispersing step.
The aqueous polyurethane dispersion of the present invention can be used for printing ink, aqueous coating composition, aqueous adhesive composition, aqueous fiber processing agent composition (adhesive composition for printing, adhesive composition for nonwoven fabric, sizing agent composition for reinforcing fiber, adhesive composition for antibacterial agent, raw material composition for artificial leather and synthetic leather, etc.), aqueous coating composition (water-repellent coating composition, hydrophobic coating composition, antifouling coating composition, etc.), battery adhesive, aqueous paper treatment agent composition, aqueous ink composition, etc. In particular, the aqueous ink composition can be suitably used as an inkjet ink composition, an aqueous printing ink composition for gravure printing or the like, an aqueous coating composition, a paste for printing, or a nonaqueous electrolyte secondary battery electrode binder.
The coating film is obtained, for example, by coating a substrate (plastic film or the like) and heating and/or curing as needed.
In the case of being used for these applications, 1 or 2 or more of other resins, crosslinking agents, catalysts, pigments, pigment dispersants, viscosity regulators, antifoaming agents, leveling agents, preservatives, deterioration inhibitors, stabilizers, antifreezes, and the like may be contained as necessary.
< inkjet ink composition >
The inkjet ink composition of the present invention contains the above-described aqueous polyurethane dispersion of the present invention. In the inkjet ink composition of the present invention, the polyurethane resin (U) functions as a binder, pigment-dispersing resin, or the like.
The content of the urethane resin (U) in the inkjet ink composition of the present invention is preferably 1 to 30% by weight, more preferably 2 to 15% by weight, based on the weight of the inkjet ink composition, from the viewpoints of substrate adhesion, mechanical strength and handling properties.
In addition to the aqueous polyurethane dispersion of the present invention, the inkjet ink composition of the present invention may contain a colorant, and as optional components, a humectant, a penetrant, water, and other additives.
The coloring material is not particularly limited, and dyes and pigments can be used.
The dye is not particularly limited, and an acid dye, a direct dye, a reactive dye, and a basic dye may be used, and 1 kind may be used alone or 2 or more kinds may be used in combination.
As the pigment, there may be mentioned an inorganic pigment (for example, white pigment, black pigment, gray pigment, red pigment, brown pigment, yellow pigment, green pigment, blue pigment, violet pigment, and metallic pigment) having a solubility in water of 1 or less, an organic pigment [ for example, a natural organic pigment, a synthetic organic pigment (for example, nitroso pigment, nitro pigment, pigment-based azo pigment, azo lake made of a water-soluble dye, azo lake made of a poorly soluble dye, lake made of a basic dye, lake made of an acid dye, xanthan gum lake, anthraquinone lake, pigment derived from vat dye, and phthalocyanine pigment), and the like ]. The number of these may be 1 alone or 2 or more.
In addition, as the pigment, a commercially available self-dispersible pigment having a hydrophilic functional group introduced into the pigment surface or encapsulated with a resin may be used. Examples thereof include self-dispersible pigments such as carbon black introduced with an acidic group and Cabot corporation, which are sold by various carbon black manufacturers. The dye and pigment are used in an amount of 1 or more, and the dye and pigment may be used in combination.
In order to disperse the pigment in the ink, a commercially available self-dispersible pigment is used, and examples thereof include: a method of introducing a hydrophilic functional group into a pigment to prepare a self-dispersible pigment; a method of coating the surface of the pigment with a resin to disperse the pigment; a method of dispersing a pigment using a dispersant; etc. As a method of introducing a hydrophilic functional group into a pigment to prepare a self-dispersible pigment, for example, a self-dispersible pigment in which a functional group such as a sulfone group or a carboxyl group is added to a pigment (for example, carbon) so as to be dispersible in water can be used.
As a method of coating the surface of the pigment with a resin to disperse the pigment, a method of containing the pigment in microcapsules containing a resin such as a polyurethane resin (U) and dispersing the pigment in water can be used. This may be modified as a resin-coated pigment. In this case, the pigment to be blended into the ink is not required to be coated with the resin, and the pigment to be not coated or the pigment to be partially coated may be dispersed in the ink within a range where the effect of the present invention is not impaired.
Examples of the method for dispersing the pigment using the dispersant include a method for dispersing the pigment using a known low-molecular-weight dispersant typified by a surfactant and a polymer-type dispersant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used depending on the pigment. RT-100 (nonionic surfactant) manufactured by bamboo oil company and sodium naphthalene sulfonate formaldehyde condensate can also be suitably used as a dispersant. The dispersant may be used alone or in combination of at least 2 kinds.
The inkjet ink composition of the present invention can be obtained by mixing materials such as water and an organic solvent with an aqueous polyurethane dispersion and a pigment. The pigment may be mixed with other water, a dispersant, or the like to prepare a pigment dispersion, and the aqueous polyurethane dispersion, water, an organic solvent, or the like may be mixed therewith to prepare the pigment dispersion. The pigment dispersion is obtained by dispersing water, a pigment, a dispersant, and other components as needed, and adjusting the particle diameter. Dispersing using a dispersing machine is preferable.
The pigment dispersion is preferably deaerated by filtering coarse particles by a filter, a centrifugal separator, or the like as necessary.
The content of the coloring material is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, based on the weight of the inkjet ink composition, from the viewpoint of adhesion to the substrate.
The humectant is incorporated into the inkjet ink composition to inhibit drying of the inkjet ink composition and prevent clogging of nozzles.
Examples of the humectant include high boiling point water-soluble organic solvents, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight is preferably 2000 or less), propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1, 3-propanediol, isopropylene glycol, isobutylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1,2, 6-hexanetriol, thioglycol, hexylene glycol, glycerin, erythritol, pentaerythritol, and trimethylolpropane. It should be noted that 1 or 2 or more of these high boiling point water-soluble organic solvents may be used in combination.
The content of the humectant in the inkjet ink composition is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 0.01% by weight or more and 60% by weight or less, more preferably 5% by weight or more and 50% by weight or less, from the viewpoint of drying property of the inkjet ink composition.
The penetrant, by being compounded into the inkjet ink composition, functions to promote permeation of the inkjet ink composition into the permeable medium. As the penetrating agent, an organic solvent, a surfactant, or the like can be used.
The organic solvent which can be used as the penetrating agent is not particularly limited, and may be exemplified by alkyl alcohols having 1 to 4 carbon atoms such as methanol, ethanol, isopropanol, etc.; alkyl ethers (also referred to as glycol ethers) of polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisopropyl ether, and dipropylene glycol mono-n-butyl ether; and straight-chain alkyl diols such as 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 2-pentanediol, and 1, 2-hexanediol. It should be noted that 1 or a mixture of 2 or more of these organic solvents may be used. The content of these organic solvents is preferably 30% by weight or less relative to the total weight of the inkjet ink composition, from the viewpoint of drying properties of the inkjet ink composition. More preferably 20% by weight or less, still more preferably 10% by weight or less.
Examples of the surfactant that can be used as the penetrating agent include amphoteric surfactants and nonionic surfactants. Examples of the amphoteric surfactant include imidazoline derivatives such as lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, coconut fatty acid amide propyl dimethylaminoacetic acid betaine, and polyoctylpolyaminoethyl glycine.
Examples of the nonionic surfactant include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkylallyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and polyoxyalkylene alkyl ether (polyoxypropylene polyoxyethylene alkyl ether); polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, and the like; other fluoroalkyl esters, perfluoroalkyl carboxylates, and other fluorine-containing surfactants. In addition, an acetylenic alcohol-based surfactant, an acetylenic glycol-based surfactant, and a silicon-based surfactant may also be used. The content of these surfactants is preferably in the range of 0.01 wt% to 10 wt% with respect to the total weight of the inkjet ink, more preferably 0.1 wt% to 5 wt%.
Examples of the other additives include viscosity modifiers, antifoaming agents, preservatives, deterioration inhibitors, stabilizers, and pH adjusters.
These other additives may be used alone in an amount of 1 or in an amount of 2 or more.
Examples of the viscosity modifier include rosins, alginic acid, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyacrylate, polyvinylpyrrolidone, and acacia starch.
The defoaming agent is not particularly limited, and examples thereof include silicone-based defoaming agents, polyether-based defoaming agents, fatty acid ester-based defoaming agents, and the like.
Examples of the preservative include alkylisothiazolones, chloroalkylisothiazolones, benzisothiazolones, bromonitroalcohols, oxazolidines, chloroxylenols, and the like.
Examples of the deterioration inhibitor and stabilizer (such as ultraviolet absorber and antioxidant) include hindered phenol type, hindered amine type, hydrazine type, phosphorus type, benzophenone type, and benzotriazole type deterioration inhibitor and stabilizer.
The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 or more, and examples thereof include amines such as diethanolamine and triethanolamine.
The content of the viscosity adjuster, defoamer, preservative, deterioration inhibitor, stabilizer, pH adjuster, and the like in the inkjet ink composition is preferably as small as possible in the range capable of exhibiting the additive effect, based on the weight of the inkjet ink composition, and is preferably 5 wt% or less, more preferably 3 wt% or less, respectively.
The recording medium to which the inkjet ink composition of the present invention can be applied is not particularly limited, and plain paper, glossy paper, special paper, cloth, and the like can be used. The inkjet ink composition of the present invention can be suitably used for inkjet printing of various plastic films such as polyester films, nylon films, surface-treated or untreated polypropylene films, polyethylene films, polyvinyl acetal films, acetate films, polyvinyl chloride films, and films obtained by vapor deposition of aluminum on these films.
< Water-based printing ink composition >
The aqueous printing ink composition of the present invention contains the aqueous polyurethane dispersion of the present invention. By using the polyurethane aqueous dispersion, a printing ink excellent in substrate adhesion of an image is obtained. In the aqueous printing ink composition of the present invention, the polyurethane resin (U) functions as a binder, a pigment-dispersing resin, or the like.
The content of the urethane resin (U) in the aqueous printing ink composition of the present invention is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, based on the weight of the aqueous printing ink composition, from the viewpoints of adhesion to a substrate, mechanical strength and handling properties.
To the aqueous printing ink composition of the present invention, 1 or 2 or more pigments, pigment dispersants, other resins, crosslinking agents and additives (catalysts, organic solvents, viscosity modifiers, defoamers, leveling agents, preservatives, deterioration inhibitors, stabilizers, antifreezes, etc.) which are usually preferably used for the aqueous printing ink composition may be added as needed.
The pigment is not particularly limited, and inorganic pigments, organic pigments, and the like, which are generally used in aqueous printing inks, can be preferably used. For example, there can be mentioned inorganic pigments (for example, white pigments, black pigments, gray pigments, red pigments, brown pigments, yellow pigments, green pigments, blue pigments, violet pigments, and metallic pigments) having a solubility in water of 1 or less, organic pigments [ for example, natural organic pigments, synthetic organic pigments (for example, nitroso pigments, nitro pigments, pigment type azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, azo lakes made of water-soluble dyes, azo lakes made of poorly-soluble dyes, lakes made of basic dyes, lakes made of acid dyes, xanthan lakes, anthraquinone lakes, pigments derived from vat dyes, and phthalocyanine pigments) ] and the like. The content of the pigment is preferably 5 to 40% by weight, more preferably 10 to 30% by weight or less based on the weight of the aqueous printing ink composition.
Examples of the pigment dispersant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and other emulsifying dispersants. The amount of the pigment dispersant used is preferably 10% by weight or less, more preferably 5% by weight or less, based on the weight of the aqueous printing ink composition.
Examples of the nonionic surfactant include AO addition type nonionic surfactants and polyol type nonionic surfactants. Examples of the AO addition type include an EO adduct of an aliphatic alcohol having 10 to 20 carbon atoms, an EO adduct of phenol, an EO adduct of nonylphenol, an EO adduct of an alkylamine having 8 to 22 carbon atoms, and an EO adduct of poly (oxypropylene) glycol. Examples of the polyhydric alcohol type include fatty acid (8 to 24 carbon atoms) esters (for example, glyceryl monostearate, glyceryl monooleate, sorbitan monolaurate, and the like) of polyhydric (3 to 8 or more membered) alcohols (2 to 30 carbon atoms) and alkyl (4 to 24 carbon atoms) poly (degree of polymerization 1 to 10) glycosides.
Examples of the anionic surfactant include ether carboxylic acids having a hydrocarbon group of 8 to 24 carbon atoms or salts thereof [ sodium lauryl ether acetate, sodium (poly) oxyethylene (addition mole number 1 to 100) lauryl ether acetate, etc. ]; sulfate or ether sulfate having a hydrocarbon group of 8 to 24 carbon atoms and salts thereof [ sodium lauryl sulfate, (poly) oxyethylene (addition mole number 1 to 100) triethanolamine lauryl sulfate and (poly) oxyethylene (addition mole number 1 to 100) sodium cocoanut oil fatty acid monoethanolamide sulfate, etc. ]; sulfonates having a hydrocarbon group having 8 to 24 carbon atoms [ sodium dodecylbenzenesulfonate, etc ]; sulfosuccinates having 1 or 2 hydrocarbyl groups of 8 to 24 carbon atoms; phosphate or ether phosphate having a hydrocarbon group of 8 to 24 carbon atoms and salts thereof [ sodium lauryl phosphate and sodium (poly) oxyethylene (addition mole number 1 to 100) lauryl ether phosphate, etc. ]; fatty acid salts having a hydrocarbon group having 8 to 24 carbon atoms [ sodium laurate, triethanolamine laurate, etc. ]; an acylated amino acid salt having a hydrocarbon group having 8 to 24 carbon atoms [ sodium coco fatty acid methyl taurate, sodium coco fatty acid sarcosine, triethanolamine N-coco fatty acid acyl-L-glutamate, sodium lauroyl- β -alanine, etc. ].
Examples of the cationic surfactant include quaternary ammonium salts [ stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and ethyl lanolin fatty acid aminopropyl ethyl dimethyl ammonium sulfate ].
Examples of the amphoteric surfactant include betaine type amphoteric surfactants [ e.g., cocofatty amidopropyl dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryl hydroxysulfobetaine, and lauramidoethyl hydroxyethyl carboxymethyl betaine hydroxypropyl sodium phosphate ].
Examples of the other emulsifying dispersant include polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, carboxyl group-containing (co) polymers such as sodium polyacrylate, and emulsifying dispersants having a urethane group or an ester group described in U.S. Pat. No. 5906704 [ for example, a substance obtained by linking a polycaprolactone polyol and a polyether diol with a polyisocyanate ].
Examples of the other resin include polyamide resins, nitrocellulose, acrylic resins, vinyl acetate resins, styrene maleic acid copolymer resins, chlorinated polypropylene resins, epoxy resins, and rosin resins. The amount of the other resins is preferably 30% by weight or less, more preferably 20% by weight or less, based on the weight of the aqueous printing ink composition.
Examples of the crosslinking agent include water-soluble or water-dispersible amino resins, water-soluble or water-dispersible polyepoxides, water-soluble or water-dispersible blocked polyisocyanate compounds, and polyvinyl ureas.
The amount of the crosslinking agent to be added is preferably 30% by weight or less, more preferably 0.1 to 20% by weight, based on the weight of the solid content of the aqueous polyurethane dispersion.
As the organic solvent, an organic solvent exemplified as the solvent in the above-mentioned step of obtaining the polyurethane aqueous dispersion can be used. From the viewpoints of drying speed and harmfulness of the ink, alcohol solvents (for example, ethanol and isopropanol) are preferable. The amount of the organic solvent used is preferably 50% by weight or less, more preferably 20% by weight or less, based on the weight of the aqueous printing ink composition.
Examples of the viscosity modifier include inorganic thickeners (sodium silicate, bentonite, etc.), cellulose thickeners (methylcellulose having Mn of 20,000 or more, carboxymethyl cellulose, hydroxymethyl cellulose, etc.), protein thickeners (casein, sodium caseinate, ammonium caseinate, etc.), acrylic thickeners (sodium polyacrylate and ammonium polyacrylate having Mn of 20,000 or more, etc.), and vinyl thickeners (polyvinyl alcohol having Mn of 20,000 or more, etc.).
Examples of the defoaming agent include long-chain alcohols (octanol, etc.), sorbitan derivatives (sorbitan monooleate, etc.), silicone oils (polymethylsiloxane, polyether modified silicone, etc.), and the like.
Examples of the leveling agent include an acrylic leveling agent, a vinyl leveling agent, a silicone leveling agent, and a fluorine leveling agent.
Examples of the preservative include organic nitrogen-sulfur compound-based preservatives and organic sulfur halide-based preservatives.
Examples of the deterioration inhibitor and stabilizer (such as ultraviolet absorber and antioxidant) include hindered phenol type, hindered amine type, hydrazine type, phosphorus type, benzophenone type, and benzotriazole type deterioration inhibitor and stabilizer.
Examples of the antifreeze include ethylene glycol and propylene glycol.
The contents of the viscosity modifier, defoamer, leveling agent, preservative, deterioration inhibitor, stabilizer and antifreeze are preferably 5% by weight or less, more preferably 3% by weight or less, respectively, based on the weight of the aqueous printing ink composition.
The method for producing the aqueous printing ink composition is not particularly limited, and the aqueous printing ink composition can be produced by a known method or the like, for example, by using a general ink production apparatus such as a three-roll mill, a ball mill, a sand mill, or the like.
An example of the formulation of the aqueous printing ink composition of the present invention is shown below.
Polyurethane resin (U): 5 to 40 wt% (preferably 10 to 30 wt%)
And (3) pigment: 5 to 40 wt% (preferably 10 to 30 wt%)
Pigment dispersant: 0 to 10 wt% (preferably 0 to 5 wt%)
Organic solvent: 0 to 50 wt% (preferably 0 to 20 wt%)
Water: 10 to 80 wt% (preferably 30 to 70 wt%)
Examples of the printing method using the aqueous printing ink composition of the present invention include printing methods such as special gravure printing, inkjet printing, offset printing, and thermal transfer printing used for printing of conventional plastic films.
The aqueous printing ink composition of the present invention has particularly excellent substrate adhesion to plastics, and can be suitably used for printing various plastic films such as polyolefin films (surface-treated or untreated polypropylene films, polyethylene films, etc.), polyester films, nylon films, polyvinyl acetal films, acetate films, polyvinyl chloride films, films obtained by vapor deposition of aluminum on these films, and the like.
< Water-based coating composition >
The aqueous coating composition of the present invention contains the aqueous polyurethane dispersion of the present invention described above. The aqueous coating composition may contain, if necessary, 1 or 2 or more resins selected from the group consisting of a crosslinking agent, a catalyst, a pigment dispersant, a viscosity modifier, an antifoaming agent, a wetting agent, a film-forming aid, a leveling agent, a preservative, an anti-deterioration agent, a stabilizer, an antifreezing agent, a urethane resin other than the above polyurethane resin (U), an acrylic resin, and a polyester resin, and the like.
The aqueous coating composition of the present invention is particularly suitable as an aqueous coating composition for building material coating or building coating and an aqueous coating composition for automobiles.
The coating film is obtained, for example, by coating a substrate (plastic film or the like) and heating and/or curing as needed.
As the above-mentioned crosslinking agent, specifically, at least 1 crosslinking agent selected from the group consisting of melamine resin, blocked isocyanate, and epoxy compound can be used.
The amount of the crosslinking agent to be added is preferably 30% by weight or less, more preferably 0.1 to 20% by weight, based on the weight of the solid content of the aqueous polyurethane dispersion, from the viewpoints of substrate followability and substrate adhesion.
The melamine resin may be one commonly used as a crosslinking agent. The alkyl-etherified melamine resin is preferably one in which alkyl-etherification is performed using a monohydric alcohol such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, or the like. Examples of the alkyl etherified melamine resin include U-VAN series (U-VAN 120, 20HS, 2021, 2028, 228, 28-60, and 22R, etc.) manufactured by Mitsui chemical Co., ltd.) and Cymel series (Cymel 202, 232, 235, 250, 254, 285, 303, 325, 327, 328, 350, 370, 114, 1156, 1158, etc.) manufactured by Allnex Japan, inc.
The blocked isocyanate is not particularly limited as long as it has 2 or more blocked isocyanate groups in the molecule, and examples thereof include those obtained by blocking the polyisocyanate compound exemplified as the isocyanate component (B) with a known blocking agent [ phenols, secondary or tertiary alcohols, oximes, aliphatic or aromatic secondary amines, phthalimides, lactams, active methylene compounds (dialkyl malonates and the like), pyrazole compounds (pyrazoles and 3, 5-dimethylpyrazole and the like), acidic sodium sulfite and the like ].
Examples of commercially available blocked isocyanates include the DURANATE series (DURANATE 17B-60P, TPA-B80E, MF-B60B, MF-K60B, SBB-70P, SBN-70D, SBF-70E, E-402-B80B, WM44-L70G, etc.) manufactured by Asahi Kabushiki Kaisha.
The epoxy compound is not particularly limited as long as it has 2 or more epoxy groups in the molecule, and examples thereof include resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, hydrogenated bisphenol a diglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, and polypropylene glycol diglycidyl ether.
As the pigment, various pigments such as coloring pigment, extender pigment, and luster pigment can be used. Examples of the coloring pigment include inorganic pigments (chrome yellow, iron oxide, yellow iron oxide, carbon black, titanium dioxide, etc.) and organic pigments (azo chelate pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, cyclic ketone pigments, perylene pigments, dioxane pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, etc.). Examples of extender pigments include calcium carbonate, precipitated barium sulfate, barite, talc, clay, and the like. Examples of the bright pigment include aluminum flake pigment, aluminum oxide flake pigment, mica pigment, silica flake pigment, and glass flake pigment. These pigments may be used singly or in combination of 2 or more.
Examples of the pigment dispersant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and other emulsifying dispersants. The pigment dispersant may be used alone or in combination of 1 or more than 2.
Examples of the nonionic surfactant include AO addition type nonionic surfactants and polyol type nonionic surfactants. Examples of the AO addition type include EO adducts of aliphatic alcohols having 10 to 20 carbon atoms, EO adducts of phenol, EO adducts of nonylphenol, EO adducts of alkylamines having 8 to 22 carbon atoms, EO adducts of polypropylene glycol, and the like, and examples of the polyhydric alcohol type include fatty acid (8 to 24 carbon atoms) esters of polyhydric (3 to 8-membered or more) alcohols (having 2 to 30 carbon atoms) (for example, glyceryl monostearate, glyceryl monooleate, sorbitan monolaurate, sorbitan monooleate, and the like) and alkyl (having 4 to 24 carbon atoms) poly (degree of polymerization 1 to 10) glycosides.
Examples of the anionic surfactant include ether carboxylic acids having a hydrocarbon group of 8 to 24 carbon atoms or salts thereof [ sodium lauryl ether acetate, sodium (poly) oxyethylene (addition mole number 1 to 100) lauryl ether acetate, etc. ]; sulfate or ether sulfate having a hydrocarbon group of 8 to 24 carbon atoms and salts thereof [ sodium lauryl sulfate, (poly) oxyethylene (addition mole number 1 to 100) triethanolamine lauryl sulfate and (poly) oxyethylene (addition mole number 1 to 100) sodium cocoanut oil fatty acid monoethanolamide sulfate, etc. ]; sulfonates having a hydrocarbon group having 8 to 24 carbon atoms [ sodium dodecylbenzenesulfonate, etc ]; sulfosuccinates having 1 or 2 hydrocarbyl groups of 8 to 24 carbon atoms; phosphate or ether phosphate having a hydrocarbon group of 8 to 24 carbon atoms and salts thereof [ sodium lauryl phosphate and sodium (poly) oxyethylene (addition mole number 1 to 100) lauryl ether phosphate, etc. ]; fatty acid salts having a hydrocarbon group having 8 to 24 carbon atoms [ sodium laurate, triethanolamine laurate, etc. ]; an acylated amino acid salt having a hydrocarbon group having 8 to 24 carbon atoms [ sodium coco fatty acid methyl taurate, sodium coco fatty acid sarcosine, triethanolamine N-coco fatty acid acyl-L-glutamate, sodium lauroyl- β -alanine, etc. ].
Examples of the cationic surfactant include quaternary ammonium salts [ stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and ethyl lanolin fatty acid aminopropyl ethyl dimethyl ammonium sulfate ].
Examples of the amphoteric surfactant include betaine type amphoteric surfactants [ e.g., cocofatty amidopropyl dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryl hydroxysulfobetaine, and lauramidoethyl hydroxyethyl carboxymethyl betaine hydroxypropyl sodium phosphate ].
Examples of the other emulsifying dispersant include polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, carboxyl group-containing (co) polymers such as sodium polyacrylate, and emulsifying dispersants having a urethane group or an ester group described in U.S. Pat. No. 5906704 [ for example, a substance obtained by linking a polycaprolactone polyol and a polyether diol with a polyisocyanate ].
Examples of the leveling agent include an acrylic leveling agent, a vinyl leveling agent, a silicone leveling agent, and a fluorine leveling agent.
Examples of the wetting agent include polyhydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, glycerin, etc.).
Examples of the film-forming auxiliary include ethylene glycol, alcohol ester-12 (Texanol), diethyl adipate, ethylene glycol hexyl ether, propylene glycol pentyl ether, dipropylene glycol n-butyl ether, and alcohol ester-12 (Texanol) isobutyl ether.
Examples of the viscosity modifier include inorganic thickeners (sodium silicate, bentonite, etc.), cellulose thickeners (methylcellulose having Mn of 20,000 or more, carboxymethyl cellulose, hydroxymethyl cellulose, etc.), protein thickeners (casein, sodium caseinate, ammonium caseinate, etc.), acrylic acid-based thickeners (sodium polyacrylate and ammonium polyacrylate having Mn of 20,000 or more, etc.), and vinyl-based thickeners (polyvinyl alcohol having Mn of 20,000 or more, etc.).
Examples of the defoaming agent include long-chain alcohols (octanol, etc.), sorbitan derivatives (sorbitan monooleate, etc.), silicone oils (polymethylsiloxane, polyether modified silicone, etc.), and the like.
Examples of the preservative include organic nitrogen-sulfur compound-based preservatives and organic sulfur halide-based preservatives.
Examples of the deterioration inhibitor and stabilizer (such as ultraviolet absorber and antioxidant) include hindered phenol type, hindered amine type, hydrazine type, phosphorus type, benzophenone type, and benzotriazole type deterioration inhibitor and stabilizer.
Examples of the antifreeze include ethylene glycol and propylene glycol.
Examples of the polyester resin include Vylonal MD 1480.
The content of the catalyst, pigment dispersant, wetting agent, film forming aid, leveling agent, viscosity modifier, defoaming agent, preservative, deterioration inhibitor, stabilizer, antifreezing agent and resin other than the polyurethane resin (U) is preferably as small as possible in terms of the amount of the base material adhesion in terms of the weight of the aqueous coating composition used in the application, and is more preferably 5% by weight or less, still more preferably 3% by weight or less, in each case in the range capable of exhibiting the additive effect.
< paste for printing and dyeing >
The paste for printing of the present invention contains the aqueous polyurethane dispersion of the present invention, and preferably contains a pigment and/or a dye. In the paste for printing of the present invention, the polyurethane resin (U) functions as a binder, pigment-dispersing resin, or the like.
Examples of the pigment include aqueous pigments using inorganic pigments and organic pigments. Examples of the inorganic pigment include white pigment, extender pigment, black pigment, gray pigment, red pigment, brown pigment, yellow pigment, green pigment, blue pigment, and violet pigment, and specifically, examples thereof include pigments described in items 76 to 147 of "pigment jo よ, (pigment and watercolor)" [ Showa 47, 6/10, and Co-publication Co., ltd. Examples of the organic pigment include extender pigments (alumina white, clay, etc.), precipitants (substances which change dyes into water-insoluble metal salts), natural organic pigments (carmine lake, madder lake, etc.), synthetic organic pigments (nitroso pigments, nitro pigments, azo pigments, etc.), and the like. Specifically, pigments and the like described in the publication items 150 to 186 are cited.
The dye is not particularly limited, and an acid dye, a direct dye, a reactive dye, and a basic dye may be used, and 1 kind may be used alone or 2 or more kinds may be used in combination. The content of the pigment and/or dye is preferably 10 to 20% by weight, more preferably 12 to 18% by weight, based on the weight of the paste for printing.
The paste for printing of the present invention may further contain 1 or more additive materials selected from the group consisting of other synthetic resins, viscoelastic modifiers, leveling agents, wetting agents, antifoaming agents, fillers, flame retardants, preservatives, deterioration preventing agents and stabilizers, crosslinking agents, soft water repellents, inorganic salts, and plasticizers.
Examples of the other synthetic resin include, but are not particularly limited to, acrylic resins, NBR (acrylonitrile-butadiene copolymer), SBR (styrene-butadiene copolymer), EVA (ethylene-vinyl acetate copolymer), polyolefin resins, PVA (polyvinyl alcohol), and the like. Other synthetic resins may also be used in the form of dispersions.
The content of the other synthetic resin in the paste for printing is preferably 0 to 40% by weight, more preferably 0 to 20% by weight, based on the weight of the components other than water and the organic solvent in the paste for printing.
Examples of the viscoelastic control agent include a thickener, for example, an inorganic thickener (sodium silicate, bentonite, etc.), a cellulose thickener (methylcellulose, carboxymethylcellulose, hydroxymethyl cellulose, etc., mn is usually 20,000 or more), a protein thickener (casein, sodium caseinate, ammonium caseinate, etc.), an acrylic thickener (sodium polyacrylate, ammonium polyacrylate, etc., mn is usually 20,000 or more), and a vinyl thickener (polyvinyl alcohol, etc., mn is usually 20,000 or more). Among them, acrylic thickeners and vinyl thickeners are preferable.
Examples of the leveling agent include an acrylic leveling agent, a vinyl leveling agent, a silicone leveling agent, and a fluorine leveling agent.
Examples of the wetting agent include polyhydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, glycerin, etc.).
Examples of the defoaming agent include long-chain alcohols (octanol, etc.), sorbitan derivatives (sorbitan monooleate, etc.), silicone oils (polymethylsiloxane, polyether-modified silicone, fluorine-modified silicone, etc.), and the like.
Examples of the filler include fine particles such as calcium carbonate, titanium oxide, silica, talc, ceramics, and resins, hollow beads, and the like.
Examples of the flame retardant include halogen-based, phosphorus-based, antimony-based, melamine-based, guanidine-based, and guanylurea-based flame retardants.
Examples of the preservative include organic nitrogen-sulfur compound-based preservatives and organic sulfur halide-based preservatives.
Examples of the deterioration inhibitor and stabilizer (such as ultraviolet absorber and antioxidant) include hindered phenol type, hindered amine type, hydrazine type, phosphorus type, benzophenone type, benzotriazole type and the like.
Examples of the crosslinking agent include epoxy-based, blocked isocyanate-based, melamine-based, aziridine-based, alkoxysilane-based crosslinking agents, and the like.
Examples of the softening hydrophobizing agent include silicone compounds such as polysiloxanes and modified silicone oils, and fluorine compounds such as fluoroalkyl acrylate polymers.
Examples of the inorganic salt include alkali metal salts, alkaline earth metal salts, and ammonium salts.
Examples of the plasticizer include low molecular weight compounds such as ethylene glycol, N-methylpyrrolidone and dioctyl phthalate, ester group-containing polymers such as aliphatic linear polyesters, and ether group-containing polymers such as polyethylene glycol dibenzoate.
The fiber matrix using the paste for printing of the present invention is not particularly limited, and examples thereof include natural fibers typified by cotton, wool, and the like; synthetic fibers represented by polyester, nylon, polypropylene, and the like.
The method for applying the paste for printing of the present invention to a fibrous substrate is not particularly limited, and examples thereof include dip coating, blade coating, air knife coating, bar coating, hydraulic bar coating, transfer roll coating, reverse coating, gravure coating, die coating, curtain coating, spray coating, roll coating, screen coating, and the like, and may be applied to a part or the entire surface of the substrate.
The drying condition after coating is room temperature or 25-160 ℃ for 5 minutes-1 day.
The paste for printing is characterized by excellent adhesion to polypropylene synthetic fibers, and also excellent adhesion to other substrates, and as a result, has excellent friction resistance to various fiber substrates.
The fiber product printed and dyed by using the paste for printing of the present invention is useful as clothing, shoes, leather bags, furniture, automobile interior, industrial materials, etc.
The aqueous polyurethane dispersion of the present invention has excellent adhesion to various base fibers, and therefore can be used as a shrink-proofing agent, pilling-proofing agent, binder for hook and loop, nonwoven fabric binder, reinforcing agent for other fibers, and hand feeling regulator for wool, in addition to printing paste.
< nonaqueous electrolyte secondary battery electrode Binder >
The nonaqueous electrolyte secondary battery electrode binder of the present invention may contain the aqueous polyurethane dispersion of the present invention, and may contain a binder resin other than the polyurethane resin (U).
Examples of binder resins other than the polyurethane resin (U) include starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, and the like.
The nonaqueous electrolyte secondary battery electrode binder of the present invention may contain a urethane resin (U), and the urethane resin (U) is preferably contained in the binder as an aqueous polyurethane dispersion dispersed in a medium containing water as a means for containing the urethane resin (U).
< electrode for nonaqueous electrolyte Secondary Battery >
The electrode for a nonaqueous electrolyte secondary battery of the present invention is an electrode formed using an active material, a metal current collector, and the above-described nonaqueous electrolyte secondary battery electrode binder of the present invention, and comprises the above-described polyurethane resin (U), an active material (positive electrode is a positive electrode active material, and negative electrode is a negative electrode active material), and a metal current collector. The electrode may contain a conductive additive (carbon material such as carbon black, amorphous whisker carbon, and graphite) as required.
Examples of the positive electrode active material include transition metal oxides (MnO 2 、V 2 O 5 Etc.), transition metal sulfides (MoS 2 、TiS 2 Etc.), a composite oxide composed of lithium and a transition metal (LiCoO) 2 、LiMnO 2 、LiMn 2 O 4 、LiNiO 2 、LiNi X Co (1-X) O 2 Etc.), conductive polymer materials (polyaniline, polythiophene, polypyrrole, polyacetylene, polyacene, dimercaptothiadiazole/polyaniline complex, etc.).
The negative electrode active material is not particularly limited as long as it can dope/dedope lithium ions, and examples thereof include metallic lithium, lithium alloy, tin oxide, niobium oxide, vanadium oxide, titanium oxide, silicon-based active materials (silicon-lithium alloy, siO, etc.), transition metal nitrides, and carbon-based materials (natural graphite, artificial graphite, etc.). They can be used as a composite (metal lithium-niobium oxide composite, etc.).
The metal current collector of the positive and negative electrodes may be any material having conductivity, and examples thereof include aluminum, nickel, copper, and the like. The thickness of the current collector is usually 5 to 50 μm. Examples of the shape of the current collector include films, sheets, webs, punched products, porous bodies, foam bodies, fiber groups, and molded bodies of nonwoven fabrics, in addition to foils.
The electrode for a nonaqueous electrolyte secondary battery is produced as follows.
That is, the binder paste is prepared by mixing the nonaqueous electrolyte secondary battery electrode binder of the present invention, the active material of the positive electrode or the active material of the negative electrode, if necessary, a conductive auxiliary agent, a thickener (such as carboxymethyl cellulose), and an organic solvent in no particular order at normal temperature or at a controlled temperature. Next, the binder paste is applied to a metal current collector and dried, thereby forming an electrode for a secondary battery.
The weight ratio of the urethane resin (U) to the positive electrode active material or the negative electrode active material [ urethane resin (U)/(positive electrode active material or negative electrode active material) ] is preferably 1/99 to 20/80, more preferably 5/95 to 10/90, from the viewpoints of the adhesiveness of the urethane resin (U) and the capacity of the secondary battery.
Examples of the method of applying the binder paste to the metal current collector include a method using a film coater and a doctor blade.
Further, as a method of removing water and/or an organic solvent after applying the binder paste to the metal current collector, there is a method of drying at 60 to 150 ℃, preferably 70 to 130 ℃ for 5 to 120 minutes, and further drying at 80 to 120 ℃ under reduced pressure for 1 to 12 hours, for example. The thickness of the coating film on the electrode after coating and drying is preferably 10 to 500 μm from the viewpoints of the capacity and cycle characteristics of the secondary battery to be described later. The thickness and density of the coating film on the electrode can be controlled by, for example, compression molding at a predetermined pressure using a roll press.
< nonaqueous electrolyte secondary Battery >
The nonaqueous electrolyte secondary battery of the present invention is produced by sealing the electrode (positive electrode and negative electrode) for a nonaqueous electrolyte secondary battery of the present invention, a separator, and an electrolyte in a container.
The separator may be a porous film or a nonwoven fabric, and the porous film may be polyolefin, polyimide, polyvinylidene fluoride, polyester, or the like. Examples of the nonwoven fabric include polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyamide nonwoven fabric, and glass fiber. Examples of the shape of the nonaqueous electrolyte secondary battery include a cylindrical shape, a button shape, a square shape, and a film shape.
Examples of the nonaqueous electrolyte used in the nonaqueous electrolyte secondary battery include LiPF 6 、LiBF 4 、LiClO 4 、LiAsF 6 、CF 3 SO 3 Li、(CF 3 SO 2 ) 2 The electrolyte such as N/Li is dissolved in an organic solvent (diethyl carbonate, ethylene carbonate, methylethyl carbonate, propylene carbonate, gamma-butyrolactone, etc.) alone or in combination of 2 or more kinds.
The nonaqueous electrolyte secondary battery electrode binder of the present invention is excellent in swelling resistance to an electrolyte, and in adhesion between each active material of a positive electrode and a negative electrode and each metal collector of the electrodes. The swelling resistance can be evaluated by an electrolyte swelling test described later, and the adhesion can be evaluated by a peeling test described later.
The nonaqueous electrolyte secondary battery having an electrode formed by using the nonaqueous electrolyte secondary battery electrode binder of the present invention is electrochemically stable and has excellent battery capacity retention after a high-voltage charge/discharge cycle test described later.
The aqueous polyurethane dispersion of the present invention can be suitably used for the electrode binder for nonaqueous electrolyte secondary batteries.
Examples
The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
PREPARATION EXAMPLE 1
To the reaction vessel was charged a high molecular weight polyolefin (A00-1) [ Mn:113,000, isotacticity: 50% by weight of a polyolefin (A01-1) was obtained by heating and melting the mixture by a sheathed resistance heater while introducing nitrogen gas into the liquid phase, and thermally degrading the mixture under stirring at 370℃for 85 minutes under the trade name "Vistamaxx3980", manufactured by Exxonmobil Co., ltd.).
100 parts by weight of the obtained polyolefin (A01-1) and 6.5 parts by weight of maleic anhydride (E-1) (described in terms of parts by weight obtained by subtracting the amount distilled off below in advance; the same applies to the following production examples), were charged into a reaction vessel, replaced with nitrogen, heated to 180℃under nitrogen-introducing conditions to uniformly dissolve the same, and a solution obtained by dissolving 0.5 part by weight of a radical initiator [ dicumyl peroxide, trade name "Percumyl D", manufactured by Nikko oil Co., ltd. ] (F-1) in 5 parts by weight of xylene was added dropwise over 5 minutes, followed by stirring under reflux of xylene for 1 hour. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (X-1).
Next, 100 parts by weight of the acid-modified polyolefin (X-1) and 6.4 parts by weight of 2-aminoethanol (G-1) (described in terms of parts by weight obtained by subtracting the amount distilled off below in advance; the same applies to the following production examples) were charged into the reaction vessel, and the reaction was carried out at 180℃for 1 hour under a nitrogen atmosphere.
Then, unreacted 2-aminoethanol was distilled off at 180℃under reduced pressure of 2.7kPa to obtain a polyolefin (A1-1) having hydroxyl groups.
The hydroxyl group-containing polyolefin (A1-1) had a hydroxyl group value of 29, an acid value of 0.2, mn of 3,500 and an isotacticity of 43%. In addition, the number of double bonds per 1,000 carbon atoms of the polyolefin (A01-1) used for modification was 7.5.
PREPARATION EXAMPLE 2
To the reaction vessel was charged a high molecular weight polyolefin (A00-1) [ Mn:113,000, isotacticity: 50% by weight of a polyolefin (A01-2) was obtained by heating and melting the mixture by a sheathed resistance heater while introducing nitrogen gas into the liquid phase, and thermally degrading the mixture under stirring at 380℃for 65 minutes under the trade name "Vistamaxx3980", manufactured by Exxonmobil Co., ltd. ]1000 parts by weight.
100 parts by weight of the obtained polyolefin (A01-2) and 8 parts by weight of maleic anhydride (E-1) were charged into a reaction vessel, replaced with nitrogen, and then heated to 180℃under nitrogen introduction to uniformly dissolve the polyolefin, followed by stirring for 1 hour. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (X-2).
Next, 100 parts by weight of the acid-modified polyolefin (X-2) and 6.4 parts by weight of 2-aminoethanol (G-1) were charged into the reaction vessel, and reacted at 180℃for 1 hour under a nitrogen atmosphere.
Then, unreacted 2-aminoethanol was distilled off at 180℃under reduced pressure of 2.7kPa to obtain a polyolefin (A1-2) having hydroxyl groups.
The hydroxyl group-containing polyolefin (A1-2) had a hydroxyl group value of 29, an acid value of 0.1, mn of 3,300 and an isotacticity of 43%. In addition, the number of double bonds per 1,000 carbon atoms of the polyolefin (A01-2) used for modification was 8.8.
PREPARATION EXAMPLE 3
Into the reaction vessel was charged a high molecular weight polyolefin (a 00-2) [ Mn:76,000, isotacticity: 20% by weight of "Vistamaxx6202", manufactured by Exxonmobil Co., ltd. ]1000 parts by weight, and the polyolefin (A01-3) was obtained by heating and melting the resultant mixture by a sheathed resistance heater while introducing nitrogen gas into the liquid phase and thermally degrading the resultant mixture under stirring at 400℃for 50 minutes.
100 parts by weight of the obtained polyolefin (A01-3) and 11 parts by weight of maleic anhydride (E-1) were charged into a reaction vessel, replaced with nitrogen, heated to 180℃under nitrogen atmosphere to dissolve them uniformly, and a solution obtained by dissolving 3 parts by weight of a radical initiator [ dicumyl peroxide, trade name "Percumyl D", manufactured by Nikko Co., ltd. ] (F-1) in 10 parts by weight of xylene was added dropwise over 5 minutes, followed by stirring under reflux of xylene for 1 hour. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (X-3).
Next, 100 parts by weight of the acid-modified polyolefin (X-3) and 10 parts by weight of 2-aminoethanol (G-1) were charged into the reaction vessel, and reacted at 180℃for 1 hour under a nitrogen atmosphere.
Then, unreacted 2-aminoethanol was distilled off at 180℃under reduced pressure of 2.7kPa to obtain a polyolefin (A1-3) having hydroxyl groups.
The hydroxyl group-containing polyolefin (A1-3) had a hydroxyl group value of 46, an acid value of 0.1, mn of 2,300 and an isotacticity of 18%. In addition, the number of double bonds per 1,000 carbon atoms of the polyolefin (A01-3) used for the modification was 9.5.
PREPARATION EXAMPLE 4
Into the reaction vessel was charged a high molecular weight polyolefin (a 00-2) [ Mn:76,000, isotacticity: 20% by weight of "Vistamaxx6202", manufactured by Exxonmobil Co., ltd. ]1000 parts by weight, and the polyolefin (A01-4) was obtained by heating and melting the resultant mixture by a sheathed resistance heater while introducing nitrogen gas into the liquid phase and thermally degrading the resultant mixture under stirring at 400℃for 100 minutes.
100 parts by weight of the obtained polyolefin (A01-4) and 23.5 parts by weight of maleic anhydride (E-1) were charged into a reaction vessel, replaced with nitrogen, heated to 180℃under nitrogen atmosphere to dissolve it uniformly, and a solution obtained by dissolving 3 parts by weight of a radical initiator [ dicumyl peroxide, trade name "Percumyl D", manufactured by Nikko Co., ltd. ] (F-1) in 10 parts by weight of xylene was added dropwise over 5 minutes, followed by stirring under reflux of xylene for 1 hour. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (X-4).
Next, 100 parts by weight of the acid-modified polyolefin (X-4) and 27 parts by weight of 2-aminoethanol (G-1) were charged into the reaction vessel, and reacted at 180℃for 1 hour under a nitrogen atmosphere.
Then, unreacted 2-aminoethanol was distilled off at 180℃under reduced pressure of 2.7kPa to obtain a polyolefin (A1-4) having hydroxyl groups.
The hydroxyl group-containing polyolefin (A1-4) had a hydroxyl group value of 108, an acid value of 0.2, mn of 1,050 and an isotacticity of 17%. In addition, the number of double bonds per 1,000 carbon atoms of the polyolefin (A01-4) used for modification was 22.4.
PREPARATION EXAMPLE 5
Into the reaction vessel was charged a high molecular weight polyolefin (A00-3) [ Mn:200,000 isotacticity: 33% by weight of the polyolefin (A01-5) was obtained by heating and melting the mixture by a sheathed resistance heater while introducing nitrogen gas into the liquid phase, and thermally degrading the mixture under stirring at 380℃for 80 minutes under the trade name "TAFMER S4030", 1000 parts by weight of Sanjing chemical Co., ltd.).
100 parts by weight of the obtained polyolefin (A01-5) and 4.5 parts by weight of maleic anhydride (E-1) were charged into a reaction vessel, replaced with nitrogen, heated to 180℃under nitrogen introduction to dissolve it uniformly, and a solution obtained by dissolving 0.5 parts by weight of a radical initiator [ dicumyl peroxide, trade name "Percumyl D", manufactured by Nikko Co., ltd. ] (F-1) in 5 parts by weight of xylene was added dropwise over 5 minutes, followed by stirring under reflux of xylene for 1 hour. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (X-5).
Next, 100 parts by weight of the acid-modified polyolefin (X-5) and 4.6 parts by weight of 2-aminoethanol (G-1) were charged into the reaction vessel, and reacted at 180℃for 1 hour under a nitrogen atmosphere.
Then, unreacted 2-aminoethanol was distilled off at 180℃under reduced pressure of 2.7kPa to obtain a polyolefin (A1-5) having hydroxyl groups.
The hydroxyl group-containing polyolefin (A1-5) had a hydroxyl group value of 21, an acid value of 0.2, mn of 4,500 and an isotacticity of 31%. In addition, the number of double bonds per 1,000 carbon atoms of the polyolefin (A01-5) used for modification was 5.4.
Comparative production example 1 ]
Into the reaction vessel, a high molecular weight polyolefin (ratio A00-1) [ Mn:100,000, isotacticity: 90% by weight of "SunAllomer PZA20A", manufactured by SunAllomer Co., ltd. ]1000 parts by weight was melted by heating with a sheathed resistance heater while introducing nitrogen gas into the liquid phase, and the resultant was thermally degraded under stirring at 400℃for 1200 minutes to obtain a polyolefin (ratio A01-1).
100 parts by weight of the obtained polyolefin (ratio A01-1) and 28 parts by weight of maleic anhydride (E-1) were charged into a reaction vessel, replaced with nitrogen, heated to 180℃under nitrogen introduction to dissolve it uniformly, and a solution obtained by dissolving 3 parts by weight of a radical initiator [ dicumyl peroxide, trade name "Percumyl D", manufactured by Nikko Co., ltd. ] (F-1) in 10 parts by weight of xylene was added dropwise over 5 minutes, followed by stirring under reflux of xylene for 1 hour. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (ratio X-1).
Next, 100 parts by weight of an acid-modified polyolefin (ratio X-1) and 22 parts by weight of 2-aminoethanol (G-1) were charged into the reaction vessel, and reacted at 180℃for 1 hour under a nitrogen atmosphere.
Then, unreacted 2-aminoethanol was distilled off at 180℃under reduced pressure of 2.7kPa to obtain a polyolefin having hydroxyl groups (ratio A1-1).
The hydroxyl group-containing polyolefin (ratio A1-1) had a hydroxyl number of 122, an acid value of 0.2, mn of 940 and an isotacticity of 84%. In addition, the number of double bonds per 1,000 carbon atoms of the polyolefin (ratio A01-1) used for the modification was 22.5.
Comparative production example 2 ]
A polyolefin (ratio A00-2) [ Mn ] containing 27% by weight of propylene and 73% by weight of ethylene as constituent monomers was charged into a reaction vessel: 40,000 isotacticity: 3%, under the trade name "TAFMER P0280", manufactured by Sanjing chemical Co., ltd. ]1000 parts by weight, the polyolefin (ratio A01-2) was obtained by heating and melting the mixture by a sheathed resistance heater while introducing nitrogen gas into the liquid phase and thermally degrading the mixture under stirring at 385℃for 210 minutes.
100 parts by weight of the obtained polyolefin (ratio A01-2) and 9 parts by weight of maleic anhydride (E-1) were charged into a reaction vessel, replaced with nitrogen, heated to 180℃under nitrogen introduction to uniformly dissolve the polyolefin, and a solution obtained by dissolving 0.5 part by weight of a radical initiator [ dicumyl peroxide, trade name "Percumyl D", manufactured by Nikko Co., ltd. ] (F-1) in 5 parts by weight of xylene was added dropwise over 5 minutes, followed by stirring under reflux of xylene for 1 hour. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (ratio X-2).
Next, 100 parts by weight of an acid-modified polyolefin (ratio X-2) and 10 parts by weight of 2-aminoethanol (G-1) were charged into the reaction vessel, and reacted at 180℃for 1 hour under a nitrogen atmosphere.
Then, unreacted 2-aminoethanol was distilled off at 180℃under reduced pressure of 2.7kPa to obtain a polyolefin having hydroxyl groups (ratio A1-2).
The hydroxyl group-containing polyolefin (ratio A1-2) had a hydroxyl value of 35, an acid value of 0.1, mn of 3,000 and an isotacticity of 1%. In addition, the number of double bonds per 1,000 carbon atoms of the polyolefin (ratio A01-2) used for the modification was 10.5.
Example 1 ]
(preparation of urethane prepolymer)
179.26 parts by weight of a hydroxyl group-containing polyolefin (A1-1), 92.19 parts by weight of a polymer polyol (A2-1), 82.65 parts by weight of an isocyanate component (B-1) [ IPDI, isophorone diisocyanate ], 4.18 parts by weight of [1, 4-butanediol ] as a chain extender (C), 17.03 parts by weight of [2, 2-dimethylolpropionic acid ], and 124.69 parts by weight of an organic solvent [ THF, tetrahydrofuran ] were charged into a simple pressurized reaction apparatus equipped with a stirrer and a heating device, and stirred at 85℃for 10 hours to carry out a urethanization reaction, thereby producing a THF solution (P-1) of a urethane prepolymer.
(production of polyurethane aqueous dispersion)
500.00 parts by weight of the THF solution (P-1) of the urethane prepolymer thus obtained was charged into a simple pressurized reaction apparatus equipped with a stirrer and a heating reaction apparatus, 359.28 parts by weight of THF and 12.81 parts by weight of triethylamine (neutralizing agent) were added while stirring at 50℃and, after 30 minutes of homogenization at 60rpm, 676.04 parts by weight of ion-exchanged water was slowly added with stirring at 500rpm while maintaining the temperature at 50℃to thereby emulsify, 86.82 parts by weight of the chain extender (C-3) [ 5% by weight of diethylenetriamine aqueous solution ] was added, and THF was distilled off at 65℃under reduced pressure for 12 hours to obtain the aqueous polyurethane dispersion (Q-1).
< examples 2 to 22, comparative examples 1 to 4>
Polyurethane aqueous dispersions (Q-2) to (Q-22) and (ratios Q-1) to (Q-4) were obtained in the same manner as in example 1 except that the raw materials were used in accordance with tables 1 to 4.
The respective aqueous polyurethane dispersions (Q-1) to (Q-22) and (ratio Q-1) to (ratio Q-4) obtained were evaluated in accordance with the following procedures. The results are shown in tables 1 to 4.
The volume average particle diameter (Dv) of the polyurethane resin was measured using a laser diffraction particle size distribution measuring instrument "LA-750" (manufactured by horiba ltd).
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The raw materials used in the examples and comparative examples of tables 1 to 4 are as follows.
Polymer polyol (A2-1):
kuraray Polyol P-2010: poly (3-methyl-1, 5-pentanediol, adipic acid polycondensate) having Mn=2,000 [ manufactured by KURARAY Co., ltd ]
Polymer polyol (A4-1):
ETERNACOLL UH-200: mn=2,000 polyhexamethylene carbonate diol (product of Yu Kogyo Xing Co., ltd.)
Polymer polyol (A5-1):
PTMG2000: poly (oxytetramethylene) glycol having Mn=2,000 [ Mitsubishi chemical Co., ltd ]
Polymer polyol (A5-2):
PTMG3000: poly (oxytetramethylene) glycol having Mn=3,000 [ Mitsubishi chemical Co., ltd ]
Polymer polyol (A6-1):
ACTFLOW UT-1001: mn=2,000 polyacrylic acid glycol (manufactured by Zodiac chemical Co., ltd.)
Polymer polyol (A6-2):
ARUFON UH-2032: polyacrylic acid glycol having mn=2,000 [ manufactured by eastern asia Synthesis Co., ltd ]
Polyester polyol (RA-1):
kuraray Polyol P-2020: poly (3-methyl-1, 5-pentanediol, terephthalic acid polycondensate) with mn=2,000 [ KURARAY corporation ]
Catalyst:
neostann U-600: bismuth tris (2-ethylhexanoate) (manufactured by Ridong chemical Co., ltd.)
And (2) a surfactant:
EMULMIN 50: ethylene Oxide (EO) adduct of higher alcohol (Sanyo chemical industry Co., ltd.)
[1] Adhesion of
The surface-treated polypropylene film (OPP) [ PYLEN P-2161 (30 μm thick) manufactured by Toyo Kabushiki Kaisha ], the surface-treated polyester film (PET) [ ESPET E-5102 (12 μm thick) manufactured by Toyo Kaisha) and the surface-treated nylon film [ HARDEN N-1130 (15 μm thick) manufactured by Toyo Kaisha) ] were each coated (covered) with an aqueous polyurethane dispersion so that the film thickness after drying was 50 μm, and after drying for 7 days in an atmosphere of 25℃and 50% RH, the film was cured at a temperature of 5 ℃ (+ -2 ℃) and a relative humidity of 10% (+ -10%), and a chequer plate cellophane tape (registered trademark) peeling test was performed at a temperature of 5 ℃ + -2 ℃) and a relative humidity of 10% (+ -10%), to evaluate the adhesion (total of 100 squares) to the substrate.
Conditions other than temperature and humidity were evaluated according to the following evaluation criteria using cellophane tape (registered trademark) according to JIS K5600-5-6 (manufactured by Mikubang Co., ltd.).
< evaluation criterion >
And (3) the following materials: the number of non-peeled square pieces is 100
O: the number of non-peeled square checks is 90 to 99
X: the number of non-peeled square pieces is less than 90
[2] Storage stability of aqueous Dispersion (40 ℃ C., high temperature)
30g of the aqueous polyurethane dispersion was placed in a screw vial [50mL (diameter of the vial: 35 mm. Times. Height: 78 mm) ] and stored at 40℃for 7 days. The "storage stability at 40℃was obtained from the measurement results of the volume average particle diameters (Dv) (unit: μm) before and after storage according to the following calculation formula, and the evaluation was performed according to the following evaluation criteria.
(storage stability at 40 ℃) = (volume average particle diameter after storage) ×100/(volume average particle diameter before storage)
< evaluation criterion >
O: less than 150%
X: 150% or more
[3] Storage stability of aqueous dispersion (10 ℃ C., low temperature)
30g of the aqueous polyurethane dispersion (Q) was placed in a screw vial [50mL (diameter of the vial: 35 mm. Times. Height: 78 mm) ] and stored at 10℃for 7 days. The "storage stability at 10℃was obtained from the measurement results of the volume average particle diameters (Dv) (unit: μm) before and after storage according to the following calculation formula, and the evaluation was performed according to the following evaluation criteria.
(storage stability at 10 ℃) (%) = (volume average particle diameter after storage) ×100/(volume average particle diameter before storage)
< evaluation criterion >
O: less than 150%
X: 150% or more
As is clear from the results of tables 3 and 4, the aqueous polyurethane dispersion (Q) of the example was excellent in both the adhesion to various types of substrates (particularly, polypropylene substrates) and the storage stability (high temperature, low temperature) as compared with the comparative example. On the other hand, it was found that the aqueous polyurethane dispersion of the comparative example was inferior in adhesion to a polypropylene substrate and in storage stability (high temperature and low temperature).
< evaluation of inkjet ink compositions of examples 23 to 44 and comparative examples 5 to 8 >
(production of inkjet ink composition)
Using the aqueous polyurethane dispersions (Q-1) to (Q-22) or (ratio Q-1) to (ratio Q-4) obtained in examples 1 to 22 or comparative examples 1 to 4, the pigments [ aqueous carbon Black dispersions { Aquara-Black 162, manufactured by Tokida carbon Co., ltd., solid content 20% by weight ], propylene glycol as a humectant, glycerin and ion-exchanged water were put into a container and mixed for 10 minutes to prepare inkjet ink compositions (I-1) to (I-22) and inkjet ink compositions for comparison (ratio I-1) to (ratio I-4).
The respective obtained inkjet ink compositions (I) were evaluated according to the following procedure. The results are shown in tables 5 and 6.
[1] Adhesion of images Using inkjet ink composition (I)
The inkjet ink composition was applied onto a surface-treated polypropylene film (OPP) by a bar coater so as to have a thickness of 2 μm (thickness: 30 μm) (PYLEN P-2161, manufactured by Toyo Kagaku Co., ltd.), a surface-treated polyester film (PET) [ ESPET E-5102, manufactured by Toyo Kagaku Co., ltd.) (thickness: 12 μm) ] and a surface-treated nylon film (HARDEN N-1130, manufactured by Toyo Kagaku Co., ltd.) (thickness: 15 μm) ] by a bar coater, and after drying at 100℃for 10 minutes, a peeling test of a cellophane tape (registered trademark) was performed to evaluate adhesion to a substrate (total of 100 squares).
The conditions were evaluated according to the following < evaluation criteria > using cellophane tape (registered trademark) (manufactured by Miq corporation) in accordance with JIS K5600-5-6.
< evaluation criterion >
And (3) the following materials: the number of non-peeled square pieces is 100
O: the number of non-peeled square checks is 90 to 99
X: the number of non-peeled square pieces is less than 90
[2] Storage stability of inkjet ink compositions
30g of the ink jet ink composition (I) thus prepared was placed in a screw vial [50mL (diameter of the vial: 35 mm. Times. Height: 78 mm) ] and stored at 50℃for 14 days. The viscosity change rate was calculated from the measurement results of the viscosity before and after storage according to the following formula, and the storage stability was evaluated according to the following criteria.
The viscosity was measured at a constant temperature of 25℃using an E-type viscometer (model TV-25 viscometer manufactured by Dong machine industries Co.).
(viscosity change rate) (%) = { (absolute value of viscosity after storage-viscosity before storage } ×100/(viscosity before storage)
< evaluation criterion >
O: the viscosity change rate is less than 10 percent
X: the change rate of viscosity is more than 10 percent
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From the results of tables 5 and 6, it is apparent that the inkjet ink composition (I) containing the polyurethane aqueous dispersion (Q) of the example was excellent in adhesion to various types of substrates (particularly polypropylene substrates) and also excellent in storage stability. On the other hand, it is found that the ink jet ink composition of the comparative example has poor adhesion to a polypropylene substrate and poor storage stability. In addition, it was found that the ink jet ink composition (comparative example 8) produced using the polyol containing the polyester polyol having the structural unit represented by the general formula (1) was poor in storage stability.
< evaluation of aqueous printing ink compositions of examples 45 to 66 and comparative examples 9 to 12 >
(preparation of aqueous printing ink composition)
The aqueous polyurethane dispersions (Q-1) to (Q-22) and (ratio Q-1) to (ratio Q-4) obtained in examples 1 to 22 or comparative examples 1 to 4 were used, respectively, to obtain ion-exchanged water, isopropyl alcohol or ethanol, pigment blue 15 as shown in tables 7 and 8: 3. as a pigment dispersant, "CARRYBON L-400" [ Sanyo chemical industry Co., ltd.) and 100 parts by weight of glass beads were put into a polyethylene container, and kneaded for 1 hour by a paint shaker (Paint Conditioner) [ Red Devil Co., ltd.) to obtain aqueous printing ink compositions (S-1) to (S-22) and (ratios S-1) to (S-4).
The aqueous printing ink compositions (S-1) to (S-22) and (ratio S-1) to (ratio S-4) thus obtained were evaluated according to the following procedures. The results are shown in tables 7 and 8.
[1] Image adhesion Using aqueous printing ink composition (S)
The adhesion to a substrate (total 100 squares) was evaluated by applying an aqueous printing ink composition (S) to a 20 μm solid plate at a speed of 50m/min using a gravure printer (manufactured by R K Print Coat Instruments Co.) on a surface-treated polypropylene film (OPP) [ PYLEN P-2161 (30 μm thick) ], a surface-treated polyester film (PET) [ ESPET E-5102 (12 μm thick) ] manufactured by Toyobo Co., ltd.) and a surface-treated nylon film [ HARDEN N-1130 (15 μm thick) ] manufactured by Toyobo Co., ltd.) and drying the resultant film with a dryer, and then performing a chequer cellophane tape (registered trademark) peeling test.
Conditions other than temperature and humidity were evaluated according to the following < evaluation criteria > using cellophane tape (registered trademark) (manufactured by Miq corporation) in accordance with JIS K5600-5-6.
< evaluation criterion >
And (3) the following materials: the number of non-peeled square pieces is 100
O: the number of non-peeled square checks is 90 to 99
X: the number of non-peeled square pieces is less than 90
[2] Storage stability of aqueous printing ink composition (S)
30g of the aqueous printing ink composition (S) thus prepared was put into a screw vial [50mL (diameter of the vial: 35 mm. Times. Height: 78 mm) ] and stored at 50℃for 14 days. The viscosity change rate was calculated from the measurement results of the viscosity before and after storage according to the following formula, and the storage stability was evaluated according to the following criteria.
The viscosity was measured using a type B viscometer at a constant temperature of 25 ℃.
(viscosity change rate) (%) = { (absolute value of viscosity after storage-viscosity before storage } ×100/(viscosity before storage)
< evaluation criterion >
O: the viscosity change rate is less than 10 percent
X: the change rate of viscosity is more than 10 percent
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From the results of tables 7 and 8, it is clear that the aqueous printing ink composition (S) containing the aqueous polyurethane dispersion (Q) of the example is excellent in adhesion to various types of substrates (particularly polypropylene substrates) and also excellent in storage stability. On the other hand, it is found that the aqueous printing ink composition of the comparative example sometimes has poor adhesion to a polypropylene substrate and also has poor storage stability. In addition, it was found that the aqueous printing ink composition (comparative example 12) produced using the polyol containing the polyester polyol having the structural unit represented by the general formula (1) was poor in storage stability.
< evaluation of Water-based coating compositions of examples 67 to 88 and comparative examples 13 to 16 >
< method for evaluating Normal temperature Dry Water-based coating composition >
1. Preparation of aqueous coating composition for weather resistance test (aqueous coating composition for coating building Material or coating building Material)
To a polyethylene vessel, 20 parts of ion-exchanged water, 66 parts of titanium oxide, 6 parts of an aqueous solution having a solid content of 10% adjusted in advance to "ortan 731" (manufactured by dow chemical Co.) as a pigment dispersant, "SN Defoamer 777" (manufactured by SAN NOPCO corporation) as a defoaming agent, 0.2 parts of ethylene glycol as a wetting agent, and 500 parts of zirconia beads were added, and kneaded for 1 hour by a paint shaker [ Red Devil corporation ]. The resulting dispersion was filtered through a wire mesh having a mesh opening of 75 μm, whereby zirconia beads were removed to obtain a pigment dispersion.
Using the aqueous polyurethane dispersions (Q-1) to (Q-22) and (ratio Q-1) to (ratio Q-4) obtained in examples 1 to 22 or comparative examples 1 to 4, respectively, 55.6 parts of each of the aqueous polyurethane dispersions (produced by co. Ex. E-TEC, 35% solids) which had been adjusted to a solid content of 24% by weight with ion-exchanged water, 38.6 parts of each of the acrylic emulsions (produced by co. Ex. AE-TEC, 35% solids), 25.6 parts of the pigment dispersion (produced by co. M. E-TEC), 2.2 parts of an aqueous solution (produced by co. M. E-Ashland Specialty Chemicals) which had been adjusted to a solid content of 4% by weight with a thickener, "adeku UH-420" produced by ADEKA, 4% by co. Adek as a thickener) and 1.1 part of an aqueous solution (produced by co. M. E.m. O., 10% by weight) which had been adjusted to a solid content of 10% by weight with 0.9 parts of texol (produced by co. E-m. E-TEC, 2, 4-trimethyl-1, 3-pentanediol 2-methylpropionate) as a film-forming aid were added to a container made of glass, and the aqueous paint was obtained by mixing (produced by co. M. 4) at a ratio of 0.3 to 3 m. T (T) from T-4 by mixing).
2. Method for evaluating weather resistance
The aqueous coating composition for weather resistance test was applied to a glass plate (10 cm long by 10cm wide by 0.5cm thick) by a bar coater so that the film thickness after drying was 80. Mu.m. The sample was dried in a constant temperature and humidity oven at 25℃and 50% RH for 24 hours, to thereby obtain a sample for evaluation.
A weather resistance tester [ SUV-W151 manufactured by Kawasaki electric Co., ltd. ":]the obtained samples for evaluation were subjected to weather resistance test [ test conditions: the composition was subjected to irradiation at an intensity of 75mW/cm at 73 ℃ X50% RH 2 After 3.8 hours of irradiation, 10 cycles were repeated with 1 cycle of no irradiation at 38 ℃ x 95% RH for 1.0 hour]The gloss before and after the test was measured, and the retention of the gloss was calculated by the following formula. The glossiness was measured using a glossmeter [ VG-1D manufactured by Nippon Denshoku Kogyo Co., ltd.]The measurement was performed under the condition of incidence/reflection angle=60 °/60 °. The retention of gloss was evaluated according to the following criteria.
Retention of gloss (%) =gloss after weather resistance test/gloss before weather resistance test×100
And (3) the following materials: the retention of glossiness is 70% or more
And (2) the following steps: the retention of glossiness is 50% or more and less than 70%
Delta: the retention of glossiness is 30% or more and less than 50%
X: the retention of gloss is less than 30%
< method for evaluating adhesion to Polypropylene >
The weather-resistant aqueous coating composition was applied to a commercially available polypropylene sample by a bar coater so that the film thickness was 20. Mu.m, and dried in a constant temperature and humidity oven at 25℃and 50% RH for 24 hours to obtain a coated test piece. 6 perpendicular cuts were made at 1mm intervals on the coated surface, and then peel-off test was performed by using Cellotap (registered trademark), and the number of residual coated films 1mm square was examined. The adhesion (total of 25 squares) was evaluated according to the following criteria.
And (3) the following materials: the residue number is more than 24
O: the residue number is 20 or more and less than 24
Delta: the residue number is 15 or more and less than 20
X: the residue number is less than 15
< method for evaluating adhesion to Steel sheet >
The surface of a commercially available sample of a cold-rolled steel sheet was polished with a waterproof sand paper, degreased with toluene, and then the weather-resistant aqueous coating composition was applied to the surface by a bar coater so that the film thickness was 20. Mu.m, and dried in a constant temperature and humidity oven at 25℃and 50% RH for 24 hours, whereby a test piece having a coating film formed thereon was obtained. 6 perpendicular cuts were made at 1mm intervals on the coated surface, and then peel-off test was performed by using Cellotap (registered trademark), and the number of residual coated films 1mm square was examined. The adhesion (total of 25 squares) was evaluated according to the following criteria.
And (3) the following materials: the residue number is more than 24
O: the residue number is 20 or more and less than 24
Delta: the residue number is 15 or more and less than 20
X: the residue number is less than 15
From the results shown in tables 9 to 10, it is clear that the aqueous coating composition containing the aqueous polyurethane dispersion (Q) of the example was excellent in adhesion to various substrates (particularly polypropylene substrates) and also excellent in weather resistance. On the other hand, it was found that the aqueous coating compositions of comparative examples 13 to 15 had poor adhesion to polypropylene substrates. In addition, it was found that the aqueous coating composition (comparative example 16) produced using the polyol containing the polyester polyol having the structural unit represented by the general formula (1) was poor in weather resistance.
< evaluation of aqueous coating compositions of examples 89 to 110 and comparative examples 17 to 20 >
< method for evaluating baking aqueous coating composition >
1. Preparation of Water-based coating composition for evaluation of adhesion (Water-based coating composition for automobile)
70 parts of rutile type titanium dioxide, "Disperbyk190" (manufactured by BYK-Chemie Japan Co., ltd.) 10 parts, 0.5 part of carbon black [ Orion Engineered Carbons Co., ltd. "FW200P" ] and 34.3 parts of ion-exchanged water were premixed and then dispersed for 30 minutes by a paint mixer to obtain a pigment dispersion paste. The aqueous polyurethane dispersions (Q-1) to (Q-22) and (ratio Q-1) to (ratio Q-4) obtained in examples 1 to 22 and comparative examples 1 to 4 were used, respectively, 116.7 parts of each of the aqueous polyurethane dispersions (V-based MD 1480) (manufactured by Toyo-yo Co., ltd., polyester resin) and 23.3 parts of "Cymel 327" (manufactured by Allnex Japan Co., ltd.) each of which was adjusted to a solid content concentration of 24 wt% with ion-exchanged water were added, and the mixture was uniformly mixed, and then N, N-dimethyl-2-aminoethanol was added to adjust the pH of the coating to 8.0 to 9.0, thereby obtaining aqueous coating compositions (Y-1) to (Y-22) and (ratio Y-1) to (Y-4) for evaluating adhesion.
< method for evaluating adhesion to an electrodeposited sheet >
The aqueous coating composition for adhesion evaluation was applied to a commercial cationic electrodeposition coating sample by a bar coater so that the film thickness was 20. Mu.m, preheated at 80℃for 5 minutes, and then heat-cured at 120℃for 30 minutes to obtain a test piece having a coating film formed thereon. 6 perpendicular cuts were made at 1mm intervals on the coated surface, and then peel-off test was performed by using Cellotap (registered trademark), and the number of residual coated films 1mm square was examined. The adhesion (total of 25 squares) was evaluated according to the following criteria.
And (3) the following materials: the residue number is more than 24
O: the residue number is 20 or more and less than 24
Delta: the residue number is 15 or more and less than 20
X: the residue number is less than 15
< method for evaluating adhesion to Polypropylene >
The aqueous coating composition for adhesion evaluation was applied to a commercially available polypropylene sample by a bar coater so that the film thickness was 20. Mu.m, preheated at 80℃for 5 minutes, and then cured by heating at 120℃for 30 minutes, to obtain a coated test piece. 6 perpendicular cuts were made at 1mm intervals on the coated surface, and then peel-off test was performed by using Cellotap (registered trademark), and the number of residual coated films 1mm square was examined. The adhesion (total of 25 squares) was evaluated according to the following criteria.
And (3) the following materials: the residue number is more than 24
O: the residue number is 20 or more and less than 24
Delta: the residue number is 15 or more and less than 20
X: the residue number is less than 15
< method for evaluating storage stability >
The viscosity (V1) of the aqueous coating composition for evaluating adhesion was measured. After storing the composition at 40℃for 10 days, the viscosity (V2) was measured. The thickening ratio was calculated from the following formula, and the storage stability was evaluated according to the following criteria.
Thickening ratio (%) = (V2-V1)/v1×100
O: a thickening ratio of-50% to +50%
Delta: -a thickening ratio of less than or equal to 100% less than or equal to-50% or +50% < thickening ratio of less than or equal to +100% >
X: thickening ratio of < -100% or +100% < thickening ratio
< conditions for measuring viscosity >
Measurement device: b-type viscometer
Rotational speed: 60rpm
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From the results in tables 11 to 12, it is clear that the aqueous coating composition containing the aqueous polyurethane dispersion (Q) of the example was excellent in adhesion to various substrates (particularly polypropylene substrates) and also excellent in storage stability. On the other hand, it was found that the aqueous coating compositions of comparative examples 17 to 19 were poor in adhesion to polypropylene substrates and also poor in storage stability. In addition, it was found that the aqueous coating composition (comparative example 20) produced using the polyol containing the polyester polyol having the structural unit represented by the general formula (1) was poor in storage stability.
< evaluation of printing paste of examples 111 to 132 and comparative examples 21 to 24 >
(preparation of paste for printing and dyeing)
Using the aqueous polyurethane dispersions (Q-1) to (Q-22) and (ratio Q-1) to (ratio Q-4) obtained in examples 1 to 22 or comparative examples 1 to 4, respectively, 8.9 parts of a viscoelastic regulator ("SN-THICKENER" manufactured by SAN NOPCO Co., ltd.), 44.6 parts of titanium oxide, and 18.9 parts of a pigment ("NLRed FR3R-D" manufactured by Song Co., ltd.) were mixed with 100 parts of each of the aqueous polyurethane dispersions (ratio Q-1) to (ratio Q-4) which were adjusted to a solid content of 24% by weight with ion-exchanged water in advance, to obtain pastes (V-1) to (V-22) and (ratio V-1) to (ratio V-4) for printing.
The printing pastes (V-1) to (V-22) and (ratio V-1) to (ratio V-4) were evaluated according to the following procedure. The results are shown in tables 13 and 14.
[1] Friction fastness of paste (V) for printing and dyeing
The paste for printing, which was prepared as described above, was applied to various kinds of fiber cloth such as polypropylene fiber cloth, polyester fiber cloth, and nylon fiber cloth by a bar coater so that the film thickness was 0.2mm in a die of plain weave cotton cloth at 2cm×10 cm. It was dried with a tenter at 140℃for 5 minutes, thereby obtaining a printed fiber cloth. Using the obtained fiber cloth, a dry test and a wet test were carried out in accordance with the method prescribed in JIS L0849 (type II), and the contamination of the fiber cloth for friction was evaluated based on the gray scale for contamination (1 to 5 grade). "5" is the least color transfer, and "1" is the most severe color transfer.
[2] Storage stability of paste (V) for printing
30g of the prepared paste (V) for printing was placed in a screw vial [50mL (diameter of the vial: 35 mm. Times. Height: 78 mm) ] and stored at 50℃for 14 days. The viscosity change rate was calculated from the measurement results of the viscosity before and after storage according to the following formula, and the storage stability was evaluated according to the following criteria.
The viscosity was measured using a type B viscometer at a constant temperature of 25 ℃.
(viscosity change rate) (%) = { (absolute value of viscosity after storage-viscosity before storage } ×100/(viscosity before storage)
< evaluation criterion >
O: the viscosity change rate is less than 10 percent
X: the change rate of viscosity is more than 10 percent
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From the results in tables 13 and 14, it is clear that the paste for printing containing the aqueous polyurethane dispersion (Q) of the example was excellent in adhesion (friction fastness) to various kinds of substrates (particularly polypropylene substrates) and also excellent in storage stability. On the other hand, it was found that the printing pastes of comparative examples 21 to 23 were poor in adhesion to polypropylene substrates and also poor in storage stability. Further, it was found that the paste for printing (comparative example 24) produced using the polyol containing the polyester polyol having the structural unit represented by the general formula (1) was poor in storage stability.
< evaluation of electrodes for nonaqueous electrolyte secondary batteries of examples 133 to 154 and comparative examples 25 to 28 >
[1] Electrolyte swelling test (evaluation of swelling resistance)
The aqueous polyurethane dispersions (Q-1) to (Q-22) and (Q-1) to (Q-4) obtained in examples 1 to 22 or comparative examples 1 to 4, respectively, were used, and the nonaqueous electrolyte secondary battery electrode binders (L-1) to (L-22) and (L-1) to (L-1) each contained the aqueous polyurethane dispersions (Q-1) to (Q-22) and (Q-1) to (Q-4) in amounts such that the film thickness after drying reached 200 μm, respectively, were cast into polypropylene molds having a length of 10cm X a width of 20cm X a depth of 1 cm. After drying at room temperature for 12 hours, the film thus obtained was cut into 2cm×8cm pieces by a circulation dryer and dried by heating at 105 ℃ for 3 hours, and the weight (W0) was measured by an electronic balance capable of measuring 4 bits after the decimal point. To 100 parts by weight of a mixed solvent of ethylene carbonate, dimethyl carbonate and methylethyl carbonate (volume ratio 3:3:2), 3 parts by weight of ethylene carbonate was added, and further lithium hexafluorophosphate was dissolved so as to have a concentration of 1mol/L, and the test piece was immersed in the dissolved electrolyte at 50℃for 24 hours. The weight (W1) of the test piece after the impregnation with the electrolyte was measured, and the increase was determined by the following formula, and evaluated as an electrolyte expansion rate (%) according to the following criteria.
Electrolyte expansion ratio (%) = [ (W1) - (W0) ]×100/(W0)
W0: weight of test piece before electrolyte impregnation
W1: weight of test piece after electrolyte impregnation
Evaluation criterion
And (3) the following materials: the expansion rate of the electrolyte is less than 10%.
O: the expansion rate of the electrolyte is more than 10% and less than 15%.
Delta: the expansion rate of the electrolyte is more than 15% and less than 25%.
X: the expansion rate of the electrolyte is more than 25%.
[2] Peeling test (evaluation of adhesion)
< preparation of Positive electrode for evaluation of adhesion >
The aqueous polyurethane dispersions (Q-1) to (Q-22) and (ratio Q-1) to (ratio Q-4) were diluted with ion-exchanged water to a solid content concentration of 24% by weight, respectively, to prepare dispersions, and 20.8 parts by weight of each of the obtained nonaqueous electrolyte secondary battery electrode binders (L-1) to (L-22) and (ratio L-1) to (ratio L-4) were prepared by mixing, 90.0 parts by weight of lithium cobaltate [ trade name "Cellseed C", manufactured by Japanese chemical Co., ltd.) as a positive electrode active material, and acetylene BLACK [ "DENKA BLACK", manufactured by Denka Co., ltd.) as a conductive aid. The following is the same. 5.0 parts by weight of water and 25 parts by weight of ion-exchanged water were mixed and kneaded for 5 minutes by a kneader (a da from Thinky corporation) to prepare a slurry for positive electrode. The slurry was applied to one surface of an aluminum electrolytic foil having a thickness of 20 μm by a film applicator so that the thickness after drying was about 10 μm, and after drying at 80℃for 1 hour, the film was dried at 80℃for 2 hours under reduced pressure (1.3 kPa) to obtain a test piece of a positive electrode having a film thickness of 30 μm, in which an active material layer was formed on the aluminum electrolytic foil.
< preparation of negative electrode for evaluation of adhesion >
The above polyurethane aqueous dispersions (Q-1) to (Q-22) and (ratio Q-1) to (ratio Q-4) were diluted with ion-exchanged water to a solid content concentration of 24% by weight, respectively, to prepare dispersions, 31.3 parts by weight of each of the obtained nonaqueous electrolyte secondary battery electrode binders (L-1) to (L-22) and (ratio L-1) to (ratio L-4), 92.5 parts by weight of graphite powder [ trade names "CGC-20", nippon Graphite Industries, ltd. Product ] as a negative electrode active material, and 25 parts by weight of ion-exchanged water were mixed, and thereafter, a negative electrode slurry was prepared in the same manner as the above positive electrode. The slurry was applied to one surface of a copper foil having a thickness of 20 μm by a film applicator so that the thickness after drying was about 10 μm, and after drying at 80℃for 1 hour, the film was dried at 80℃for 2 hours under reduced pressure (1.3 kPa) to obtain a test piece of a negative electrode having a film thickness of 30 μm and having an active material layer formed on the copper foil.
< peel test (evaluation of adhesion) >
The positive electrode and the negative electrode of the obtained secondary battery were cut into a shape of 20mm in the longitudinal direction and 20mm in the transverse direction, and slits were cut every 1mm by a cutter to prepare a 100-cell checkerboard. The cellophane tape (registered trademark) was attached to the checkerboard, and the tape was peeled off at a time, whereby the number of non-peeled off pieces in 100 pieces was evaluated according to the following criteria.
< evaluation criterion >
And (3) the following materials: the number of non-peeled square checks is 98-100
O: the number of non-peeled square checks is 90 to 98
X: the number of non-peeled square pieces is less than 90
[3] Evaluation of high-Voltage charge-discharge cycle characteristics
< preparation of lithium ion Battery for evaluation of high-Voltage Charge-discharge cycle characteristics of Positive electrode >
For the positive electrode, a part of the positive electrode test piece produced for evaluating the adhesion was die-cut into piecesBut is used. For the negative electrode, 92.5 parts by weight of graphite powder, 7.5 parts by weight of polyvinylidene fluoride (SIGMA-ALDRICH Co., ltd.) and 1-methyl-2-pyrrolidone (Tokyo chemical industry Co., ltd.)]200 parts by weight ofAfter the slurry was sufficiently mixed in a mortar to obtain a slurry, the obtained slurry was applied to one surface of a copper foil having a thickness of 20 μm with a wire rod in the atmosphere, dried at 80℃for 1 hour, dried at 80℃for 2 hours under reduced pressure (1.3 kPa), and punched and cut into pieces>And is manufactured.
The positive electrode and the negative electrode were disposed at both ends in a 2032 button cell with the coated surfaces facing each other, and a separator (polypropylene nonwoven fabric) was interposed between the electrodes to prepare a cell for a lithium ion battery. LiPF as an electrolyte was dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 1:1) so as to reach 12 wt% based on the weight of the mixed solvent 6 And (5) preparing an electrolyte. And (3) injecting and sealing the prepared electrolyte into the battery cell to prepare the lithium ion battery for evaluating the high-voltage charge-discharge cycle characteristics of the positive electrode.
< preparation of lithium ion Battery for evaluation of high-Voltage charge-discharge cycle characteristics of negative electrode >
For the positive electrode, 90.0 parts by weight of lithium cobaltate, 5 parts by weight of acetylene black and 5 parts by weight of polyvinylidene fluoride were thoroughly mixed in a mortar, then 70.0 parts by weight of 1-methyl-2-pyrrolidone was added, and further thoroughly mixed in the mortar to obtain a slurry, the obtained slurry was applied to one surface of an aluminum electrolytic foil having a thickness of 20 μm with a wire rod in the atmosphere, dried at 80℃for 1 hour, and further dried at 80℃for 2 hours under reduced pressure (1.3 kPa), and die-cut to obtain a productAnd is manufactured. For the negative electrode, a part of the negative electrode test piece produced in the adhesion evaluation was punched out to +.>But is used. Lithium ion battery for evaluating high-voltage charge-discharge cycle characteristics of negative electrode was produced in the same manner as in the production of lithium ion battery for evaluating high-voltage charge-discharge cycle characteristics of positive electrode except that the positive electrode and negative electrode were used。
< evaluation of high-Voltage charge-discharge cycle characteristics >
The lithium ion battery fabricated as described above was charged to a voltage of 4.5V at a current of 0.1C in a constant temperature bath at 25 ℃ using a charge/discharge measuring device "battery analyzer 1470 type" (manufactured by TOYO Corporation), and after stopping for 10 minutes, the battery was discharged to a battery voltage of 3.5V at a current of 0.1C, and the charge/discharge was repeated. The battery capacity at the time of initial charge and the battery capacity at the time of 100 th cycle charge at this time were measured, and the high-voltage charge-discharge cycle characteristics were calculated from the following equation. The high-voltage charge-discharge cycle characteristics were evaluated according to the following criteria.
High voltage charge-discharge cycle characteristic (%) = (battery capacity at 100 th cycle charge/battery capacity at initial charge) ×100
Evaluation criterion
And (3) the following materials: the high-voltage charge-discharge cycle characteristic (%) is 95% or more.
O: the high-voltage charge-discharge cycle characteristic (%) is 90% or more and less than 95%.
Delta: the high-voltage charge-discharge cycle characteristic (%) is 85% or more and less than 90%.
X: the high-voltage charge-discharge cycle characteristic (%) is less than 85%.
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As is clear from the results of tables 15 and 16, when the aqueous polyurethane dispersion (Q) of the example was used, the aqueous polyurethane dispersion (Q) was superior in (1) resistance to swelling with an electrolyte and (2) adhesion between each active material of the positive and negative electrodes and each metal current collector of each electrode, as compared with the comparative example. Further, when the aqueous polyurethane dispersion (Q) of example was used, it was found that (3) a secondary battery having an electrode formed using the nonaqueous electrolyte secondary battery electrode binder was also excellent in high-voltage charge-discharge cycle characteristics as compared with comparative example.
Industrial applicability
The aqueous polyurethane dispersion of the present invention can be suitably used for an inkjet ink composition, an aqueous printing ink composition such as a gravure ink, an aqueous coating composition, a paste for printing, and a nonaqueous electrolyte secondary battery electrode binder; an electrode for a nonaqueous electrolyte secondary battery formed using the above-described nonaqueous electrolyte secondary battery electrode binder; the nonaqueous electrolyte secondary battery having the electrode for nonaqueous electrolyte secondary battery.

Claims (10)

1. An aqueous polyurethane dispersion comprising water and a polyurethane resin (U), wherein the polyurethane resin (U) is obtained by reacting an active hydrogen group-containing compound component (W) with an isocyanate component (B), the active hydrogen group-containing compound component (W) comprises a polymer polyol (A), the polymer polyol (A) is a polyol which comprises a hydroxyl group-containing polyolefin (A1) and does not comprise a polyester polyol (RA) having a structural unit represented by the following general formula (1), the weight ratio of ethylene to an alpha-olefin having 3 to 8 carbon atoms, namely ethylene/alpha-olefin, of the hydroxyl group-containing polyolefin (A1) is 5/95 to 40/60, the isotacticity of the alpha-olefin portion of the hydroxyl group-containing polyolefin (A1) is 1 to 50%,
[ chemical 1]
2. The aqueous polyurethane dispersion according to claim 1, wherein the hydroxyl group-containing polyolefin (A1) has a hydroxyl value of 12mgKOH/g to 120mgKOH/g.
3. An inkjet ink composition comprising the aqueous polyurethane dispersion according to claim 1 or 2.
4. An aqueous printing ink composition comprising the aqueous polyurethane dispersion according to claim 1 or 2.
5. An aqueous coating composition comprising the aqueous polyurethane dispersion according to claim 1 or 2.
6. The aqueous coating composition according to claim 5, further comprising at least 1 crosslinking agent selected from the group consisting of melamine resins, blocked isocyanates and epoxy compounds.
7. A paste for printing comprising the aqueous polyurethane dispersion according to claim 1 or 2.
8. A nonaqueous electrolyte secondary battery electrode binder comprising the aqueous polyurethane dispersion according to claim 1 or 2.
9. An electrode for a nonaqueous electrolyte secondary battery, which is formed using an active material, a metal collector, and the nonaqueous electrolyte secondary battery electrode binder according to claim 8.
10. A nonaqueous electrolyte secondary battery comprising an electrolyte, a separator, and the electrode for nonaqueous electrolyte secondary batteries according to claim 9.
CN202080077839.9A 2019-11-12 2020-11-12 Polyurethane aqueous dispersion, inkjet ink composition, aqueous printing ink composition, and aqueous coating composition Active CN114698377B (en)

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JPH0782424A (en) * 1993-09-16 1995-03-28 Ube Rekisen Kk Master batch composition
JPH10110024A (en) * 1996-10-08 1998-04-28 Nippon Polyurethane Ind Co Ltd Water-dispersible polyurethane resin composition, and adhesive and coating material prepared by using the same
JP2002241691A (en) * 2001-02-21 2002-08-28 Sanyo Chem Ind Ltd Coating agent for polyolefin
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JP2006274048A (en) * 2005-03-29 2006-10-12 Sanyo Chem Ind Ltd Binder for printing ink, and printing ink composition

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JPH0753856B2 (en) * 1992-03-11 1995-06-07 保土谷化学工業株式会社 Method for adhering polyolefin material with aqueous polyurethane resin
JP6965329B2 (en) * 2018-12-19 2021-11-10 三洋化成工業株式会社 Polyurethane resin aqueous dispersion and printing ink using it

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JPH0782424A (en) * 1993-09-16 1995-03-28 Ube Rekisen Kk Master batch composition
JPH10110024A (en) * 1996-10-08 1998-04-28 Nippon Polyurethane Ind Co Ltd Water-dispersible polyurethane resin composition, and adhesive and coating material prepared by using the same
JP2002241691A (en) * 2001-02-21 2002-08-28 Sanyo Chem Ind Ltd Coating agent for polyolefin
CN1791634A (en) * 2003-05-22 2006-06-21 尤尼吉可株式会社 Aqueous polyolefin resin dispersion, process for producing the same, and water-based coating material comprising the same
JP2006274048A (en) * 2005-03-29 2006-10-12 Sanyo Chem Ind Ltd Binder for printing ink, and printing ink composition

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