CN108864919B - Composite, aqueous resin composition, and coating material - Google Patents

Composite, aqueous resin composition, and coating material Download PDF

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CN108864919B
CN108864919B CN201810442616.2A CN201810442616A CN108864919B CN 108864919 B CN108864919 B CN 108864919B CN 201810442616 A CN201810442616 A CN 201810442616A CN 108864919 B CN108864919 B CN 108864919B
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CN108864919A (en
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工藤英介
猪古智洋
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Nihon Parkerizing Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7692—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing at least one isocyanate or isothiocyanate group linked to an aromatic ring by means of an aliphatic group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation

Abstract

The invention aims to provide a composite body which is useful for forming a coating film with excellent corrosion resistance, heat resistance and solvent resistance, and an aqueous resin composition (including a coating) containing the composite body. The above object is achieved by a composite comprising an unsaturated polymerizable monomer polymer and a cationic group-containing polyurethane resin, wherein the cationic group-containing polyurethane resin comprises a structural unit derived from a specific polyisocyanate, a structural unit derived from a specific polyol, a structural unit derived from 2 or more specific diols, and a structural unit derived from a specific tertiary amine compound and/or a salt thereof.

Description

Composite, aqueous resin composition, and coating material
Technical Field
The present invention relates to a composite, and an aqueous resin composition and a coating material containing the composite.
Background
Conventionally, techniques have been proposed relating to aqueous resin compositions having good appearance of coating films and excellent blending stability with unsaturated polymerizable monomer polymers. For example, patent document 1 discloses a technique relating to an aqueous resin composition in which an unsaturated polymerizable monomer polymer is emulsified with a polyurethane resin containing a cationic group.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2012 and 1584
Disclosure of Invention
Problems to be solved by the invention
The aqueous resin composition described in patent document 1 cannot form a coating film having excellent corrosion resistance, heat resistance, and solvent resistance. Accordingly, an object of the present invention is to provide a composite useful for forming a coating film excellent in corrosion resistance, heat resistance and solvent resistance, and an aqueous resin composition (including a coating material) containing the composite.
Means for solving the problems
The present invention for achieving the above object includes the following aspects.
[1] A composite comprising an unsaturated polymerizable monomer polymer and a cationic group-containing polyurethane resin,
the cationic group-containing polyurethane resin comprises:
structural units derived from a polyisocyanate having a cyclohexane ring structure represented by the following formula (1),
A structural unit derived from a polyol represented by the following formula (2),
Structural units derived from 2 or more compounds selected from diols represented by the following formulae (3) and (4), and
a structural unit derived from a tertiary amine compound represented by the following formula (5) and/or a salt thereof.
Formula (1): O-C-N-R1－N＝C＝O
In the formula (1), R1with-R2－R3－R4Is represented by (A) to (R)2Is a single bond or alkylene, R3Is expressed by the following formula,
Figure GDA0003202175040000021
wherein, in the formula, R5、R6And R7Independently a hydrogen atom or an alkyl group.
R4Is a single bond, alkylene or a group represented by the following formula.
Figure GDA0003202175040000022
Wherein the left bonding site is bonded to R3And (4) bonding.
Formula (2):
Figure GDA0003202175040000023
in the formula (2), n is an integer,
R8with-R9－R10－R11-to.
R9Is a single bond,
Figure GDA0003202175040000024
or-R13-CO-。
In that
Figure GDA0003202175040000025
Middle, right bonding site and R10Is bonded at-R13in-CO-, the right-hand bonding site is bonded to R10And (4) bonding.
Wherein R is12Is a linear or branched alkylene radical, R13is-R18-O-or
Figure GDA0003202175040000026
And R is18Is a straight chain or branched chain alkylene, x is an integer of 1 to 5, and l is an integer of 2 to 4.
in-R18in-O-, the right bonding site is bonded to CO.
In that
Figure GDA0003202175040000031
The right bonding site of the center is bonded to CO.
R10Is a group represented by the following formula.
Figure GDA0003202175040000032
R11Is composed of
A single bond, a,
Figure GDA0003202175040000033
Figure GDA0003202175040000034
or-CO-R13-，
Wherein, except for the single bond, the bonding site on the left side is bonded to R10And (4) bonding.
R12Is a linear or branched alkylene radical, R13is-R18-O-or
Figure GDA0003202175040000035
And R is15And R16Independently a hydrogen atom, an alkyl group, a haloalkyl group or a phenyl group, R17Is a hydrogen atom, an alkyl group or a phenyl group, R18Is a linear or branched alkylene group, x is an integer of 1 to 5, and 1 is an integer of 2 to 4.
in-R18in-O-, the right bonding site is bonded to CO.
In that
Figure GDA0003202175040000036
The right bonding site of the center is bonded to CO.
R14Is a hydrogen atom, an alkyl group, a phenyl group,
Figure GDA0003202175040000037
Figure GDA0003202175040000038
Wherein R is18Is a linear or branched alkylene group, and 1 is an integer of 2 to 4.
Formula (3): HO-R19-H (3)
R in the formula (3)19Is composed of
Figure GDA0003202175040000041
Wherein the bonding site on each left side is bonded to OH.
R20Independently is an alkylene group,
Figure GDA0003202175040000042
Or an adamantane ring, R21Is an alkylene group, m is an integer of 2 to 4, and n is an integer.
Formula (4): HO-R22-OH
Formula (4)In, R22Is composed of
Alkylene, or a mixture thereof,
Figure GDA0003202175040000043
An adamantane ring,
Figure GDA0003202175040000044
Wherein y is 2 or 3, and z is an integer of 1-6.
Formula (5):
Figure GDA0003202175040000045
in the formula, R23Is alkyl, aminoalkyl, hydroxyalkyl,
Figure GDA0003202175040000046
Figure GDA0003202175040000047
R24Is hydroxyalkyl, aminoalkyl or N-alkylaminoalkyl.
[2] The composite according to [1], wherein the 2 or more kinds of diols include diol (C-1) represented by the formula (3) and having a weight average molecular weight of more than 600 and diol (C-2) represented by the formula (4) and having a weight average molecular weight of 600 or less.
[3] An aqueous resin composition comprising the composite according to [1] or [2 ].
[4] A coating material comprising the composite according to [1] or [2 ].
Effects of the invention
According to the present invention, a composite useful for forming a coating film excellent in corrosion resistance, heat resistance and solvent resistance, and an aqueous resin composition (including a coating material) containing the composite can be provided.
Detailed Description
Hereinafter, the present invention will be described in detail by showing specific embodiments.
The composite according to one embodiment of the present invention includes an unsaturated polymerizable monomer polymer and a cationic group-containing polyurethane resin. By using the aqueous resin composition containing the composite according to one embodiment of the present invention, a coating film having excellent corrosion resistance, heat resistance and solvent resistance can be formed. The cationic group-containing polyurethane resin comprises: structural units derived from a polyisocyanate having a cyclohexane ring structure represented by formula (1), structural units derived from a polyol represented by formula (2), structural units derived from 2 or more compounds selected from diols represented by formulae (3) and (4), and structural units derived from a tertiary amine compound represented by formula (5) and/or a salt thereof.
< unsaturated polymerizable monomer Polymer >
The unsaturated polymerizable monomer polymer according to one embodiment of the present invention is obtained by polymerizing an unsaturated polymerizable monomer.
Examples of the unsaturated polymerizable monomer constituting the unsaturated polymerizable monomer polymer according to one embodiment of the present invention include a carboxylic acid group-containing unsaturated polymerizable monomer, an esterified product of the carboxylic acid group-containing unsaturated polymerizable monomer, and a vinyl compound.
Examples of the unsaturated polymerizable monomer having a carboxylic acid group include (meth) acrylic acid containing methacrylic acid, crotonic acid, maleic acid, and itaconic acid.
Examples of the ester compound of the carboxylic acid group-containing unsaturated polymerizable monomer include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, bicyclo [3,3,1] nonyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, n-butyl (meth) acrylate, n-butyl) acrylate, butyl (meth) acrylate, n-butyl (meth) acrylate, butyl (meth) acrylate, butyl acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, ethoxypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, propoxypropylene glycol (meth) acrylate, and mixtures thereof, Mono (meth) acrylates such as oxypropylpolypropylene glycol (meth) acrylate; di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate; tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerol tri (meth) acrylate; tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; and hexa (meth) acrylate compounds such as sorbitol hexa (meth) acrylate.
Examples of the vinyl compound include vinyl acetate, vinyl propionate, styrene, α -methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, butadiene, and isoprene.
These unsaturated polymerizable monomers may be used alone or in combination of 2 or more.
The polymerization of the unsaturated polymerizable monomer can be carried out by using a known polymerization initiator in addition to the heating.
As the polymerization initiator, for example: azo initiators such as 2,2 '-azobisisobutyronitrile, 2' -azobis (2-methylpropionamidine) disulfide, 2 '-azobis (2-amidinopropane) dihydrochloride, 2' -azobis [ 2- (5-methyl-2-imidazolin-2-yl) propane ] dihydrochloride, and 2,2 '-azobis (N, N' -dimethyleneisobutylamidine); substituted ethane initiators such as phenyl-substituted ethane. Furthermore, it is also possible to use: persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; and a radical polymerization initiator such as a peroxide such as hydrogen peroxide, t-butyl hydroperoxide or cumene hydroperoxide. In addition, it is also possible to use a combination of these radical polymerization initiators with sulfites such as sodium sulfite; bisulfite such as sodium bisulfite; metal salts such as cuprous sulfate and ferrous sulfate; a redox initiator comprising a combination of reducing agents such as an organic reducing agent such as L-ascorbic acid.
As a method for polymerizing the unsaturated polymerizable monomer, a known method such as emulsion polymerization is used.
The polymerization temperature is suitably adjusted depending on the kind of the polymerization initiator, and is preferably in the range of, for example, 20 to 100 ℃.
The amount of the polymerization initiator is preferably 0.005 to 1 part by weight, for example, based on 100 parts by weight of the unsaturated polymerizable monomer.
In the production of the composite according to one embodiment of the present invention, the polymerization of the unsaturated polymerizable monomer is carried out simultaneously with or after the formation reaction of the cationic group-containing polyurethane resin described later.
As the cationic group-containing polyurethane resin contained in the composite according to one embodiment of the present invention, the following polyurethane resins are used.
< cationic group-containing polyurethane resin >
Typically, the cationic group-containing polyurethane resin according to one embodiment of the present invention is obtained by reacting a urethane prepolymer, an ionizing agent, and water. In this case, a polyamine compound excluding the tertiary amine compound may be contained as necessary to promote the reaction. Specifically, the isocyanate group contained in the urethane prepolymer reacts with an amine produced with water or a polyamine compound contained as needed to form a urea bond. In addition, a cationic group is introduced by neutralizing a moiety derived from the tertiary amine compound represented by formula (5) contained in the urethane prepolymer with an ionizing agent. Thus, a polyurethane resin containing a cationic group was obtained.
< urethane prepolymer >
The urethane prepolymer is a component for producing the cationic group-containing polyurethane resin according to one embodiment of the present invention, and is obtained by reacting at least a polyisocyanate having a cyclohexane ring structure, a polyol containing no nitrogen atom and a benzene ring, 2 or more kinds of diols containing no benzene ring and no nitrogen atom, and a tertiary amine compound having 2 or more active hydrogens and/or a salt thereof.
Expressed otherwise, the urethane prepolymer comprises: structural units derived from a polyisocyanate having a cyclohexane ring structure represented by formula (1), structural units derived from a polyol represented by formula (2), structural units derived from 2 or more compounds selected from diols represented by formulae (3) and (4), and structural units derived from a tertiary amine compound represented by formula (5) and/or a salt thereof.
Specifically, hydroxyl groups contained in the polyol represented by formula (2) (hereinafter also simply referred to as "polyol") and the diols represented by formulae (3) and (4) (hereinafter also simply referred to as "diol") are reacted with isocyanate groups contained in the polyisocyanate having a cyclohexane ring structure represented by formula (1) (hereinafter also simply referred to as "polyisocyanate") to form urethane bonds. Further, an isocyanate group contained in the polyisocyanate reacts with a tertiary amine compound represented by formula (5) (hereinafter also simply referred to as "tertiary amine compound" or "tertiary amine") and/or a hydrogen atom (active hydrogen) contained in a salt thereof to form a urethane bond, a urea bond, or the like.
The urethane prepolymer used in the present embodiment is a urethane prepolymer having isocyanate groups derived from a polyisocyanate for the purpose of reacting with water (any polyamine compound not including a tertiary amine may be used) as described above.
(polyisocyanate)
The polyisocyanate is used for producing a urethane prepolymer, which is represented by the following formula (1).
Formula (1): O-C-N-R1－N＝C＝O
In the formula (1), R1with-R2－R3－R4Is represented by (A) to (R)2Is a single bond or alkylene, R3Is a group of the formula,
Figure GDA0003202175040000081
wherein, in the formula, R5、R6And R7Independently a hydrogen atom or an alkyl group.
R4Is a single bond, alkylene or a group represented by the following formula.
Figure GDA0003202175040000082
Wherein the left bonding site is bonded to R3And (4) bonding.
R1Preferably, it is
Figure GDA0003202175040000091
Wherein R in the formula5、R6And R7Independently a hydrogen atom or a methyl group, more preferably R in the formula5、R6And R7All are hydrogen atoms or methyl groups.
The cyclohexane ring structure also includes a bicyclic structure having a cyclohexane structure. In addition, the polyisocyanate may contain a plurality of cyclohexane ring structures.
(kind of polyisocyanate)
The polyisocyanate is not particularly limited as long as it is a polyisocyanate represented by formula (1) having 1 or more cyclohexane rings and 2 or more isocyanate groups, and examples thereof include isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, 1, 3-diisocyanatocyclohexane, 1, 4-diisocyanatocyclohexane, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate, dicyclohexylmethane 4, 4' -diisocyanate, and the like. The polyisocyanate represented by formula (1) may be used in combination with a polyisocyanate not contained in formula (1), that is, a dimer such as a uretdione structure, a trimer such as an isocyanurate structure, or a polyisocyanate having 3 or more isocyanate groups in 1 molecule as an adduct using a polyfunctional polyol.
The polyisocyanate may be used alone in 1 kind or in combination of 2 or more kinds.
Among the above, the polyisocyanate is preferably at least 1 compound selected from isophorone diisocyanate and dicyclohexylmethane 4, 4' -diisocyanate.
(amount of polyisocyanate to be charged)
In the production of a urethane prepolymer described later, the amount of polyisocyanate added is preferably 31 to 70% by mass, more preferably 40 to 65% by mass, based on the total amount of polyisocyanate, polyol, 2 or more kinds of diols, and tertiary amine compound and/or salt thereof used in the production of the urethane prepolymer.
That is, in the urethane prepolymer used in the present embodiment, the amount of the structural unit derived from the polyisocyanate present (in terms of mass) is preferably 31 to 70%, and more preferably 40 to 65% in the urethane prepolymer.
In the present embodiment, when the "polyol of triol or more containing no benzene ring and no nitrogen atom" described later is used in the production of the urethane prepolymer, the amount of the polyol of triol or more containing no benzene ring and no nitrogen atom is calculated as the total amount.
(polyhydric alcohol)
The polyol is used for producing a urethane prepolymer, and is represented by the following formula (2).
Formula (2):
Figure GDA0003202175040000101
in the formula (2), n is an integer, R8with-R9-R10-R11Is represented by (A) to (R)9Is a single bond,
Figure GDA0003202175040000102
or-R13-CO-。
In that
Figure GDA0003202175040000103
Middle, right bonding site and R10Is bonded at-R13in-CO-, the right-hand bonding site is bonded to R10Bonding is carried out on the raw materials,
wherein R is12Is a linear or branched alkylene radical, R13is-R18-O-or
Figure GDA0003202175040000104
And R is18Is a straight-chain or branched alkylene group, x is an integer of 1 to 5, 1 is an integer of 2 to 4,
in-R18in-O-, the right bonding site is bonded to CO,
in that
Figure GDA0003202175040000105
The right bonding site of the center is bonded to CO.
R10Is a group of the formula,
Figure GDA0003202175040000106
R11is composed of
A single bond, a,
Figure GDA0003202175040000111
Figure GDA0003202175040000112
or-CO-R13-，
Wherein, except for the single bond, the bonding site on the left side is bonded to R10Bonding is carried out on the raw materials,
R12is a linear or branched alkylene radical, R13is-R18-O-or
Figure GDA0003202175040000113
And R is15And R16Independently a hydrogen atom, an alkyl group, a haloalkyl group or a phenyl group, R17Is a hydrogen atom, an alkyl group or a phenyl group, R18Is a straight-chain or branched alkylene group, x is an integer of 1 to 5, 1 is an integer of 2 to 4,
in-R18in-O-, the right bonding site is bonded to CO,
in that
Figure GDA0003202175040000114
The right bonding site of the center is bonded to CO.
R14Is a hydrogen atom, an alkyl group, a phenyl group,
Figure GDA0003202175040000115
Figure GDA0003202175040000116
Wherein R is18Is a linear or branched alkylene group, and 1 is an integer of 2 to 4.
In the above formula (2), R8Preferably, it is
Figure GDA0003202175040000117
(the bonding site on the right side is bonded to 0H),
Figure GDA0003202175040000118
R12Preferably ethylene or isopropylene. R14Preferably a hydrogen atom, a methyl group, an iso-groupPropyl or phenyl. R15Preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a phenyl group. R16Preferably a hydrogen atom, methyl, ethyl, trifluoromethyl or phenyl. R17Preferably a hydrogen atom, a methyl group, an isopropyl group or a phenyl group.
(kind of polyol)
The polyol is not particularly limited as long as it is a polyol represented by formula (2) having 1 or more benzene rings and 2 or more hydroxyl groups and no nitrogen atom, and examples thereof include: aromatic polyols such as resorcinol, 2-methylresorcinol, bisphenol a, bisphenol S, and bisphenol F; polyether polyols having a benzene ring such as bisphenol a-ethylene oxide 2 mol adduct, bisphenol a-ethylene oxide 4 mol adduct, bisphenol a-ethylene oxide 6 mol adduct, bisphenol a-ethylene oxide 10 mol adduct, bisphenol a-propylene oxide 2 mol adduct, bisphenol a-propylene oxide 4 mol adduct, bisphenol a-propylene oxide 6 mol adduct, bisphenol a-propylene oxide 10 mol adduct, and the like; polyester polyols having a benzene ring, which are obtained by polycondensation of an aromatic polycarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, or the like, and a polyhydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2-methylpropanediol, neopentyl glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methylpentanediol, or the like; polycarbonate polyols having a benzene ring obtained by an ester exchange reaction between ethylene carbonate and a polyol such as bisphenol a.
The polyhydric alcohol may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Among the above, the polyol is preferably a polyether polyol having a benzene ring.
(amount of polyol to be added)
In the production of a urethane prepolymer described later, the amount of the polyol to be charged may be, for example, usually 1 to 35% by mass, more preferably 3 to 25% by mass, based on the total amount of the polyisocyanate, the polyol, the 2 or more kinds of diols, and the tertiary amine compound and/or the salt thereof used in the production of the urethane prepolymer. That is, in the urethane prepolymer used in the present embodiment, the amount of the structural unit derived from the polyol of formula (2) present (in terms of mass) is usually 1 to 35%, preferably 3 to 25% in the urethane prepolymer.
In the present embodiment, when the "polyol containing not less than triol having no benzene ring and no nitrogen atom" described later is used for producing the urethane prepolymer, the amount of the polyol containing not less than triol having no benzene ring and no nitrogen atom is calculated as the total amount.
(diol)
Diols represented by the formulae (3) and (4) are used for producing the urethane prepolymer. In the production of the urethane prepolymer, 2 or more compounds selected from the diols represented by the formulae (3) and (4) are used.
Formula (3): HO-R19-H (3)
In the formula (3), R19Is composed of
Figure GDA0003202175040000131
Wherein the bonding site on the left side of each is bonded to OH,
R20independently is an alkylene group,
Figure GDA0003202175040000132
Or an adamantane ring, R21Is an alkylene group, m is an integer of 2 to 4, and n is an integer.
Formula (4): HO-R22-OH (4)
In the formula (4), R22Is composed of
Alkylene, or a mixture thereof,
Figure GDA0003202175040000133
An adamantane ring,
Figure GDA0003202175040000134
Wherein y is 2 or 3, and z is an integer of 1-6.
As the at least 2 kinds of diols used in the production of the urethane prepolymer, a diol having a weight average molecular weight of more than 600 and a diol having a weight average molecular weight of 600 or less are preferably used, and more preferably, a diol (C-1) represented by formula (3) and having a weight average molecular weight of more than 600 and a diol (C-2) represented by formula (4) and having a weight average molecular weight of 600 or less are used.
The diol (C-1) is more preferably a diol having a weight average molecular weight of 800 or more and 4000 or less. The diol (C-2) is more preferably a diol having a weight average molecular weight of 60 or more and 400 or less.
Unless otherwise specified, the weight average molecular weight of each component in the present embodiment is a value measured by GPC (gel permeation chromatography) and converted to polystyrene.
(specific Compounds of diols (C-1) and (C-2))
As the diol (C-1), for example, polyether diol, polyester diol, polycarbonate diol and the like can be used.
Examples of the polyether glycol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol (polytetramethylene ether glycol). Polyether glycols are produced by addition polymerization of alkylene oxides such as ethylene oxide or propylene oxide in the presence of a basic catalyst.
Examples of the polyester diol include polyester diols produced by an esterification reaction of an aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, or an unsaturated carboxylic acid such as sebacic acid with an alcohol such as ethylene glycol, propylene glycol, tetraethylene glycol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, cyclohexyldimethanol, or 1, 3-adamantanediol.
Examples of the polycarbonate diol include those produced by ring-opening polymerization of a cyclic ester such as e-caprolactone with a diol, and specifically, those produced by reacting dimethyl carbonate, diethyl carbonate, diphenyl carbonate, or the like with one of the above-mentioned polyester diols.
Examples of the diol (C-2) include: alkyl diols such as ethylene glycol (62.07g/mol), propylene glycol (76.09g/mol), 1, 5-pentanediol (104.15g/mol), 1, 6-hexanediol (118.17g/mol), 1, 7-heptanediol (132.2g/mol), 1, 8-octanediol (146.23g/mol), 1, 9-nonanediol (160.25g/mol), 1, 10-decanediol (174.28g/mol), neopentyl glycol (104.15g/mol), 2-methyl-1, 3-propanediol (90.12g/mol), 3-methyl-1, 5-pentanediol (118.17g/mol), 1, 4-cyclohexanedimethanol (146.14g/mol), 1, 3-adamantanediol (168.23 g/mol); polyalkylene glycols such as diethylene glycol (106.12g/mol), triethylene glycol (150.17g/mol), tetraethylene glycol (194.23g/mol), pentaethylene glycol (238.28g/mol), hexaethylene glycol (282.33g/mol), heptaethylene glycol (323.28g/mol), and dipropylene glycol (134.17 g/mol); dimethylolpropionic acid (134g/mol), and the like.
As the diol (C-1), polyether diols such as polyethylene glycol, polypropylene glycol and polybutylene glycol are preferable. As the diol (C-2), a polyalkylene glycol is preferable.
(amount of diol to be added)
In the production of the urethane prepolymer, the amount of the 2 or more diols to be added may be, for example, 2 to 60% by mass, preferably 4 to 55% by mass, and more preferably 7 to 50% by mass, based on the total amount of the polyisocyanate, the polyol, the 2 or more diols, and the tertiary amine compound and/or the salt thereof used in the production of the urethane prepolymer. That is, in the urethane prepolymer used in the present embodiment, the amount of the structural unit derived from 2 or more kinds of diols present (in terms of mass) is usually 2 to 60%, preferably 4 to 55%, and more preferably 7 to 50% in the urethane prepolymer.
In the production of the urethane prepolymer, the amount of the diol (C-1) added in the case of using the polyisocyanate, the polyol, 2 or more kinds of diols and the tertiary amine compound and/or the salt thereof used in the production of the urethane prepolymer may be, for example, usually 1 to 50% by mass, preferably 3 to 40% by mass, and more preferably 5 to 30% by mass.
That is, in the urethane prepolymer used in the present embodiment, the amount of the structural unit of the diol (C-1) present (in terms of mass) is usually 1 to 50%, preferably 3 to 40%, and more preferably 5 to 30% in the urethane prepolymer.
In addition, in the production of the urethane prepolymer, the amount of the diol (C-2) to be added when used may be, for example, 1 to 25% by mass, preferably 1 to 20% by mass, and more preferably 2 to 15% by mass, based on the total amount of the polyisocyanate, the polyol, the 2 or more kinds of diols, and the tertiary amine compound and/or the salt thereof used in the production of the urethane prepolymer.
That is, in the urethane prepolymer used in the present embodiment, the amount of the structural unit of the diol (C-2) present (in terms of mass) is usually 1 to 25%, preferably 1 to 20%, and more preferably 2 to 15% in the urethane prepolymer.
In the case where "a polyol of triol or more containing no benzene ring and no nitrogen atom" described later is used in the production of the urethane prepolymer according to one embodiment of the present invention, the amount of the polyol of triol or more containing no benzene ring and no nitrogen atom is calculated as the total amount.
(Tertiary amine compound or salt thereof)
The tertiary amine compound and/or a salt thereof is used for producing the urethane prepolymer, and is represented by the following formula (5).
Formula (5):
Figure GDA0003202175040000161
in the formula, R23Is alkyl, aminoalkyl, hydroxyalkyl,
Figure GDA0003202175040000162
Figure GDA0003202175040000163
R24Is hydroxyalkyl, aminoalkyl or N-alkylaminoalkyl.
R23The aminoalkyl group in (A) is preferably- (CH)2)2－NH2Or- (CH)2)3－NH2。R24The aminoalkyl group in (A) is preferably- (CH)2)2－NH2。R23And R24The hydroxyalkyl group in (A) is preferably- (CH)2)2－OH。R24The N-alkylaminoalkyl group in (1) is preferably- (CH)2)2－NH－CH3。
The urethane prepolymer into which a group derived from the tertiary amine compound and/or a salt thereof is introduced is obtained by reacting the active hydrogen of the tertiary amine compound and a salt thereof with the polyisocyanate.
The tertiary amine compound and/or a salt thereof preferably contains 2 or more active hydrogens, and for example, preferably contains 2 or more substituents having active hydrogens such as amino groups, hydroxyl groups, and N-alkylamino groups. Further, as the N-alkylamino group, a 2-methylamino group is preferable.
(amount of tertiary amine compound and/or salt thereof to be charged)
In the production of the urethane prepolymer described later, the amount of the tertiary amine compound and/or a salt thereof to be added may be, for example, usually 1 to 20% by mass, preferably 2 to 15% by mass, based on the total amount of the polyisocyanate, the polyol, the 2 or more kinds of diols, and the tertiary amine compound and/or a salt thereof used in the production of the urethane prepolymer.
That is, in the urethane prepolymer used in the present embodiment, the amount of the structural unit derived from the tertiary amine compound of the formula (5) and/or the salt thereof present (in terms of mass) is usually 1 to 20%, preferably 2 to 15% in the urethane prepolymer.
In the case where "a polyol of triol or more containing no benzene ring and no nitrogen atom" described later is used in the production of the urethane prepolymer according to one embodiment of the present invention, the amount of the polyol of triol or more containing no benzene ring and no nitrogen atom is calculated as the total amount.
(kind of tertiary amine Compound)
The tertiary amine compound is not particularly limited as long as it is a tertiary amine having 2 or more active hydrogens, and examples thereof include: n-aminoalkyldialkanolammonium salts such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-t-butyldiethanolamine, and N- (3-aminopropyl) diethanolamine; trialkanolamines which may have substituents, such as triethanolamine, N' -tetrakis (2-hydroxyethyl) ethylenediamine, bis (2-hydroxyethyl) aminotri (hydroxymethyl) methane, 1-bis (2-hydroxyethyl) amino 2-propanol, and the like; tertiary amines such as 2,2 '-diamino-N-methyldiethylamine, N', N ″ -trimethyldiethylenetriamine, tris (2-aminoethyl) amine, and the like. These tertiary amines may be used in the form of salts with organic acids such as formic acid and acetic acid, and inorganic acids such as hydrochloric acid and sulfuric acid, or those quaternized with alkylating agents such as dimethyl sulfate, diethyl sulfate and methyl iodide. As the tertiary amine compound, N-aminoalkyldialkanolamines are preferable, and N-methyldiethanolamine is particularly preferable.
The cationic group-containing polyurethane resin of the present embodiment is a polyurethane resin obtained by neutralizing a part or all of a structural moiety (tertiary amine) derived from a tertiary amine compound with an acid or the like. As the acid used at this time, for example: organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, malic acid, malonic acid, and adipic acid; organic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid and the like; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, bromic acid, and phosphoric acid. These acids may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
In addition, a part or all of the structural moiety (tertiary amine) derived from the tertiary amine compound may be quaternized. Specific examples of the quaternizing agent used in the quaternization include: sulfuric acid esters such as dimethyl sulfate and diethyl sulfate; alkyl halides such as methyl chloride, benzyl chloride, methyl bromide, benzyl bromide, and methyl iodide; and carbonates such as dimethyl carbonate and diethyl carbonate. These quaternizing agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds. In addition, an acid as a neutralizing agent and a quaternizing agent may be used in combination.
In the present specification, these acids and quaternizing agents are sometimes referred to as ionizing agents.
In the present specification, "alkyl" contained in "alkyl" or haloalkyl, aminoalkyl, hydroxyalkyl, N-alkylaminoalkyl and the like is not particularly limited, and is usually an alkyl group having 20 or less carbon atoms, and may be an alkyl group having 12 or less carbon atoms, or may be an alkyl group having 6 or less carbon atoms. Typically, there are mentioned methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, 3-methylpentyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.
The "alkylene group" is not particularly limited, and is usually an alkylene group having 20 or less carbon atoms, and may be an alkylene group having 12 or less carbon atoms, or an alkylene group having 6 or less carbon atoms. Typically, ethylene, propylene, butylene, isobutylene, tert-butylene, sec-butylene, pentylene, isopentylene, neopentylene, hexylene, isohexylene, 3-methylpentylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, and the like are mentioned.
Examples of the haloalkyl group include those wherein 1 or more hydrogen atoms in the alkyl group are substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
(other Components that can be used for producing urethane prepolymer)
In the production of the urethane prepolymer of the present embodiment, other components than those described above may be used. Examples of the other components include polyisocyanates other than the above-mentioned polyisocyanates, polyols other than the above-mentioned polyols and diols and not containing a benzene ring and a nitrogen atom, organic solvents, polyamine compounds other than the above-mentioned tertiary amine compounds, ionizing agents, acids, organic metal compounds, and the like.
(polyisocyanates other than polyisocyanates)
The polyisocyanate other than the above-mentioned polyisocyanate is not particularly limited, and examples thereof include: aliphatic diisocyanates such as 1, 4-tetramethylene diisocyanate, ethyl (2, 6-diisocyanato) hexanoate, 1, 6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate or 2,4, 4-trimethylhexamethylene diisocyanate; aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, diphenylmethane-4, 4 '-diisocyanate, 1, 3-bis (2-isocyanate-2-propyl) benzene, naphthalene-1, 5-diisocyanate, diphenyl-4, 4' -diisocyanate, 4 '-diisocyanate-3, 3' -dimethylbiphenyl, 3-methyl-diphenylmethane-4, 4 '-diisocyanate, diphenyl ether-4, 4' -diisocyanate, and tetramethylxylylene diisocyanate; aliphatic triisocyanates such as 1,3, 6-hexamethylene triisocyanate, 1, 8-diisocyanate-4-isocyanatomethyloctane and ethyl 2-isocyanato (2, 6-diisocyanato) hexanoate; aromatic triisocyanates such as triphenylmethane triisocyanate and tris (isocyanatophenyl) thiophosphate, and the like. The polyisocyanate other than the above-mentioned polyisocyanate may be a dimer such as a uretdione structure, a trimer such as an isocyanurate structure, or a polyisocyanate having 3 or more isocyanate groups in 1 molecule as an adduct using a polyfunctional polyol.
Among these, aromatic polyisocyanates such as aromatic diisocyanates and aromatic triisocyanates are preferably used, and aromatic diisocyanates are more preferably used. The content of the other component and the amount of the structure derived from the other component in the urethane prepolymer may be appropriately set by those skilled in the art within a range not to impair the effects of the present invention.
(polyols other than the polyol represented by the above formula (2) and the diols represented by the above formulae (3) and (4))
As the polyhydric alcohol other than the polyhydric alcohol represented by the above formula (2) and the diols represented by the above formulae (3) and (4), polyhydric alcohols of triols or more containing no benzene ring and no nitrogen atom can be used, and examples thereof include trimethylolpropane, pentaerythritol, and the like.
Among the polyhydric alcohols not less than triols containing no benzene ring and no nitrogen atom, Trimethylolpropane (TMP) is preferred. When a polyol containing not less than a triol containing no benzene ring and no nitrogen atom is used for producing a urethane prepolymer, the amount of the polyol to be added is preferably 0.5 to 18% by mass, more preferably 3 to 15% by mass, based on the total amount of the polyisocyanate, the polyol, 2 or more kinds of diols, the tertiary amine compound and/or a salt thereof, and the polyol containing not less than a triol containing no benzene ring and no nitrogen atom used for producing a urethane prepolymer. That is, in the urethane prepolymer used in the present embodiment, the amount (in terms of mass) of the structural unit derived from a polyol containing no benzene ring and no nitrogen atom and not less than triol is usually 0.5 to 18%, preferably 3 to 15% in the urethane prepolymer.
The urethane prepolymer and the cationic group-containing polyurethane resin according to the present embodiment preferably have a branched structure. As a method for introducing a branched structure, a method using a polyol of at least triol not containing a benzene ring and a nitrogen atom as described above is exemplified, but the method is not limited thereto.
In the production of the urethane prepolymer and/or the production of the cationic group-containing polyurethane resin, an organic solvent may be used. The organic solvent is used as a solvent for reacting the above components. Such an organic solvent is not particularly limited, and examples thereof include: ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as tetrahydrofuran and 1, 4-dioxane; nitrile solvents such as acetonitrile and acrylonitrile; acrylate solvents such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate; amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide.
From the viewpoint of reducing the load on the environment, these organic solvents can be removed by a reduced pressure distillation method as necessary after the production of the urethane prepolymer or the cationic group-containing polyurethane resin.
The composite and the aqueous resin composition of the present embodiment can be produced by the following methods.
A urethane prepolymer having an isocyanate group at the end is produced by dissolving and reacting a polyisocyanate, a polyol, 2 or more diols, a tertiary amine compound and/or a salt thereof, and the like in an organic solvent.
As the organic solvent, any organic solvent such as acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, or butyl acetate may be used.
Next, an unsaturated polymerizable monomer is added to the urethane prepolymer having an isocyanate group at the end to prepare a uniform solution, then a part or all of the tertiary amine in the urethane prepolymer having an isocyanate group at the end is ionized by an ionizing agent, and water is added to emulsify the mixture, and if necessary, a polyamine compound is added to perform a chain extension reaction, whereby a polyurethane resin containing a cationic group can be produced.
When the unsaturated polymerizable monomer does not contain an active hydrogen group in the molecule, the unsaturated polymerizable monomer may be mixed when other components (polyisocyanate, polyol, 2 or more kinds of diols, tertiary amine compound and/or salt thereof, and the like) are mixed.
Further, an aqueous resin composition containing the composite according to one embodiment of the present invention can be produced by polymerizing an unsaturated polymerizable monomer simultaneously with or after chain extension to produce an unsaturated polymerizable monomer polymer, and then distilling off the organic solvent under reduced pressure.
In the present specification, the term "composite" refers to a composite polymer emulsion of a cationic group-containing polyurethane resin and an unsaturated polymerizable monomer polymer. More specifically, it means: a composite polymer emulsion obtained by emulsifying an unsaturated polymerizable monomer polymer using a cationic group-containing polyurethane resin as an emulsifier.
In the production of the composite according to one embodiment of the present invention, it is preferably adjusted toTotal mass (Y) of each component used in production of urethane prepolymerM) With the mass (X) of the unsaturated polymerizable monomerM) Ratio of [ X ]M/YM]In the range of 20/80 to 60/40, more preferably adjusted to [ X ]M/YM]Is in the range of 30/70-60/40.
(polyamine Compound)
The polyamine compound used as a chain extender for producing the cationic group-containing polyurethane resin is not particularly limited, and for example: ethylenediamine, 1, 2-propylenediamine, 1, 6-hexamethylenediamine, piperazine, 2, 5-dimethylpiperazine, isophoronediamine, 4 ' -dicyclohexylmethanediamine, 3 ' -dimethyl-4, 4 ' -dicyclohexylmethanediamine, 1, 4-cyclohexanediamine, 1, 3-bisaminomethylcyclohexane, 2-aminoethylaminopropyltrimethoxysilane; n-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, 1, 6-hexamethylene bis-hydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; beta-semicarbazide propionohydrazide, 3-semicarbazide propylcarbazate, semicarbazide-3-semicarbazide methyl-3, 5, 5-trimethylcyclohexane, and the like. Among them, hydrazine or ethylenediamine is preferably used.
When a chain extender is used, the amount of the polyamine compound to be added is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the urethane prepolymer.
Further, in the aqueous resin composition according to one embodiment of the present invention, various additives generally used may be used as necessary. Examples of such additives include weather-resistant agents, antibacterial agents, antifungal agents, pigments, fillers, rust-proofing agents, dyes, film-forming aids, inorganic crosslinking agents, organic crosslinking agents (e.g., blocked isocyanate-based crosslinking agents, epoxy-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, melamine-based crosslinking agents, etc.), silane coupling agents, antiblocking agents, viscosity modifiers, leveling agents, defoaming agents, dispersion stabilizers, light stabilizers, antioxidants, ultraviolet absorbers, inorganic fillers, organic fillers, plasticizers, lubricants, antistatic agents, and the like.
The aqueous resin composition according to the present embodiment can be widely used as a general coating material, and is particularly suitable as a coating material for a metal surface treatment agent and the like.
The aqueous resin composition according to the present embodiment preferably contains the composite as an active ingredient for various applications such as a coating material.
Examples
The composite according to the present embodiment, and the aqueous resin composition and the coating material containing the composite will be described in detail below with reference to examples. However, the present invention is not limited to the embodiment.
Before preparing the coating materials of examples and comparative examples, the synthesis methods of the respective composites used in the preparation of the respective coating materials are shown below.
< Synthesis example 1 >
37.8g of bisphenol A-polyoxyethylene 2 mol adduct (Newpol BPE-20T, manufactured by Sanyo chemical Co., Ltd.), 40.3g of polyethylene glycol (PEG2000, manufactured by first Industrial pharmaceutical Co., Ltd.), 17.6g of diethylene glycol (diethylene glycol, manufactured by Nippon catalyst Co., Ltd.), 17.6g of N-methyldiethanolamine (amino alcohol MDA, manufactured by Nippon emulsifier Co., Ltd.), 138.7g of isophorone diisocyanate (Desmodur I, manufactured by Bayer Co., Ltd.), and 168g of methyl methacrylate (manufactured by Kanto chemical Co., Ltd.) were added to 150g of methyl ethyl ketone and sufficiently dissolved. After the mixed solution was reacted at 50 ℃ for about 5 hours, it was confirmed that 3 mass% or less of isocyanate groups were contained. Subsequently, the solution was cooled to 45 ℃ and 10g of dimethyl sulfate was added. Subsequently, 1500g of water was added, 1.3g of potassium persulfate was added, and the mixture was reacted at 75 ℃ for 3 hours, and then methyl ethyl ketone was removed by reduced pressure distillation at 50 ℃ to obtain an aqueous resin composition containing 25% of nonvolatile components (including a complex). The content of the isocyanate group may be determined in accordance with JIS K7301: 1995, 2g of the reaction solution was dissolved in dimethylformamide, 10ml of n-dibutylamine-toluene solution was added, and then titration was performed with 0.5mol/L hydrochloric acid solution using bromophenol blue as an indicator, and the following formula was used for calculation.
[ number 1]
Figure GDA0003202175040000221
(wherein A represents the volume of hydrochloric acid solution required for titration of the amount (mass) of isocyanate used for preparing a predetermined amount of a reaction solution, B represents the volume of hydrochloric acid solution required for titration of a reaction solution, f represents "1", N represents the molar concentration of a hydrochloric acid standard solution, and S represents the mass of a reaction solution.)
< Synthesis examples 2 to 45 >
Aqueous resin compositions of synthesis examples 2 to 45 containing 25% of nonvolatile components (including composite) were obtained in the same manner as in synthesis example 1, except that the components and the amounts (mass%) added shown in tables 1 and 2 were changed.
< Synthesis example 46 >
An aqueous resin composition of synthesis example 46 containing 25% of nonvolatile components (including a composite) was obtained in the same manner as in synthesis example 1, except that 10g of 85% phosphoric acid was used in place of 10g of dimethyl sulfate in each component and the amount (mass%) shown in Table 2.
< Synthesis example 47 >
An aqueous resin composition of Synthesis example 47 containing 25% of nonvolatile components (including composite) was obtained in the same manner as in Synthesis example 1, except that 4g of formic acid was used in place of 10g of dimethyl sulfate in each component and amount (mass%) shown in Table 2.
< comparative Synthesis examples 1 to 4 >
Aqueous resin compositions of comparative synthesis examples 1 to 4 containing 25% of nonvolatile components (including composite) were obtained in the same manner as in synthesis example 1, except that the components and the amounts (mass%) added were as shown in table 3.
The components described in tables 1 to 3 are shown below. The amounts (% by mass) of the components used in the production of the urethane prepolymers described in tables 1 to 3 were calculated based on the total amount of the components (a) to (E) below.
< polyisocyanate (A; hereinafter, a part of polyisocyanate having a cyclohexane ring structure) >)
A1: isophorone diisocyanate (Desmodur I, manufactured by Bayer corporation)
A2: dicyclohexylmethane 4, 4' -diisocyanate (Desmodur W, manufactured by Bayer Corp.)
A3: 1, 3-bis (isocyanatomethyl) cyclohexane (Takenate 600, manufactured by Mitsui chemical Co., Ltd.)
A4: hexamethylene diisocyanate (50M-HDI manufactured by Asahi Chemicals Co., Ltd.)
< polyol (B) >
B1: bisphenol A-polyoxyethylene 2 mol adduct (Newpol BPE20T, Sanyo chemical industry Co., Ltd.)
B2: aromatic dibasic acid polyester polyol (テスラック (TL series) 2508-70, manufactured by Hitachi chemical Co., Ltd.)
B3: polycarbonate diol (Nippollan 981, manufactured by Tosoh Co., Ltd.)
< diol (C; the following is a diol containing no benzene ring and no nitrogen atom) >)
C1: polyethylene glycol (PEG2000, Mw2000, manufactured by Sanyo chemical industries Co., Ltd.)
C2: polyethylene glycol (PEG400, Mw400, manufactured by Sanyo chemical industries Co., Ltd.)
C3: polyethylene glycol (PEG1000, Mw1000, manufactured by Sanyo chemical industries Co., Ltd.)
C4: polyethylene glycol (PEG4000, Mw4000, manufactured by Sanyo chemical industries Co., Ltd.)
C5: polyester polyol (Nippollan 4040, Mw2000, manufactured by Tosoh corporation)
C6: polycarbonate diol (Nippollan 982R, Mw2000, manufactured by Tosoh corporation)
C7: ethylene glycol (ethylene glycol, Mw62, manufactured by Nippon catalyst Co., Ltd.)
C8: diethylene glycol (diethylene glycol, Mw106, manufactured by Nippon catalyst Co., Ltd.)
< Tertiary amine (D) >)
D1: n-methyldiethanolamine (aminoalcohol MDA, manufactured by Japan emulsifier Co., Ltd.)
< other polyhydric alcohols (E) > (triols containing no benzene rings and no nitrogen atoms)
E1: trimethylolpropane (TMP, Perstorp Co., Ltd.)
< unsaturated polymerizable monomer (X) >)
x 1: methyl methacrylate (manufactured by Kanto chemical Co., Ltd.)
x 2: butyl acrylate (manufactured by Kanto chemical Co., Ltd.)
x 3: methyl methacrylate + styrene (manufactured by kanto chemical corporation) [ mass ratio 1: 1]
< Material under test (Metal Material) >)
The following metal materials were used as test materials.
GI: hot-dip galvanized steel sheet (thickness: 0.6mm, plating adhesion amount: 50g/m on one side)2)
EG: electrogalvanized steel sheet (sheet thickness: 0.6mm, plating adhesion amount: 20g/m on one side)2)
GL: 55% molten aluminum-zinc alloy plated steel sheet (thickness: 0.4mm, plating adhesion amount: 75g/m on one side)2)
< preparation of coating >
To 100 parts by mass of each of the aqueous resin compositions of synthetic examples and comparative synthetic examples, 186 parts by mass of water, 20 parts by mass of colloidal silica, 10 parts by mass of 75% phosphoric acid, and 10 parts by mass of a silane coupling agent (KBM-403, manufactured by shin-Etsu Silicone Co., Ltd.) were added and mixed thoroughly to prepare coatings of examples and comparative examples, respectively.
< surface treatment >
Various test materials were degreased by spraying water at 60 ℃ for 10 seconds using an alkali degreaser [ a solution prepared by mixing FINE CLEANER E6406 (manufactured by jakeka rice-flour-industries, japan) with water in an amount of 20g/L ]. Thereafter, water was sprayed for 10 seconds, thereby performing water washing. Various paints were applied to each test material after washing with water by a bar coating method, and then dried at 150 ℃ (PMT: the maximum plate temperature of the test material at the time of sintering), thereby forming a coating film having a thickness of 2 μm.
< evaluation test >
(Corrosion resistance)
Various corrosion resistance tests were carried out on the various treated sheets (Nos. 1 to 53) having been surface-treated as described above. The evaluation methods and evaluation criteria are as follows.
Plane section Corrosion resistance test
The area ratio (%) of white rust generated after 120-hour neutral salt water spraying was determined based on the salt water spray test method (JIS-Z-2371: 2015), and the corrosion resistance of the flat surface portion was evaluated according to the following criteria. In this evaluation, C or more is defined as "pass".
A: less than 5 percent
B: more than 5 percent and less than 10 percent
C: more than 10 percent and less than 30 percent
D: over 30 percent
Corrosion resistance test of worked part
After 6mm extrusion processing of each of the treated plates by means of a cup drawing testing machine, neutral salt water spraying was carried out for 72 hours by a salt water spray test method (JIS-Z-2371: 2015), and the area ratio (%) of white rust generated was determined, and the corrosion resistance of the processed portion was evaluated by the following criteria. In this evaluation, C or more is defined as "pass".
AA: less than 5 percent
A: more than 5 percent and less than 10 percent
B: more than 10 percent and less than 20 percent
C: more than 20 percent and less than 30 percent
D: over 30 percent
Corrosion resistance test of alkali-degreased part
The treated plate was sprayed with an alkali degreasing agent (the same as the alkali degreasing agent used for the surface treatment) for 2 minutes, washed with water, and dried. Then, neutral saline spray was performed for 72 hours based on the saline spray test method (JIS-Z-2371: 2015), and the area ratio (%) of white rust generated was determined, and the alkali resistance was evaluated according to the following criteria. In this evaluation, C or more is defined as "pass".
A: less than 5 percent
B: more than 5 percent and less than 10 percent
C: more than 10 percent and less than 30 percent
D: over 30 percent
(test for resistance to Heat discoloration (Heat resistance))
The treated plate was heated in an oven at 200 ℃ for 1 hour, and the color difference (. DELTA.E) before and after heating was determined using a color difference meter (manufactured by Nippon Denshoku Co., Ltd.), and the heat resistance was evaluated based on the following evaluation criteria. In this evaluation, C or more was defined as "acceptable".
A: delta E deficiency of 2
B: delta E is 2 or more and less than 3
C: delta E is 3 or more and less than 5
D: delta E is 5 or more
(solvent resistance test)
While being pressed against various processing plates with a load of 1kg, gauze impregnated with Methyl Ethyl Ketone (MEK) was slid 10 times in a reciprocating manner, and then a color difference (Δ E) before and after the sliding was obtained using a color difference meter, and solvent resistance was evaluated based on the following evaluation criteria. In this evaluation, C or more was defined as "acceptable".
A: delta E less than 0.5
B: delta E is 0.5 or more and less than 1
C: delta E is 1 or more and less than 2
D: delta E is 2 or more
< evaluation result >
The results of the above evaluation tests are shown in tables 4 to 6 below.
Figure GDA0003202175040000271
Figure GDA0003202175040000281
Figure GDA0003202175040000291
TABLE 4
Figure GDA0003202175040000301
TABLE 5
Figure GDA0003202175040000302
TABLE 6
Figure GDA0003202175040000311

Claims (3)

1. A composite comprising an unsaturated polymerizable monomer polymer and a cationic group-containing polyurethane resin,
the cationic group-containing polyurethane resin comprises:
structural units derived from a polyisocyanate having a cyclohexane ring structure represented by the following formula (1),
A structural unit derived from a polyol represented by the following formula (2),
Structural units derived from 2 or more compounds selected from diols represented by the following formulae (3) and (4), and
a structural unit derived from a tertiary amine compound represented by the following formula (5) and/or a salt thereof,
the weight average molecular weight of the diol represented by the formula (3) is 800 or more and 4000 or less,
the weight average molecular weight of the diol represented by the formula (4) is 60 or more and 400 or less,
the cationic group-containing polyurethane resin is a polymer of a urethane prepolymer,
in the urethane prepolymer, the amount of the structural unit derived from a diol represented by the formula (3) is 3 to 40% by mass, and the amount of the structural unit derived from a diol represented by the formula (4) is 1 to 20% by mass,
formula (1): O-C-N-R1－N＝C＝O
In the formula (1), R1with-R2－R3－R4Is represented by (A) to (R)2Is a single bond or alkylene, R3Is expressed by the following formula,
Figure FDA0003202175030000011
wherein, in the formula, R5、R6And R7Independently a hydrogen atom or an alkyl group,
R4is a single bond, alkylene or a group represented by the formula,
Figure FDA0003202175030000012
wherein the left bonding site is bonded to R3Bonding is carried out on the raw materials,
formula (2):
Figure FDA0003202175030000021
in the formula (2), n is an integer,
R8with-R9-R10-R11To represent (a) a (b) to (a),
R9is a single bond,
Figure FDA0003202175030000022
or-R13-CO-，
In that
Figure FDA00032021750300000210
Middle, right bonding site and R10Is bonded at-R13-CO-middle, rightBonding site of side and R10Bonding is carried out on the raw materials,
wherein R is12Is a linear or branched alkylene radical, R13is-R18-O-or
Figure FDA0003202175030000023
And R is18Is a straight-chain or branched alkylene group, x is an integer of 1 to 5, 1 is an integer of 2 to 4,
in-R18in-O-, the right bonding site is bonded to CO,
in that
Figure FDA0003202175030000024
In the middle, the bonding site on the right side is bonded with CO,
R10is a group of the formula,
Figure FDA0003202175030000025
R11is composed of
A single bond, a,
Figure FDA0003202175030000026
Figure FDA0003202175030000027
or-CO-R13-
Wherein, except for the single bond, the bonding site on the left side is bonded to R10Bonding is carried out on the raw materials,
R12is a linear or branched alkylene radical, R13is-R18-O-or
Figure FDA0003202175030000028
And R is15And R16Independently a hydrogen atom, an alkyl group, a haloalkyl group or a phenyl group, R17Is a hydrogen atom, an alkyl group or a phenyl group, R18Is a straight chain or branched chain alkylene group, x is an integer of 1 to 5, 1 is a whole number of 2 to 4The number of the first and second groups is,
in-R18in-O-, the right bonding site is bonded to CO,
in that
Figure FDA0003202175030000029
In the middle, the bonding site on the right side is bonded with CO,
R14is a hydrogen atom, an alkyl group, a phenyl group,
Figure FDA0003202175030000031
Figure FDA0003202175030000032
Wherein R is18Is a straight chain or branched chain alkylene group, l is an integer of 2 to 4,
formula (3): HO-R19－H (3)
In the formula (3), R19Is composed of
Figure FDA0003202175030000033
Wherein the bonding site on the left side is bonded to OH,
m is an integer of 2 to 4, n is an integer,
formula (4): HO-R22－OH
In the formula (4), R22Is composed of
Alkylene, or a mixture thereof,
Figure FDA0003202175030000034
An adamantane ring,
Figure FDA0003202175030000035
Wherein y is 2 or 3, z is an integer of 1 to 6,
formula (5):
Figure FDA0003202175030000036
in the formula, R23Is alkyl, aminoalkyl, hydroxyalkyl,
Figure FDA0003202175030000037
-C(CH2OH)3Or
Figure FDA0003202175030000038
R24Is hydroxyalkyl, aminoalkyl or N-alkylaminoalkyl.
2. An aqueous resin composition comprising the composite according to claim 1.
3. A coating comprising the composite of claim 1.
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