CN118373963A - Blocked polyisocyanate composition, blocked polyisocyanate composition aqueous dispersion, water-based coating composition, and coating film - Google Patents
Blocked polyisocyanate composition, blocked polyisocyanate composition aqueous dispersion, water-based coating composition, and coating film Download PDFInfo
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- CN118373963A CN118373963A CN202410089931.7A CN202410089931A CN118373963A CN 118373963 A CN118373963 A CN 118373963A CN 202410089931 A CN202410089931 A CN 202410089931A CN 118373963 A CN118373963 A CN 118373963A
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- bpi
- blocked polyisocyanate
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
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- HXSACZWWBYWLIS-UHFFFAOYSA-N oxadiazine-4,5,6-trione Chemical group O=C1ON=NC(=O)C1=O HXSACZWWBYWLIS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- 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
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D175/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a blocked polyisocyanate composition, an aqueous blocked polyisocyanate composition dispersion, an aqueous coating composition and a coating film. A blocked polyisocyanate composition containing a component (A), a component (B), a component (C), a component (D) and a component (E) and satisfying the following conditions (1) to (3). (1) The mass ratio ((A)/(B)) of the structural unit derived from the component (A) to the structural unit derived from the component (B) is 60/40 or more and 90/10 or less. (2) The content of the structural unit derived from the component (C) is 0.1 mass% or more and 10 mass% or less relative to the total mass of the blocked polyisocyanate composition. (3) The content of the component (D) is 0.05 mass% or more and 6.5 mass% or less relative to the total mass of the blocked polyisocyanate composition.
Description
Technical Field
The present invention relates to a blocked polyisocyanate composition, an aqueous blocked polyisocyanate composition dispersion, an aqueous coating composition, and a coating film.
Background
Two-component polyurethane coating compositions using a polyisocyanate composition derived from an aliphatic diisocyanate as a curing agent have been used in a wide variety of fields such as coating materials, inks, adhesives, and adhesives, because they exhibit excellent properties in terms of chemical resistance, flexibility, weather resistance, and the like. Further, the composition is used in various fields such as construction, heavy corrosion protection, automobiles, industrial applications, and repair thereof in a two-component type or a one-component type form that is curable at normal temperature depending on the use conditions.
In recent years, from the viewpoint of reducing global environmental load, it has been desired to increase the water content of a polyisocyanate used as a curing agent in a urethane coating composition which has been conventionally used in the form of a solvent-based coating.
However, since urethane coating compositions are difficult to disperse in water, development of polyisocyanate compositions having hydrophilic groups is underway (for example, see patent document 1, patent document 2, and the like).
Among them, the curing agent for heat-curing the one-component coating composition has the following advantages: the isocyanate groups are protected with a blocking agent, and if necessary, the isocyanate groups are regenerated by heat treatment, and the reaction with the hydroxyl groups of the polyol as the main agent is performed to rapidly cure the isocyanate groups, thereby obtaining a coating film. From the viewpoint of environmental protection, it is highly desired to make the heat-curable one-component type aqueous.
One of the methods for making the blocked polyisocyanate aqueous is to add at least 1 ionic hydrophilic group selected from the group consisting of nonionic and cationic groups to the blocked polyisocyanate (for example, refer to patent document 3).
Patent document 3 discloses: the blocked polyisocyanate having a cationic group introduced therein can be cured at a low temperature when blended into a coating material.
Further, it is disclosed that a coating film using a blocked polyisocyanate having a nonionic hydrophilic group is excellent in curability and water resistance (see patent document 4, patent document 5, etc.).
Prior art literature
Patent literature
Patent document 1: international publication No. 01/88006
Patent document 2: international publication No. 2016/104485
Patent document 3: japanese patent No. 5344875
Patent document 4: japanese patent laid-open publication No. 2011-231264
Patent document 5: japanese patent laid-open No. 2020-143231
Disclosure of Invention
Problems to be solved by the invention
However, the blocked polyisocyanate using a cationic hydrophilic group disclosed in patent document 3 has insufficient dispersibility and curability in water, and there is room for improvement. In addition, the water resistance and compatibility with the aqueous base agent at the time of producing a coating film have not been verified.
In addition, the compatibility between the blocked polyisocyanate and the main agent and the dispersibility in water described in patent documents 4 and 5 using a nonionic hydrophilic group have room for improvement, and the adhesion to a coated substrate and the storage stability have not been verified.
The purpose of the present invention is to provide a blocked polyisocyanate composition which can be easily dispersed in water, has excellent compatibility with a polyol main agent, has excellent storage stability of a curing agent itself, is easily adhered to a coated substrate, and has excellent curability and water resistance when a coating film is produced, and to provide an aqueous blocked polyisocyanate composition dispersion, an aqueous coating composition and a coating film using the blocked polyisocyanate composition.
Solution for solving the problem
That is, the present invention includes the following means.
[1] A blocked polyisocyanate composition which contains the following components (A), (B), (C), (D) and (E) and satisfies the following conditions (1) to (3).
(A) The components are as follows: polyisocyanates derived from aliphatic diisocyanates.
(B) The components are as follows: nonionic hydrophilic compounds containing active hydrogen groups.
(C) The components are as follows: difunctional or higher polyether polyols.
(D) The components are as follows: monohydric alcohols obtained by polymerizing alkylene oxides having 3 or more carbon atoms.
(E) The components are as follows: pyrazole compounds.
(1) The mass ratio ((A)/(B)) of the structural unit derived from the component (A) to the structural unit derived from the component (B) is 60/40 or more and 90/10 or less.
(2) The content of the structural unit derived from the component (C) is 0.1 mass% or more and 10 mass% or less relative to the total mass of the blocked polyisocyanate composition.
(3) The content of the component (D) is 0.05 mass% or more and 6.5 mass% or less relative to the total mass of the blocked polyisocyanate composition.
[2] The blocked polyisocyanate composition according to [1], wherein the component (B) has 5 to 20 alkylene oxide repeating units.
[3] The blocked polyisocyanate composition according to [1] or [2], wherein the number average molecular weight of the component (C) is 300 to 3000.
[4] The blocked polyisocyanate composition according to any one of [1] to [3], wherein the number average molecular weight of the component (D) is 300 to 2000.
[5] The blocked polyisocyanate composition according to any one of [1] to [4], wherein the content of the component (D) is less than 1% by mass relative to the total mass of the blocked polyisocyanate composition.
[6] An aqueous blocked polyisocyanate composition dispersion comprising the blocked polyisocyanate composition of any one of [1] to [5] and ion-exchanged water, wherein the proportion of the ion-exchanged water in the entire blocked polyisocyanate composition aqueous dispersion is 50% by mass or more and 90% by mass or less.
[7] A water-based coating composition comprising the blocked polyisocyanate composition according to any one of [1] to [5 ].
[8] A coating film obtained by curing the aqueous coating composition according to [7 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a blocked polyisocyanate composition which can be easily dispersed in water, has excellent compatibility with a polyol main agent, has excellent storage stability of a curing agent itself, is easily adhered to a coated substrate, and has excellent curability and water resistance when a coating film is produced, an aqueous blocked polyisocyanate composition dispersion, an aqueous coating composition, and a coating film each using the blocked polyisocyanate composition.
Detailed Description
The mode for carrying out the present invention (hereinafter also referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following embodiments. The present invention can be implemented by appropriately modifying the scope of the gist thereof.
In the present specification, "polyol" means a compound having 2 or more hydroxyl groups (-OH).
In the present specification, the term "polyisocyanate" refers to a reaction product formed by bonding a plurality of monomer compounds (monomers) having 1 or more isocyanate groups (-NCO).
< Blocked polyisocyanate composition >
The blocked polyisocyanate composition of the present embodiment contains the following component (A), component (B), component (C), component (D), and component (E).
(A) The components are as follows: polyisocyanates derived from aliphatic diisocyanates.
(B) The components are as follows: nonionic hydrophilic compounds containing active hydrogen groups.
(C) The components are as follows: difunctional or higher polyether polyols.
(D) The components are as follows: monohydric alcohols obtained by polymerizing alkylene oxides having 3 or more carbon atoms.
(E) The components are as follows: pyrazole compounds.
Hereinafter, the "blocked polyisocyanate composition" is sometimes simply referred to as "BPI composition".
When the numerical range is described as "1 to 10 mass%" or "1 to 10 mass%", for example, a range of 1 to 10 mass% is indicated, and a numerical range including a lower limit value, i.e., 1 mass%, and an upper limit value, i.e., 10 mass%.
The BPI composition of the present embodiment satisfies the following (1) to (3).
(1) The mass ratio ((A)/(B)) of the structural unit derived from the component (A) to the structural unit derived from the component (B) is 60/40 to 90/10.
(2) The content of the structural unit derived from the component (C) is 0.1 to 10% by mass relative to the total mass of the BPI composition.
(3) The content of the component (D) is 0.05 to 6.5% relative to the total mass of the BPI composition.
Regarding (1), (A)/(B) is 60/40 or more, preferably 63/37 or more, more preferably 65/35 or more. On the other hand, (A)/(B) is 90/10 or less, preferably 85/15 or less, more preferably 80/20 or less.
The upper limit and the lower limit may be arbitrarily combined.
As examples of combinations, 60/40-90/10, 63/37-85/15, 65/35-80/20.
When (a)/(B) is within the above range, a BPI composition that can be easily dispersed in water, has excellent compatibility with a main agent, and has excellent curability and water resistance when a coating film is formed can be provided.
(A) The value/(B) can be calculated by 1 H-NMR measurement.
As a specific assay, a CDCl 3 solution (deuterated chloroform) of the BPI composition is first prepared.
Next, the resulting solution was subjected to 1 H-NMR measurement under the following measurement conditions, and methylene groups derived from the component (A), methylene groups derived from the component (B) and methyl groups derived from the component (B) were confirmed.
Characteristic peaks (chemical shift values) of each composition are: the methylene group derived from the component (A) was in the vicinity of 1.4ppm, the methylene group derived from the component (B) was in the vicinity of 3.5ppm, and the methyl group derived from the component (B) was in the vicinity of 3.4 ppm.
When 1 H-NMR of methylene derived from component (A) is represented by x, 1 H-NMR of methylene derived from component (B) is represented by y, and 1 H-NMR of methyl derived from component (B) is represented by z, the following formula can be used to calculate (A)/(B).
(A)/(B)＝[(x×168)/4]/[(y×44)/4+(z×76)/3]
Regarding (2), the content of the structural unit derived from the component (C) is 0.1 to 10% by mass, preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass, relative to the total mass of the BPI composition.
When the content of the structural unit derived from the component (C) is within the above range, the curing property tends to be good when a coating film is formed.
The content of the structural unit derived from component (C) can be measured by the method described in examples described later.
The content of the component (3) (D) is preferably less than 1% by mass, preferably 0.99% by mass or less, more preferably 0.95% by mass or less, still more preferably 0.9% by mass or less, and particularly preferably 0.88% by mass or less, based on the total mass of the BPI composition.
The content of the component (3) (D) is, for example, 0.05 mass% or more, 0.10 mass% or more, 0.15 mass% or more, 0.2 mass% or more, or 0.25 mass% or more, relative to the total mass of the BPI composition.
The upper limit and the lower limit may be arbitrarily combined.
As an example of the combination, the content of the component (D) is 0.05 mass% or more and less than 1 mass%, 0.10 to 0.99 mass%, 0.15 to 0.95 mass%, 0.2 to 0.9 mass%, 0.25 to 0.88 mass% with respect to the total mass of the BPI composition.
(D) When the content of the component (A) is within the above range, compatibility with the main agent tends to be good.
(D) The content of the component (c) can be measured by the method described in examples described later.
Details of the constituent components of the BPI composition of this embodiment are described below.
Component (A)
(A) The component (a) is a polyisocyanate derived from an aliphatic diisocyanate.
The aliphatic diisocyanate is not limited to the following examples, and examples thereof include 1, 4-diisocyanatobutane, 1, 5-diisocyanato pentane, ethyl (2, 6-diisocyanato) caproate, HDI, 1, 9-diisocyanato nonane, 1, 12-diisocyanato dodecane, 2, 4-or 2, 4-trimethyl-1, 6-diisocyanatohexane, and the like.
These aliphatic diisocyanates may be used singly or in combination of two or more. Among them, HDI is preferable from the viewpoints of weather resistance and industrial availability. The aliphatic diisocyanate may be used alone or in combination of two or more.
Examples of the polyisocyanate derived from an aliphatic diisocyanate include, but are not limited to, a polyisocyanate having a uretdione structure obtained by cyclizing and dimerizing 2 isocyanate groups, a polyisocyanate having an isocyanurate structure obtained by cyclizing and trimerizing 3 isocyanate groups, a polyisocyanate having an iminooxadiazinedione structure obtained by cyclizing and trimerizing 3 isocyanate groups, a polyisocyanate having a biuret structure obtained by reacting 3 isocyanate groups with 1 water molecule, a polyisocyanate having an oxadiazinetrione structure obtained by reacting 2 isocyanate groups with 1 molecule of carbon dioxide, a polyisocyanate having a urethane structure obtained by reacting 1 isocyanate group with 1 hydroxyl group, a polyisocyanate having an allophanate structure obtained by reacting 2 isocyanate groups with 1 hydroxyl group, a polyisocyanate having an acylurea structure obtained by reacting 1 isocyanate group with 1 carboxyl group, a polyisocyanate having an urea structure obtained by reacting 1 isocyanate group with 1 primary amine or secondary amine, and the like. These polyisocyanates may be used singly or in combination of two or more.
The term "polyisocyanate" as used herein includes, in addition to the polyisocyanate derived from only the aliphatic diisocyanate, the polyisocyanate obtained by reacting the aliphatic diisocyanate with a compound other than the diisocyanate (for example, an alcohol such as a monohydric alcohol, water, or an amine).
The isocyanate component other than the component (a) may contain a polyisocyanate derived from an aliphatic diisocyanate or an aliphatic triisocyanate.
Examples of the alicyclic diisocyanate include 1, 3-or 1, 4-bis (isocyanatomethyl) cyclohexane (hereinafter, sometimes simply referred to as "hydrogenated XDI"), 1, 3-or 1, 4-diisocyanatocyclohexane, 3, 5-trimethyl 1-isocyanato-3- (isocyanatomethyl) cyclohexane (hereinafter, sometimes simply referred to as "IPDI"), 4-4' -diisocyanato-dicyclohexylmethane (hereinafter, sometimes simply referred to as "hydrogenated MDI"), and 2, 5-or 2, 6-diisocyanatomethyl norbornane. These alicyclic diisocyanates may be used singly or in combination of two or more.
Examples of aliphatic triisocyanates include 1,3, 6-triisocyanatohexane, 1, 8-diisocyanato-4-isocyanatomethyloctane, 2-isocyanatoethyl-2, 6-diisocyanato-caproate, and the like. These aliphatic triisocyanates may be used singly or in combination of two or more.
Component (B)
(B) The component (C) is a nonionic hydrophilic compound containing active hydrogen groups. Examples of the component (B) include poly (oxyalkylene) monoalkyl ether. Among them, from the viewpoint of reducing the viscosity of the blocked polyisocyanate composition, the poly (oxyalkylene) monoalkyl ether is preferably a compound represented by the following general formula (I) (hereinafter, sometimes referred to as "compound (I)").
HO-(R11O)n11-R12···(I)
In the general formula (I), R 11 is an alkylene group having 1 to 4 carbon atoms, and R 12 is an alkyl group having 1 to 4 carbon atoms.
The polyalkylene glycol alkyl ether is not a single component, but an aggregate of substances having different values of n11 (hereinafter, sometimes referred to as "polymerization degree n11" or simply "n 11") indicating the polymerization degree of alkylene oxide. Therefore, in the general formula (I), the polymerization degree n11 of the alkylene oxide is shown as its average (average value). The average number of n11 is preferably 5 to 20.
In the general formula (I) of R 11, R 11 is an alkylene group having 1 to 4 carbon atoms, and from the viewpoint of imparting hydrophilicity, an alkylene group having 2 carbon atoms, that is, an ethylene group is preferable.
In the general formula (I) of R 12, R 12 is an alkyl group having 1 to 4 carbon atoms, and from the viewpoint of imparting hydrophilicity, an alkyl group having 1 carbon atoms, i.e., a methyl group is preferable.
·n11
The average number of n11 is preferably 5.0 or more, more preferably 5.2 or more, further preferably 5.4 or more, and particularly preferably 6.0 or more from the viewpoints of water dispersibility, water dispersion stability, and appearance of a coating film.
On the other hand, the average number of n11 is preferably 30 or less, more preferably 26 or less, still more preferably 23 or less, still more preferably 20 or less, and still more preferably 18 or less, from the viewpoint of the coating film hardness.
(B) The component preferably has 5 to 30 alkylene oxide repeating units. That is, the average number of n11 is preferably 5.0 to 30, more preferably 5.2 to 26, further preferably 5.4 to 23, further preferably 6.0 to 20, particularly preferably 6.0 to 18. When the average number of n11 is equal to or greater than the lower limit, the emulsifying power is further increased, so that the dispersibility is further improved, and the dispersion can be more easily performed. Therefore, dispersibility in the base agent is further improved, and the appearance of the coating film tends to be more excellent. On the other hand, when the average number of n11 is equal to or less than the upper limit, excessive viscosity increase such as gelation can be further prevented, and dispersion tends to be easier. Further, the hardness of the coating film tends to be more excellent.
Examples of commercial products of the poly (oxyalkylene) alkyl ether include: trade names "UNIOX M400", "UNIOX M550", "UNIOX M1000", "UNIOX M2000" manufactured by japan oil and fat corporation; trade names "MPG-081", "MPG-130", "TN-555", etc. manufactured by Japanese emulsifier Co.
(B) The amount of the poly (oxyalkylene) monoalkyl ether introduced into the composition can be calculated, for example, by the following method.
Specifically, the BPI composition of this embodiment was obtained from the peak area ratio of the unincorporated polyisocyanate, the polyisocyanate into which 1 monofunctional polyoxyalkylene polyether alcohol was introduced, the polyisocyanate into which 2 monofunctional polyoxyalkylene polyether alcohols were introduced, and the polyisocyanate into which 3 or more monofunctional polyoxyalkylene polyether alcohols were introduced at 220nm by Liquid Chromatography (LC) as a sample. The LC-based measurement conditions include, for example, the following conditions.
(Measurement conditions)
LC device: UPLC (trade name) manufactured by Waters corporation
Column: manufactured by Waters Co., ltd ACQUITY UPLC HSS T, 3.8 μm
C18 inner diameter 2.1mm x length 50mm
Flow rate: 0.3mL/min
Mobile phase: a=10 mM aqueous ammonium acetate solution, b=acetonitrile
Gradient conditions: the initial mobile phase composition was a/b=98/2, and the ratio of B was linearly increased after sample injection to a/b=0/100 after 10 minutes.
The detection method comprises the following steps: LED array detector with measuring wavelength of 220nm
The BPI composition has good water dispersibility by introducing a hydrophilic group (polyalkylene oxide unit) derived from a poly (oxyalkylene) monoalkyl ether into the component (B).
In the present specification, "water dispersibility" means a property that a BPI composition can be O/W type and dispersed in water. The water dispersibility can be evaluated by, for example, adding the BPI composition to water and mechanically stirring the mixture using a rod, a hand mixer, or the like to confirm whether the composition is dispersed in water, as shown in examples described later. The term "O/W type" as used herein refers to an oil-in-water emulsion in which water is used as a continuous phase.
Component (C)
(C) The component (C) is a polyether polyol having a difunctional or higher functionality. The difunctional or higher polyether polyol is not particularly limited, and examples thereof include: a difunctional polyether polyol obtained by subjecting an alkylene oxide alone or a mixture thereof and a dihydric hydroxyl compound alone or a mixture thereof to addition polymerization of at least 1 selected from the group consisting of random addition and end-capping addition using a catalyst; difunctional polyether polyols obtained by reacting alkylene oxides with diamine compounds; and so-called difunctional polymer polyols obtained by polymerizing acrylamide or the like using these difunctional polyether polyols as a medium.
Examples of the catalyst include alkali metal hydroxides, strong base catalysts, complex metal cyanide compounds, and the like. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the strong basic catalyst include alkoxides and alkylamines. Examples of the complex metal cyanide compound complex include metalloporphyrin and zinc hexacyanocobaltate complex.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide. Examples of the diamine compound include ethylenediamine.
(C) The number average molecular weight of the component is preferably 300 to 3000, more preferably 350 to 2500, still more preferably 400 to 2000. When the number average molecular weight of the component (C) is in the above range, flexibility and handleability tend to be more excellent. The number average molecular weight can be measured by the method described in examples described below.
Component (D)
(D) The component (C) is a monohydric alcohol obtained by polymerizing an alkylene oxide having 3 or more carbon atoms. (D) The components are derived from a starting monohydric alcohol and an alkylene oxide having 3 or more carbon atoms. The carbon number of the starting monohydric alcohol is1 to 10, preferably 2 to 8, and more preferably 4 to 8. These specific monohydric alcohols include alcohols such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, and the like.
The alkylene oxide having 3 or more carbon atoms includes, for example, ethylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, etc., and propylene oxide is preferable.
For example, these alkylene oxides are obtained by adding the above-mentioned starting monohydric alcohol alone or in combination with a strong basic catalyst such as a hydroxide, alkoxide, or alkylamine of lithium, sodium, or potassium, a complex metal cyanide complex such as metalloporphyrin, or zinc hexacyanocobaltate complex, or the like.
(D) The number average molecular weight of the component (A) is preferably 300 to 2000, more preferably 300 to 1500, still more preferably 350 to 1000.
(D) When the number average molecular weight of the component (a) is less than 300, the compatibility of the obtained BPI composition with the polyol may be reduced, and when the number average molecular weight exceeds 2000, the hardness of the coating film may be reduced.
The aqueous blocked polyisocyanate having a highly polar bond to which the component (D) is added has excellent compatibility with a polyol. The hydrophilic group of the aqueous blocked polyisocyanate and the bond formed by the isocyanate group and the blocking agent inhibit compatibility with the polyol.
(D) The molecular weight of the component is large and oxygen is present in the repeating units of the molecular chain. This is thought to make the (D) component accessible to the portion of the aqueous blocked polyisocyanate where the compatibility is low, improving the compatibility with the polyol as a whole.
Examples of the commercial products of monohydric alcohols obtained by polymerizing alkylene oxides having 3 or more carbon atoms include trade names "LEOCON 1015H" of lion Wang Teshu chemical Co., ltd., trade names "LEOCON SX1050" and "LEOCON SX1060" of AGC Co., ltd., trade names "BLAUNON P-101M" and "BLAUNON P-171" of green wood oil industry Co., ltd.
Component (E)
(E) The component (A) is a pyrazole compound.
In the BPI composition, at least a part of the isocyanate groups of component (A) is blocked by component (E).
Examples of the pyrazole compound include pyrazole, 3-methylpyrazole, 3, 5-dimethylpyrazole, and the like. These pyrazole compounds may be used singly or in combination of two or more. Among them, 3, 5-dimethylpyrazole is preferable as the component (E) because it tends to have more excellent curability in low-temperature drying or short-time drying.
Component (F)
The BPI composition may contain component (F) as an optional component. (F) The component (C) is a mildew inhibitor, and isothiazoline compound and imidazole compound can be used.
As the isothiazoline-based compound, commercially available products are generally used, and specific commercially available products include "Biocut-TR120" from Caon, japan, and "PROXEL GXL", "PROXEL BDN" from ARCHCHEMICALS, and ""KLARIX 4000"、"ROZONE 2000"、"ROCIMA 252"、"ROCIMA 200"、"ROCIMA 345"、"ROCIMA 350"、"ROCIMA 553"、"BIOBAN 551S"、"SKANE M-8" from Dow chemical company.
The imidazole compound is particularly excellent in mold resistance. As the imidazole-based compound, commercially available products are generally used, and specific commercially available products include "Biocut-N35", "Biocut-AF40", "DX-2" from the company Caesalpinia, and "ROCIMA 363" from the company Dow.
When the BPI composition contains the component (F), the content of the component (F) is, for example, 0.01 to 10.0 parts by mass in the total amount of the BPI composition.
Process for producing BPI composition
The BPI composition is not particularly limited, and can be obtained by reacting a component (a), a component (B), a component (C), a component (D), a component (E), and optionally a component (F).
The reaction of the isocyanate group of the component (A) with the component (B), the reaction of the component (C) with the component (D) and the reaction of the isocyanate group of the component (A) with the component (D) may be carried out simultaneously, or the 2 nd reaction may be carried out after any reaction is carried out in advance.
Among them, it is preferable to carry out the reaction of the component (A) with the component (B), the component (C) and the component (D) and to carry out the reaction with the component (E) after the completion of the reaction.
The component (a) may be an aliphatic diisocyanate, or a polyisocyanate derived from an aliphatic diisocyanate in advance may be used in the reaction.
In the reaction step, an organic metal salt, a tertiary amine compound, and an alkali metal alkoxide may be used as a catalyst. Examples of the metal contained in the organometallic salt include tin, zinc, and lead. Examples of the alkali metal include sodium.
The reaction temperature in the reaction step is preferably-20 to 150℃and more preferably 30 to 100 ℃. When the reaction temperature is not less than the lower limit, the reactivity tends to be further improved. On the other hand, when the reaction temperature is not higher than the upper limit, side reactions tend to be more effectively suppressed.
[ Effective isocyanate group (NCO) content ]
The effective NCO content in the BPI composition of the present embodiment is not particularly limited, but is preferably 1 to 15% by mass, more preferably 1.5 to 10% by mass, and even more preferably 2 to 8% by mass, from the viewpoint of improving the storage stability of the BPI composition.
The effective NCO content can be calculated by the method described in examples described later.
The BPI composition may be used as a curing agent for coating compositions, particularly aqueous two-component polyurethane coating compositions.
The BPI composition can be used in curable compositions such as an adhesive composition, and a molding composition; various surface treatment agent compositions such as a fiber treatment agent; various elastomer compositions; crosslinking agents for foam compositions and the like; a modifying agent; additives, and the like.
The adhesive composition containing the BPI composition is not particularly limited, and can be used for, for example, automobiles, building materials, home appliances, woodworking products, laminates for solar cells, and the like. Among them, in order to exhibit various functions, various films and plates as adherends are required to be laminated on an optical member for use in liquid crystal displays of home appliances such as televisions, computers, digital cameras, and cellular phones. Therefore, various films and plates as adherends are required to have sufficient adhesiveness or tackiness, and the adhesive composition containing the BPI composition can be preferably used for adhesion of optical members in liquid crystal display applications of home appliances and the like.
Aqueous dispersion of blocked polyisocyanate composition
The BPI composition can be made into an aqueous dispersion dispersed in ion-exchanged water. The content of the ion-exchanged water is preferably 50 to 90% by mass, more preferably 45 to 80% by mass, and still more preferably 40 to 75% by mass, relative to the entire aqueous dispersion. When the content is less than 50% by mass, the viscosity of the isocyanate composition is too high and the handleability may be deteriorated. If the amount exceeds 90% by mass, the effective NCO% and viscosity of the isocyanate composition may be low, and blending with the base polyol may be difficult.
Water-based coating composition
The water-based coating composition of the present embodiment contains a BPI composition and 1 or more main agents. The aqueous coating composition of the present embodiment can provide a coating film having excellent compatibility between the BPI composition as a curing agent and a main agent and excellent curability, adhesion, and water resistance by having the above-described configuration.
Main agent
As the main agent used in the aqueous coating composition, an aqueous polyol is preferable. As aqueous polyols, all substances which contain hydroxyl groups in the form of latices, emulsions, dispersions, water-soluble resins are included. Specific examples of the aqueous polyol include polyvinylidene chloride copolymer, polyvinyl chloride copolymer, vinyl acetate copolymer, water-soluble acrylic resin, water-soluble polyester resin, urethane dispersion, acrylic emulsion, fluorine copolymer emulsion, styrene butadiene copolymer latex, acrylonitrile butadiene copolymer, rubber latex, polybutadiene copolymer, urethane acrylic emulsion, and copolymers or mixtures thereof.
Among them, the aqueous polyol is preferably in the form of a latex, emulsion or dispersion from the viewpoint of excellent handleability and water resistance. Among them, acrylic emulsion, fluorocopolymer emulsion, urethane dispersion, or polymers thereof are particularly preferable because they are particularly excellent in weather resistance, gloss and toughness when a coating film is formed.
When the aqueous polyols are used in the form of latices, emulsions or dispersions, the lower limit of their particle size is preferably 5nm, more preferably 10nm, still more preferably 40nm. On the other hand, the upper limit of the particle diameter is preferably 1.0. Mu.m, more preferably 500nm, and still more preferably 300nm.
That is, the particle diameter is preferably 5 to 1.0. Mu.m, more preferably 10 to 500nm, still more preferably 40 to 300nm.
When the particle diameter is in the above range, the gloss is higher and the water resistance is also more excellent when a coating film is formed. In addition, stability as a latex, emulsion or dispersion also becomes more sufficient.
The lower limit of the hydroxyl value of the aqueous polyol is preferably 1mgKOH/g, more preferably 5mgKOH/g, still more preferably 10mgKOH/g. On the other hand, the upper limit of the hydroxyl value is preferably 300mgKOH/g, more preferably 200mgKOH/g, still more preferably 150mgKOH/g.
That is, the hydroxyl value of the aqueous polyol is preferably 1 to 300mgKOH/g, more preferably 5 to 200mgKOH/g, still more preferably 10 to 150mgKOH/g.
When the hydroxyl value of the aqueous polyol is in the above range, the crosslinking point becomes more sufficient, and a softer and stronger coating film can be obtained.
In the aqueous coating composition of the present embodiment, the lower limit of the molar ratio of isocyanate groups to hydroxyl groups of the aqueous polyol (isocyanate groups/hydroxyl groups) of the BPI composition is preferably 0.3, more preferably 0.5, and still more preferably 0.6. On the other hand, the upper limit of the molar ratio is preferably 5.0, more preferably 3.0, and further preferably 2.5.
That is, the molar ratio of isocyanate groups (isocyanate groups/hydroxyl groups) of the polyisocyanate composition to hydroxyl groups of the aqueous polyol is preferably 0.3 to 5.0, more preferably 0.5 to 3.0, and still more preferably 0.6 to 2.5.
When the molar ratio (isocyanate group/hydroxyl group) is within the above range, the crosslinking point becomes more sufficient, and a coating film which is softer and stronger can be obtained.
The aqueous coating composition of the present embodiment may contain various known and customary additives for coating materials, in addition to the BPI composition and the main agent, depending on the application, the method of use, and the like. Examples of the additives for coating materials include thickeners, leveling agents, thixotropic agents, antifoaming agents, freeze stabilizers, matting agents, crosslinking reaction catalysts, antiskinning agents, dispersants, wetting agents, light stabilizers, antioxidants, ultraviolet absorbers, fillers, plasticizers, lubricants, reducing agents, preservatives, mildewcides, deodorants, anti-yellowing agents, antistatic agents, and antistatic agents. These additives can be appropriately selected and used within a range that does not interfere with the effects exerted by the water-based coating composition of the present embodiment.
Process for producing aqueous coating composition
The aqueous coating composition of the present embodiment is prepared, for example, by first adding the above-mentioned coating additive to an aqueous dispersion of a main agent or an aqueous solution thereof, if necessary. Next, the BPI composition was added as a curing agent, and water and a solvent were further added as needed. Then, the aqueous coating composition can be obtained by forcibly stirring with a stirrer.
< Usage purposes >
The aqueous coating composition of the present embodiment is not limited to the following, for example, the coating composition is suitably used as a primer, a primer for a middle paint or a top paint for a coating material to be coated formed by molding various raw materials by a coating method such as roll coating, curtain coating, spray coating, electrostatic coating or spin-cup coating. Further, the present invention is useful as a paint for imparting aesthetic properties, weather resistance, acid resistance, rust resistance, chipping resistance, and the like to precoated metals including rust-resistant steel sheets, automotive, plastic coatings, and the like. Further, the urethane raw material is useful as an adhesive, a fiber treatment, a synthetic leather treatment, an elastomer, a foam, a surface treatment agent, or the like.
As a material of a coating object to be coated of the water-based coating composition, glass; various metals such as aluminum, iron, galvanized steel sheet, copper, stainless steel, etc.; porous members such as wood, paper, mortar, stone, etc.; members subjected to fluorine coating, urethane coating, acrylic urethane, and the like; a cured silicone material, a cured modified silicone material, a cured urethane material, and the like; rubber such as vinyl chloride, natural rubber, and synthetic rubber; leather such as natural leather and artificial leather; fibers such as plant fibers, animal fibers, carbon fibers, and glass fibers; films and sheets of resins such as nonwoven fabrics, polyesters, acrylics, polycarbonates, cellulose triacetate, and polyolefins; an ultraviolet curable acrylic resin layer; a layer formed of an ink such as a printing ink or UV ink.
< Coating film >)
The coating film of the present embodiment is formed by curing the aqueous coating composition. The coating film of the present embodiment has good curability and water resistance.
The coating film of the present embodiment is obtained by applying the aqueous coating composition to an adherend and drying the adherend. The coating method may be the same as described in the application of the aqueous coating composition. The adherend may be the same as the one described in the application of the aqueous coating composition.
[ Example ]
Specific examples and comparative examples are shown below to describe the present embodiment in more detail, but the present embodiment is not limited to the following examples and comparative examples as long as the gist of the present embodiment is not exceeded. The physical properties and evaluations in examples and comparative examples were measured and evaluated as follows.
Method for measuring physical Properties
Physical Property 1
As physical properties 1, the isocyanate group (NCO) content (mass%) of the polyisocyanate was measured.
1 To 3g of polyisocyanate (Wg) were precisely weighed into a conical flask. Next, 20mL of toluene was added to the flask to dissolve the polyisocyanate. Next, 10mL of a toluene solution of 2 equivalents of di-n-butylamine was added, mixed, and then left at room temperature for 15 minutes. Next, 70mL of isopropyl alcohol was added to the flask and mixed. The liquid was added dropwise to the indicator with 1 equivalent of hydrochloric acid solution (factor F). The titration value was set to V2mL.
Then, the same operation was performed without polyisocyanate, and the titration value was set to V1mL.
Next, the NCO content of the polyisocyanate was calculated by the following formula.
NCO content (% by mass) = (V1-V2) ×f×42/(w×1000) ×100)
[ Physical Property 2] nonvolatile component
As physical property 2, the nonvolatile content of the BPI composition was measured.
The nonvolatile content of the BPI composition was determined as follows. First, an aluminum dish having a bottom diameter of 38mm was precisely weighed, and then about 1g of each blocked polyisocyanate component was placed on the aluminum dish, and precise weighing was performed in this state (W1). Then, the blocked polyisocyanate component was adjusted to a uniform thickness and then kept in an oven at 105℃for 1 hour. Next, the aluminum dish was allowed to stand at room temperature, and then the blocked polyisocyanate component (W2) remaining on the aluminum dish was precisely weighed. Next, the nonvolatile content of the blocked polyisocyanate component was calculated by the following formula.
Nonvolatile component (mass%) =w2/w1×100
[ Physical Property 3]
As physical property 3, the effective isocyanate group (NCO) content of the BPI composition was measured.
The effective NCO content of the BPI composition was determined as follows. The effective NCO content (mass%) referred to herein means: the amount of blocked isocyanate groups capable of participating in the crosslinking reaction in the blocked polyisocyanate component after the blocking reaction is quantified, and the effective NCO content is calculated from the following formula, expressed as mass% of isocyanate groups.
In the following formula, "S" represents a nonvolatile component (mass%) of the blocked polyisocyanate component. "W1" means the mass (g) of the polyisocyanate used in the reaction. "A" represents the isocyanate group content (mass%) of the polyisocyanate. "W2" means the mass (g) of the blocked polyisocyanate after the blocking reaction.
Effective NCO content (% by mass) = { S× (W1×A) }/W2
[ Physical Property 4]
As physical properties 4, the mass ratio ((a)/(B)) of the structural unit derived from the component (a) to the structural unit derived from the component (B) was measured.
The mass ratio ((A)/(B)) of the structural unit derived from the component (A) to the structural unit derived from the component (B) was calculated by 1 H-NMR measurement.
As a specific assay, a solution of CDCl 3 of the BPI composition is first prepared. Next, 1H-NMR measurement was performed on the obtained solution under the following measurement conditions, and the methylene group derived from the component (A) and the methylene group and the methyl group derived from the component (B) were confirmed.
Regarding the characteristic peaks (chemical shift values) of the respective compositions, the methylene group derived from the component (A) was around 1.4ppm, the methylene group derived from the component (B) was around 3.5ppm, and the methyl group derived from the component (B) was around 3.4 ppm. When 1 H-NMR of methylene derived from component (A) is represented by x, 1 H-NMR of methylene derived from component (B) is represented by y, and 1 H-NMR of methyl derived from component (B) is represented by z, the following formula is used to calculate (A)/(B).
(A)/(B)＝[(x×168)/4]/[(y×44)/4+(z×76)/3]
[ Physical Property 5]
As physical properties 5, the content of the structural unit derived from the component (C) was measured.
The content of the structural unit derived from the component (C) is calculated from the content of the structural unit derived from the component (A), the component (B), the component (C) and the component (D) and the compounding amount of the component (E) by the following formula. In the following formulae, (a) to (E) represent the blending amounts (g) of the respective components.
Content (mass%) of structural unit derived from (C) polyol
＝[(C)/((A)+(B)+(C)+(D)+(E))]×100
[ Physical Property 6]
As physical properties 6, the content of the structural unit derived from the component (D) was measured.
The content of the structural unit derived from the component (D) is calculated from the content of the structural units derived from the component (A), the component (B), the component (C) and the component (D), and the compounding amount of the component (E) is calculated by the following formula. In the following formulae, (a) to (E) represent the blending amounts (g) of the respective components.
Content (mass%) of structural unit derived from (D) monohydric alcohol
＝[(D)/((A)+(B)+(C)+(D)+(E))]×100
[ Production of aqueous one-component polyurethane coating composition ]
The aqueous acrylic resin dispersion (solid content 42%, resin component hydroxyl value 66mgKOH/g, acid value 16 mgKOH/g) obtained in Synthesis example 6 described below was blended in such a ratio that the functional group ratio (NCO/OH) was 1.0 to the BPI compositions obtained in the examples and comparative examples. Further, deionized water was added to the mixture in such a ratio that the solid content was 40%, and the mixture was stirred at 1000rpm for 5 minutes with a stirring blade, thereby preparing an aqueous one-component polyurethane coating composition.
[ Evaluation 1] Water dispersibility
Regarding the water dispersibility of the BPI composition, the transmittance was measured by a spectrophotometer (the transmittance at a wavelength of 550nm is represented by "T550%", and the measurement instrument "UV-160" (trade name manufactured by shimadzu corporation), cell length=20 mm, and distilled water were used as controls) and evaluated according to the following criteria.
(Evaluation criterion)
And (3) the following materials: the T550% transmittance is 70% or more.
And (2) the following steps: t550% transmittance is 50% or more and less than 70%.
Delta: t550% transmittance is 30% or more and less than 50%.
X: t550% transmittance is less than 30%.
[ Evaluation 2] compatibility with Main agent
Each aqueous one-component polyurethane coating composition was applied to a glass plate with an applicator so as to be 50. Mu.m, and baked at 130℃for 30 minutes to obtain a cured coating film. Regarding the transparency of the produced coating film, haze value was measured using a SUGA tester haze meter (HMG-2 DP). Evaluation was performed according to the following criteria.
(Evaluation criterion)
And (3) the following materials: the haze value is less than 1.0%.
O: the haze value is 1.0% or more and less than 3.0%.
Delta: the haze value is 3.0% or more and less than 5.0%.
X: the haze value is 5.0% or more.
[ Evaluation 3] curability of coating film
Each aqueous one-component polyurethane coating composition was applied to a polypropylene plate by an applicator so that the resin film thickness became 50 μm, and baked at 130℃for 30 minutes to obtain a cured coating film. Next, the prepared coating film was immersed in acetone at 23 ℃ for 24 hours, and then the mass of the undissolved portion was divided by the mass before immersion, whereby the proportion (mass%) of the undissolved portion was calculated. The curability of the coating film was evaluated according to the following evaluation criteria.
(Evaluation criterion)
And (3) the following materials: 90 mass% or more.
O: 80 mass% or more and less than 90 mass%.
Delta: 70 mass% or more and less than 80 mass%.
X: less than 70 mass%.
[ Evaluation 4] Water resistance of coating film
Each aqueous one-component polyurethane coating composition was applied to a glass plate by an applicator so that the resin film thickness became 50 μm, and baked at 130℃for 30 minutes to obtain a cured coating film. Then, a rubber ring was placed on the prepared coating film, and deionized water was added dropwise to the center. After 24 hours of treatment at 40 ℃, the water resistance of the coating film was evaluated according to the following evaluation criteria, based on the state of foaming occurring between the glass substrate and the coating film.
(Evaluation criterion)
And (3) the following materials: the appearance is unchanged.
O: slightly white turbidity with no foaming and swelling.
Delta: the local part is cloudy and has foaming and swelling.
X: the whole surface is cloudy and has foaming and swelling.
[ Evaluation 5] adhesion to substrate
Each aqueous one-component polyurethane coating composition was applied to a mild steel sheet with an applicator so that the resin film thickness became 50 μm, left standing at room temperature for 15 minutes, and then baked at 130℃for 30 minutes to obtain a cured coating film. The adhesion test was carried out based on JIS K5600-5-6.
(Evaluation criterion)
And (3) the following materials: of the 100 squares, more than 90 squares remain on the substrate.
O: of the 100 squares, 70 or more and less than 90 squares remain on the substrate.
Delta: of the 100 squares, 50 or more and less than 70 squares remain on the substrate.
X: of the 100 squares, less than 50 squares remain on the substrate.
[ Evaluation 6] storage stability
Each of the aqueous blocked isocyanate compositions was filled in a glass container, and stored in a sealed state at 40 ℃ for 4 weeks, and the appearance and viscosity change after time were measured at 25 ℃ using an E-type viscometer available from eastern machine industry co. The measurement was performed by using an E-type viscometer (TOKIMEC Co., ltd.) and a standard rotor (1℃34'. Times.R 24) was used as the rotor. The rotational speeds are shown below.
100R.p.m. (less than 128 mPa. S)
50R.p.m. (128 mPas or more but less than 256 mPas)
20R.p.m. (256 mPas or more but less than 640 mPas)
10R.p.m. (640 mPas or more but less than 1,280 mPas)
5R.p.m. (1,280 mPa. S or more but less than 2,560 mPa. S)
The evaluation was performed according to the following evaluation criteria.
(Evaluation criterion)
And (3) the following materials: no appearance change and viscosity change.
O: no change in appearance, and a change in viscosity of 20% or less relative to that before storage.
Delta: there are several cloudiness, graining, and a change in viscosity of within 50% relative to that before storage.
X: the viscosity of the aqueous dispersion was 100% or more with respect to the viscosity before storage.
The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.
In the examples and comparative examples, "part" and "%" are mass references unless otherwise specified.
< Use Material >)
Various materials represented by abbreviations shown in synthesis examples, examples and tables 1 to 4 were prepared.
HDI: hexamethylene diisocyanate.
PG1: polyethylene oxide polyol having hydroxyl groups at one end and having a resin component hydroxyl value of 81mgKOH/g and a number average molecular weight of 690.
PG2: a polyethylene oxide polyol having a hydroxyl group at one end, a resin component having a hydroxyl value of 130mgKOH/g and a number average molecular weight of 430.
POL1: difunctional polyether polyol, hydroxyl value 280mgKOH/g, viscosity 70 mPa.s, number average molecular weight 400.
POL2: difunctional polyether polyol, hydroxyl number 112mgKOH/g, viscosity 145 mPa.s, number average molecular weight 1000.
POL3: difunctional polyether polyol, hydroxyl number 56mgKOH/g, viscosity 305 mPa.s, number average molecular weight 2000.
JP-508T: 2-ethylhexyl acid phosphate, manufactured by chemical industry Co., ltd.
PPL1: the polypropylene oxide 2-ethylhexyl ether which is a monohydric alcohol obtained by polymerizing an alkylene oxide having 3 or more carbon atoms has a hydroxyl value of 70KOH/g and a number average molecular weight of 800.
PPL2: the polypropylene oxide 2-ethylhexyl ether which is a monohydric alcohol obtained by polymerizing an alkylene oxide having 3 or more carbon atoms has a hydroxyl value of 94mgKOH/g and a number average molecular weight of 600.
PCL:2 functional polyester polyol, number average molecular weight 2000, manufactured by dic corporation.
PCD: polycarbonate diol, number average molecular weight 2000.
ROCIMA553,553: 2-methyl-4-isothiazolin-3-one and 2-n-octyl-4-isothiazolin-3-one, manufactured by the Dow chemical company.
LH-10: borches LH-10, dibutyl tin dilaurate, manufactured by Borches sam Co
XK-614: K-KAT XK-614, zinc-amine Compound, manufactured by Nanje chemical Co., ltd
Production of (A) isocyanate component
Synthesis example 1 production of polyisocyanate Pa-1
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas blowing tube and a dropping funnel was set to a nitrogen atmosphere, 1000g of HDI was charged, 1.8 parts of 2-ethylhexanol was charged, the temperature in the reactor was kept at 75℃with stirring, and ammonium tetramethyloctoate was added, and phosphoric acid was added at a point when the yield reached 38%, to stop the reaction. The reaction solution was filtered, and then unreacted HDI was removed by a thin film evaporator to obtain isocyanurate type polyisocyanate Pa-1. The NCO content of the obtained Pa-1 was 22.1% by mass.
Synthesis example 2 production of polyisocyanate Pa-2
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas blowing tube and a dropping funnel was set to a nitrogen gas atmosphere, 1000g of HDI and 32g of 2-ethylhexanol were charged, the temperature in the reactor was kept at 80℃with stirring, and tetramethyl ammonium octoate as a catalyst for the isocyanurate reaction was added, and phosphoric acid was added at a time when the yield reached 28% to stop the reaction. The reaction solution was filtered, and then unreacted HDI was removed by a thin film evaporator to obtain polyisocyanate Pa-2. The NCO content of the obtained Pa-2 was 20.7% by mass.
Synthesis example 3 production of polyisocyanate Pa-3
The reaction was started by charging 1000g of HDI, 333.3g of a mixed solution of methyl cellosolve and trimethyl phosphate (methyl cellosolve/trimethyl phosphate=1/1) into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas blowing pipe, and a dropping funnel under a nitrogen gas atmosphere, maintaining the temperature in the reactor at 140 ℃ with stirring, and adding 12.0g of ion-exchanged water. The reaction was stopped by cooling at the point when the yield reached 33%. The reaction solution was filtered, and then unreacted HDI was removed by a thin film evaporator to obtain polyisocyanate Pa-3. The NCO content of the obtained Pa-3 was 22.4% by mass.
PREPARATION EXAMPLE 4 preparation of polyisocyanate Pa-4
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube and a dropping funnel was put in a nitrogen atmosphere, 1000g of HDI and 2 parts of 2-ethylhexanol were charged, the temperature in the reactor was kept at 80℃with stirring, and ammonium tetramethyloctoate as a catalyst for the isocyanurate reaction was added, and phosphoric acid was added at a point in time when the yield reached 17%, to stop the reaction. The reaction solution was filtered, and then unreacted HDI was removed by a thin film evaporator to obtain polyisocyanate Pa-4. The NCO content of the obtained Pa-4 was 23.5% by mass.
Synthesis example 5 production of polyisocyanate Pa-5
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube and a dropping funnel was put in a nitrogen atmosphere, 1000g of HDI and 3 parts of 2-ethylhexanol were charged, the temperature in the reactor was kept at 80℃with stirring, and tetramethyl ammonium octoate as a catalyst for the isocyanurate reaction was added, and phosphoric acid was added at a point in time when the yield reached 14% to stop the reaction. The reaction solution was filtered, and then unreacted HDI was removed by a thin film evaporator to obtain polyisocyanate Pa-5. The NCO content of Pa-5 thus obtained was 23.0% by mass.
< Manufacture of main agent >
Synthesis example 6 production of aqueous acrylic resin Dispersion
70 Parts by mass of deionized water, 2 parts by mass of a 40% emulsifier aqueous solution, 0.37 parts by mass of methyl methacrylate, 0.23 parts by mass of n-butyl acrylate, 0.24 parts by mass of n-butyl methacrylate, 0.15 parts by mass of 2-hydroxyethyl methacrylate and 0.01 parts by mass of acrylic acid were charged into a reaction vessel, mixed in a nitrogen gas stream, and a 3% ammonium persulfate aqueous solution was added at 60 ℃. Then, the temperature was raised to 70℃and a mixture of 29 parts by mass of methyl methacrylate, 18 parts by mass of n-butyl acrylate, 19 parts by mass of n-butyl methacrylate, 12 parts by mass of 2-hydroxyethyl methacrylate, 1 part by mass of acrylic acid, 2 parts by mass of a 40% emulsifier aqueous solution, 4 parts by mass of a 3% ammonium persulfate aqueous solution and 40 parts by mass of deionized water was added to the reaction solution over 3 hours. Then, a mixed solution composed of 7.63 parts by mass of methyl methacrylate, 3.77 parts by mass of n-butyl acrylate, 4.76 parts by mass of n-butyl methacrylate, 2.85 parts by mass of 2-hydroxyethyl methacrylate, 0.99 parts by mass of acrylic acid and 4 parts by mass of a 3% ammonium persulfate aqueous solution was added to the reaction solution over 2 hours while maintaining the temperature at 70 ℃. After aging for 1 hour, 15 parts by mass of deionized water was added to the reaction solution, and the temperature was lowered to 30 ℃. Neutralization with dimethylethanolamine gave an aqueous acrylic resin dispersion having a solids content of 42%. The aqueous acrylic resin dispersion had a resin component hydroxyl value of 66mgKOH/g, an acid value of 16mgKOH/g, a number average molecular weight of 150000, a pH of 7.1, an average particle diameter of 0.1. Mu.m, and a milky appearance. The average particle diameter is a value measured by an average particle diameter measuring device (submicron particle diameter distribution measuring device, trademark "Coulter N4Plus", manufactured by Beckmann Kort Co., ltd.).
< Preparation of BPI composition >
EXAMPLE 1 preparation of BPI composition BPa-1
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 15g of POL1, 3g of PPL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 517.5g of water and 1g of ROCIMA g of 553 were added and further stirred for 30 minutes to obtain a BPI composition BPa-1. The effective NCO content of the obtained BPI composition was 3.2% by mass, and the composition had dispersibility in water. The BPI composition BPa-1 obtained was compounded in the amount shown in Table 1 in such a manner that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
EXAMPLE 2 preparation of BPI composition BPa-2
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 15g of POL1, 3g of PPL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain BPI composition BPa-2. The effective NCO content of the obtained BPI composition was 2.4% by mass, and the composition had dispersibility in water. The obtained BPI composition BPa-2 was compounded in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0, in the compounding amounts shown in Table 1.
EXAMPLE 3 production of BPI composition BPa-3
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, and 154.0g of polyisocyanate Pa-2 obtained in Synthesis example 2, 75.9g of PG1, 15g of POL1, 3g of PPL1 and 0.01g of JP-508T were mixed and urethanized at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPa-3. The effective NCO content of the obtained BPI composition was 2.4% by mass, and the composition had dispersibility in water. The obtained BPI composition BPa-3 was compounded in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0, in the compounding amounts shown in Table 1.
EXAMPLE 4 preparation of BPI composition BPa-4
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, and 145.0g of polyisocyanate Pa-3 obtained in Synthesis example 3, 85.1g of PG1, 15g of POL1, 3g of PPL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPa-4. The effective NCO content of the obtained BPI composition was 2.3% by mass, and the composition had dispersibility in water. The obtained BPI composition BPa-4 was compounded in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0, in the compounding amounts shown in Table 1.
EXAMPLE 5 production of BPI composition BPa-5
A four-necked flask equipped with a stirrer, a thermometer and a condenser was purged with nitrogen, and 147.2g of polyisocyanate Pa-4 obtained in Synthesis example 4, 82.8g of PG1, 15g of POL1, 3g of PPL1 and 0.01g of JP-508T were mixed and urethanized at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 517.5g of ion-exchanged water and 1g of ROCIMA g of water were added and stirred for further 30 minutes to obtain a BPI composition BPa-5. The effective NCO content of the obtained BPI composition was 3.3% by mass, and the composition had dispersibility in water. The obtained BPI composition BPa-5 was compounded in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0, in the compounding amounts shown in Table 1.
EXAMPLE 6 production of BPI composition BPa-6
A four-necked flask equipped with a stirrer, a thermometer and a condenser was purged with nitrogen, and 147.2g of polyisocyanate Pa-5 obtained in Synthesis example 5, 82.8g of PG1, 15g of POL1, 3g of PPL1 and 0.01g of JP-508T were mixed and urethanized at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 517.5g of ion-exchanged water and 1g of ROCIMA g of water were added and stirred for further 30 minutes to obtain BPI composition BPa-6. The effective NCO content of the obtained BPI composition was 3.3% by mass, and the composition had dispersibility in water. The resulting BPI composition BPa-6 was compounded in the compounding amounts shown in Table 2 in such a ratio that the molar ratio of hydroxyl groups of the polyol to isocyanate groups of the BPI composition was 1.0.
EXAMPLE 7 preparation of BPI composition BPa-7
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 38.8g of POL2, 0.01g of JP-508T and 3g of PPL1 were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 58.3g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPa-7. The effective NCO content of the obtained BPI composition was 2.2% by mass, and the composition had dispersibility in water. The obtained BPI composition BPa-7 was compounded in the compounding amount shown in Table 2 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
EXAMPLE 8 production of BPI composition BPa-8
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 62.0g of POL3, 3g of PPL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 59.8g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of water and 1g of ROCIMA were added and stirred for further 30 minutes to give a BPI composition BPa-8. The effective NCO content of the obtained BPI composition was 2.1% by mass, and the composition had dispersibility in water. The obtained BPI composition BPa-8 was compounded in the compounding amount shown in Table 2 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
EXAMPLE 9 preparation of BPI composition BPa-9
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 50.0g of PG1, 15g of POL1, 3g of PPL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of water and 1g of ROCIMA were added and stirred for further 30 minutes to give a BPI composition BPa-9. The effective NCO content of the obtained BPI composition was 2.8% by mass, and the composition had dispersibility in water. The obtained BPI composition BPa-9 was compounded in the compounding amount shown in Table 2 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
EXAMPLE 10 production of BPI composition BPa-10
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG2, 15g of POL1, 3g of PPL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPa-10. The effective NCO content of the obtained BPI composition was 2.2% by mass, and the composition had dispersibility in water. The resulting BPI composition BPa-10 was compounded in the compounding amounts shown in Table 2 in such a ratio that the molar ratio of hydroxyl groups of the polyol to isocyanate groups of the BPI composition was 1.0.
EXAMPLE 11 preparation of BPI composition BPa-11
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 15g of POL1, 3g of PPL2 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPa-11. The effective NCO content of the obtained BPI composition was 2.4% by mass, and the composition had dispersibility in water. The obtained BPI composition BPa-11 was compounded in the compounding amount shown in Table 3 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
EXAMPLE 12 production of BPI composition BPa-12
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 15g of POL1, 3g of PPL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 550g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPa-12. The effective NCO content of the obtained BPI composition was 2.8% by mass, and the composition had dispersibility in water. The obtained BPI composition BPa-1 was compounded in the compounding amount shown in Table 1 in such a ratio that the molar ratio of hydroxyl groups of the polyol to the BPI composition became 1.0. The resulting BPI composition BPa-12 was compounded in the compounding amounts shown in Table 3 in such a ratio that the molar ratio of hydroxyl groups of the polyol to isocyanate groups of the BPI composition was 1.0.
Examples 13 to 17
A BPI composition BPa-2 was produced in the same manner as in example 2, except that the components were compounded in the proportions shown in Table 3. The BPI composition thus obtained was compounded in the compounding amount shown in table 3 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
Comparative example 1 production of BPI composition BPb-1
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 77.1g of PCL, 0.01g of JP-508T and 3g of PPL1 were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water, ROCIMA553 were added: 1g, and further stirred for 30 minutes to obtain BPI composition BPb-1. The effective NCO content of the obtained BPI composition was 2.0% by mass, and the composition had dispersibility in water. The obtained BPI composition BPb-1 was compounded in the compounding amount shown in Table 4 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
Comparative example 2 production of BPI composition BPb-2
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 100.8g of POL2 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction mixture was cooled to 80℃and 54.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPb-5. The effective NCO content of the obtained BPI composition was 1.5% by mass, and the composition had dispersibility in water. The obtained BPI composition BPb-2 was compounded in the compounding amount shown in Table 4 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
Comparative example 3 production of BPI composition BPb-3
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 162.2g of PG1, 15g of POL1, 3g of PPL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPb-3. The effective NCO content of the obtained BPI composition was 1.5% by mass, and the composition had dispersibility in water. The obtained BPI composition BPb-3 was compounded in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0, in the compounding amounts shown in Table 4.
Comparative example 4 production of BPI composition BPb-4
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 15g of POL1 and 3g of PPL1 were mixed, 0.01g of JP-508T was mixed, and urethanization reaction was performed at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain BPI composition BPb-4. The effective NCO content of the obtained BPI composition was 3.7% by mass, and the composition had no dispersibility in water. The obtained BPI composition BPb-4 was compounded in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0, in the compounding amounts shown in Table 4.
Comparative example 5 production of BPI composition BPb-5
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 100.8g of POL2, 3g of PPL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction mixture was cooled to 80℃and 54.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPb-5. The effective NCO content of the obtained BPI composition was 1.5% by mass, and the composition had dispersibility in water. The obtained BPI composition BPb-5 was compounded in the compounding amount shown in Table 4 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
Comparative example 6 production of BPI composition BPb-6
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 0.01g of JP-508T and 3g of PPL1 were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPb-6. The effective NCO content of the obtained BPI composition was 2.8% by mass, and the composition had dispersibility in water. The obtained BPI composition BPb-6 was compounded in the compounding amount shown in Table 5 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
Comparative example 7 production of BPI composition BPb-7
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 77.2gPCD g of PPL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPb-7. The effective NCO content of the obtained BPI composition was 2.0% by mass, and the composition had dispersibility in water. The obtained BPI composition BPb-7 was compounded in the compounding amount shown in Table 5 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
Comparative example 8 production of BPI composition BPb-8
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 15g of POL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water was added and stirred for further 30 minutes to give BPI composition BPb-8. The effective NCO content of the obtained BPI composition was 2.4% by mass, and the composition had dispersibility in water. The obtained BPI composition BPb-8 was compounded in the compounding amount shown in Table 5 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
Comparative example 9 production of BPI composition BPb-9
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 80.2g of PG1, 15g of POL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 57.6g of 3, 5-dimethylpyrazole as a blocking agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, 136g of ion-exchanged water and 1g of ROCIMA were added, and further stirred for 30 minutes to obtain a BPI composition BPb-9. The effective NCO content of the obtained BPI composition was 4.8% by mass, and the composition had no dispersibility in water. The obtained BPI composition BPb-9 was compounded in the compounding amounts shown in Table 5 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
Comparative example 10 production of BPI composition BPb-10
The inside of a four-necked flask equipped with a stirrer, a thermometer and a condenser was replaced with nitrogen gas, 150.0g of polyisocyanate Pa-1 obtained in Synthesis example 1, 100.0g of PG1, 15g of POL1, 3g of PPL1 and 0.01g of JP-508T were mixed, and urethanization reaction was carried out at 120℃for 5 hours. The reaction solution was cooled to 80℃and 35.5g of methyl ethyl ketoxime as a capping agent was added thereto and stirred. The disappearance of the characteristic absorption of isocyanate groups was confirmed by infrared spectroscopy, and 690g of ion-exchanged water and 1g of ROCIMA were added and stirred for further 30 minutes to obtain a BPI composition BPb-10. The effective NCO content of the resulting BPI composition was 2.2% by mass, which had dispersibility in water, but was somewhat cloudy. The BPI composition BPb-10 obtained was compounded in the amount shown in Table 5 in such a manner that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
Comparative example 11
A BPI composition BPa-2 was produced in the same manner as in example 2, except that the components were compounded in the proportions shown in Table 5. The BPI composition thus obtained was compounded in the compounding amount shown in table 5 in such a ratio that the molar ratio of the hydroxyl groups of the polyol to the isocyanate groups of the BPI composition was 1.0.
The BPI compositions obtained in examples and comparative examples were used to measure and evaluate various physical properties according to the methods described above. The results are shown in tables 1 to 5 below.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
According to tables 1 to 3, BPI compositions BPa-1 to BPa-11 (examples 1 to 15) have good dispersibility in water and excellent compatibility with the main agent, and the curability, adhesion to a substrate, and water resistance of the coating film are significantly improved as compared with the conventional properties.
Further, the BPI compositions BPa-1 to BPa-8 and BPa-11 to BPa-15 (examples 1 to 8 and examples 11 to 15) having (A)/(B) of 63/37 to 70/30 were particularly excellent in adhesion to the substrate.
On the other hand, as shown in tables 4 to 5, the curing property, water resistance and storage stability of the coating films of the BPI compositions BPb-5 and BPb-6 (comparative examples 5 and 6) in which the content of the structural unit derived from the component (C) was less than 0.1% or 10% by mass or more were significantly lowered.
Further, the BPI composition BPb-1 (comparative example 1) obtained by changing the component (C) to a polyester polyol had poor adhesion to the coated substrate and also had a tendency to deteriorate storage stability and appearance. The composition BPI composition BPb-7 (comparative example 7) obtained by changing the component (C) to a polycarbonate polyol was poor in curability, water resistance, and adhesion when it was coated.
Further, the BPI composition BPb-4 (comparative example 4) having a ratio of (A)/(B) of more than 90/10 does not have water dispersibility and compatibility with the base agent, and the curability and water resistance thereof are poor when the BPI composition BPb-3 (comparative example 3) having a ratio of (A)/(B) of less than 60/40 is formed into a coating film.
Further, the compatibility between the main agent and the BPI composition BPb-2 (comparative example 2) in which the component (D) is not used at all is poor, and there is a tendency that dispersibility in water and storage stability are deteriorated. (D) BPI composition BPb-2 (comparative example 11) having a component content of 7.0% tends to be poor in water resistance and adhesion to a substrate.
Industrial applicability
The BPI composition of the present embodiment can be used in curable compositions such as coating compositions, adhesive compositions, and molding compositions; various surface treatment agent compositions such as a fiber treatment agent; various elastomer compositions; crosslinking agents for foam compositions and the like; a modifying agent; additives, and the like.
Claims (8)
1. A blocked polyisocyanate composition containing the following components (A), (B), (C), (D) and (E) and satisfying the following conditions (1) to (3):
(A) The components are as follows: polyisocyanates derived from aliphatic diisocyanates;
(B) The components are as follows: a nonionic hydrophilic compound having an active hydrogen group;
(C) The components are as follows: a difunctional or higher polyether polyol;
(D) The components are as follows: monohydric alcohol obtained by polymerizing alkylene oxide having 3 or more carbon atoms;
(E) The components are as follows: pyrazole compounds;
(1) The mass ratio ((A)/(B)) of the structural unit derived from the component (A) to the structural unit derived from the component (B) is 60/40 or more and 90/10 or less;
(2) The content of the structural unit derived from the component (C) is 0.1 mass% or more and 10 mass% or less relative to the total mass of the blocked polyisocyanate composition;
(3) The content of the component (D) is 0.05 mass% or more and 6.5 mass% or less relative to the total mass of the blocked polyisocyanate composition.
2. The blocked polyisocyanate composition of claim 1 wherein component (B) has 5 to 20 alkylene oxide repeating units.
3. The blocked polyisocyanate composition according to claim 1 or 2, wherein the component (C) has a number average molecular weight of 300 to 3000.
4. The blocked polyisocyanate composition according to claim 1 or 2, wherein the number average molecular weight of the (D) component is 300 or more and 2000 or less.
5. The blocked polyisocyanate composition according to claim 1 or 2, wherein the content of the (D) component is less than 1 mass% relative to the total mass of the blocked polyisocyanate composition.
6. An aqueous blocked polyisocyanate composition dispersion comprising the blocked polyisocyanate composition according to claim 1 or 2 and ion-exchanged water, wherein the proportion of the ion-exchanged water in the entire blocked polyisocyanate composition aqueous dispersion is 50 mass% or more and 90 mass% or less.
7. A water-based coating composition comprising the blocked polyisocyanate composition according to claim 1 or 2.
8. A coating film obtained by curing the aqueous coating composition according to claim 7.
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| JP2023-008075 | 2023-01-23 | ||
| JP2023-087957 | 2023-05-29 | ||
| JP2023087957 | 2023-05-29 |
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