CN108864919B - Composites, water-based resin compositions and coatings - Google Patents

Abstract

An object of the present invention is to provide a composite useful for forming a film having excellent corrosion resistance, heat resistance, and solvent resistance, and an aqueous resin composition (including paint) containing the composite. The above-mentioned problems are solved 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 two or more specific diols, and a structural unit derived from a specific tertiary amine compound and/or a salt thereof.

Description

Composites, water-based resin compositions and coatings

technical field

The present invention relates to a composite, an aqueous resin composition and a paint containing the composite.

Background technique

Conventionally, a technique related to an aqueous resin composition having a good appearance of a coating film and excellent blending stability with an unsaturated polymerizable monomer polymer has been proposed. For example, Patent Document 1 discloses a technique related to an aqueous resin composition in which an unsaturated polymerizable monomer polymer is emulsified by a cationic group-containing polyurethane resin.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2012-1584

SUMMARY OF THE INVENTION

The problem to be solved by the invention

In the aqueous resin composition described in the above-mentioned Patent Document 1, a film excellent in corrosion resistance, heat resistance, and solvent resistance cannot be formed. Therefore, an object of the present invention is to provide a composite useful for forming a film having excellent corrosion resistance, heat resistance, and solvent resistance, and an aqueous resin composition (including paint) containing the composite.

means of solving problems

The present invention to achieve the above object includes the following aspects.

[1] A composite comprising an unsaturated polymerizable monomer polymer and a cationic group-containing polyurethane resin,

The above-mentioned cationic group-containing polyurethane resin includes:

A structural unit 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 two 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-R ¹ -N=C=O

In formula (1), R ¹ is represented by -R ² -R ³ -R ⁴ -, R ² is a single bond or an alkylene group, and R ³ is represented by the following formula:

wherein, in the formula, R ⁵ , R ⁶ and R ⁷ are independently a hydrogen atom or an alkyl group.

R ⁴ is a single bond, an alkylene group or a group represented by the following formula.

In the formula, the bonding site on the left is bonded to ^R3 .

Formula (2):

In formula (2), n is an integer,

R ⁸ is represented by -R ⁹ -R ¹⁰ -R ¹¹ -.

或-R¹³-CO-。R ⁹ is a single bond,

or -R ¹³ -CO-.

中，右侧的键合位与R¹⁰键合，在-R¹³-CO-中，右侧的键合位与R¹⁰键合。exist

In, the bonding site on the right is bonded with R ¹⁰ , and in -R ¹³ -CO-, the bonding site on the right is bonded with R ¹⁰ .

并且R¹⁸为直链或支链的亚烷基，x为1～5的整数，l为2～4的整数。Wherein, R ¹² is a straight-chain or branched alkylene group, and R ¹³ is -R ¹⁸ -O- or

In addition, R ¹⁸ is a linear or branched alkylene group, x is an integer of 1-5, and l is an integer of 2-4.

In -R ¹⁸ -O-, the bonding site on the right is bonded to CO.

中，右侧的键合位与CO键合。exist

, the bonding site on the right is bonded to CO.

R ¹⁰ is a group represented by the following formula.

R ¹¹ is

single bond,

或-CO-R¹³-，

or -CO-R ¹³ -,

Among them, except for single bonds, the bonding site on the left is bonded to R ¹⁰ .

并且R¹⁵及R¹⁶独立地为氢原子、烷基、卤代烷基或苯基，R¹⁷为氢原子、烷基或苯基，R¹⁸为直链或支链的亚烷基，x为1～5的整数，1为2～4的整数。R ¹² is straight-chain or branched alkylene, R ¹³ is -R ¹⁸ -O- or

And R ¹⁵ and R ¹⁶ are independently a hydrogen atom, an alkyl group, a haloalkyl group or a phenyl group, R ¹⁷ is a hydrogen atom, an alkyl group or a phenyl group, R ¹⁸ is a straight-chain or branched-chain alkylene group, and x is 1- An integer of 5, and 1 is an integer of 2 to 4.

In -R ¹⁸ -O-, the bonding site on the right is bonded to CO.

中，右侧的键合位与CO键合。exist

, the bonding site on the right is bonded to CO.

R ¹⁴ is a hydrogen atom, an alkyl group, a phenyl group,

Wherein, R ¹⁸ is a linear or branched alkylene group, and 1 is an integer of 2-4.

Formula (3): HO-R ¹⁹ -H (3)

In formula (3), R ¹⁹ is

Among them, the bonding site on the left side of each is bonded to OH.

或金刚烷环，R²¹为亚烷基，m为2～4的整数，n为整数。R ²⁰ is independently alkylene,

or an adamantane ring, R ²¹ is an alkylene group, m is an integer of 2 to 4, and n is an integer.

Formula (4): HO-R ²² -OH

In formula (4), R ²² is

金刚烷环、alkylene,

adamantane ring,

However, y is 2 or 3, and z is an integer of 1-6.

Formula (5):

In the formula, R ²³ is alkyl, aminoalkyl, hydroxyalkyl,

R ²⁴ is hydroxyalkyl, aminoalkyl or N-alkylaminoalkyl.

[2] The complex according to the above [1], wherein the two or more kinds of diols include a diol (C-1) represented by the above formula (3) and having a weight average molecular weight of more than 600 and a diol (C-1) represented by the above formula ( 4) and a diol (C-2) having a weight average molecular weight of 600 or less.

[3] An aqueous resin composition comprising the complex according to the above [1] or [2].

[4] A paint comprising the complex according to the above [1] or [2].

Invention effect

According to the present invention, a composite useful for forming a film having excellent corrosion resistance, heat resistance, and solvent resistance, and an aqueous resin composition (including a paint) containing the composite can be provided.

Detailed ways

Hereinafter, the present invention will be described in detail by showing specific embodiments.

The composite of one aspect 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 of one aspect of the present invention, a film excellent in corrosion resistance, heat resistance, and solvent resistance can be formed. The above-mentioned cationic group-containing polyurethane resin contains: a structural unit derived from a polyisocyanate having a cyclohexane ring structure represented by the formula (1), a structural unit derived from a polyol represented by the formula (2), and a structural unit derived from the formula ( 3) A structural unit of two or more compounds selected from the diols represented by the formula (4), and a structural unit derived from the tertiary amine compound represented by the formula (5) and/or a salt thereof.

<Unsaturated polymerizable monomer polymer>

The unsaturated polymerizable monomer polymer according to one aspect 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 aspect of the present invention include a carboxylic acid group-containing unsaturated polymerizable monomer, and the carboxylic acid group-containing unsaturated polymerizable monomer. Esterates of monomers, vinyl compounds, etc.

As a carboxylic acid group-containing unsaturated polymerizable monomer, (meth)acrylic acid containing methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc. are mentioned, for example.

Examples of esterified products of carboxylic acid group-containing unsaturated polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. Propyl ester, 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, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylate bicyclo[3,3,1 ] Nonyl ester, 2-methoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, allyl (meth)acrylate, (meth)acrylic acid Diethylaminoethyl, (meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate 3-hydroxypropyl, (meth)acrylate-4- Hydroxybutyl ester, Methoxyethylene glycol (meth)acrylate, Methoxypolyethylene glycol (meth)acrylate, Ethoxyethylene glycol (meth)acrylate, Ethoxypolyethylene glycol Alcohol (meth)acrylate, Propoxyethylene glycol (meth)acrylate, Propoxypolyethylene glycol (meth)acrylate, Methoxypropylene glycol (meth)acrylate, Methoxypolyethylene glycol (meth)acrylate Propylene Glycol (Meth)acrylate, Ethoxypropylene Glycol (Meth)acrylate, Ethoxylated Polypropylene Glycol (Meth)acrylate, Propoxypropylene Glycol (Meth)acrylate, Propoxypropylene Glycol (Methyl) ) acrylates and other mono(meth)acrylates; ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate ) acrylate, triethylene glycol di(meth)acrylate and other di(meth)acrylate compounds; trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate and other tri(meth)acrylate compounds base) acrylate compounds; tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; hexa (meth) acrylate compounds such as sorbitol hexa (meth) acrylate, and the like.

Examples of the vinyl compound include vinyl acetate, vinyl propionate, styrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, butadiene, and isoprene.

In addition, these unsaturated polymerizable monomers can be used individually or in combination of 2 or more types.

In addition to heating, the polymerization of the unsaturated polymerizable monomer can be performed by using a known polymerization initiator.

As the polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2'-azobis( 2-Amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride Azo-based initiators such as nitrogen bis(N,N'-dimethyleneisobutylamidine); substituted ethane-based initiators such as phenyl-substituted ethane, etc. In addition, persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; and radical polymerization initiators such as peroxides such as hydrogen peroxide, t-butyl hydroperoxide, and cumene hydroperoxide can also be used. In addition, reducing agents such as a combination of these radical polymerization initiators with sulfites such as sodium sulfite; bisulfites such as sodium bisulfite; metal salts such as cuprous sulfate and ferrous sulfate; and organic reducing agents such as L-ascorbic acid can also be used. Combined redox initiators.

Moreover, as a polymerization method of an unsaturated polymerizable monomer, a well-known method, such as emulsion polymerization, is used.

The polymerization temperature is appropriately adjusted according to the type of the above-mentioned polymerization initiator, but, for example, it is preferably in the range of 20°C to 100°C.

The usage-amount of the said polymerization initiator is suitable normally with respect to 100 weight part of unsaturated polymerizable monomers, for example, 0.005-1 weight part.

In the production of the composite according to one aspect of the present invention, the polymerization of the unsaturated polymerizable monomer is carried out simultaneously with or after the production reaction of the cationic group-containing polyurethane resin described later.

As the cationic group-containing urethane resin contained in the composite according to one aspect of the present invention, the following urethane resins are used.

<Cationic group-containing polyurethane resin>

Typically, the cationic group-containing polyurethane resin according to one aspect of the present invention is obtained by reacting a urethane prepolymer, an ionizing agent, and water. At this time, in order to promote the reaction, a polyamine compound excluding the tertiary amine compound may be contained as necessary. Specifically, the isocyanate group contained in the urethane prepolymer reacts with an amine produced by water or a polyamine compound contained if necessary to form a urea bond. In addition, a cationic group is introduced by neutralizing a structural moiety derived from the tertiary amine compound represented by the formula (5) contained in the urethane prepolymer with an ionizing agent. In this way, a cationic group-containing polyurethane resin is obtained.

＜Urethane Prepolymer＞

The urethane prepolymer is a component for producing the cationic group-containing urethane resin according to one aspect of the present invention, and is a polyisocyanate having at least a cyclohexane ring structure, containing no nitrogen atom and containing benzene. A component obtained by reacting a cyclic polyol, two or more diols containing no benzene ring and nitrogen atom, and a tertiary amine compound having two or more active hydrogens and/or a salt thereof.

From another viewpoint, the urethane prepolymer includes a structural unit derived from the polyisocyanate having a cyclohexane ring structure represented by the formula (1) and a structure derived from the polyol represented by the formula (2). A unit, a structural unit derived from two or more compounds selected from the diols represented by the formula (3) and the formula (4), and a structural unit derived from the tertiary amine compound represented by the formula (5) and/or a salt thereof.

Specifically, the polyol represented by the formula (2) (hereinafter also abbreviated as "polyol".) and the diol represented by the formula (3) and the formula (4) (hereinafter also abbreviated as "diol".) The hydroxyl group contained in it reacts with the isocyanate group contained in the polyisocyanate (henceforth abbreviated as "polyisocyanate") which has a cyclohexane ring structure represented by Formula (1), and forms a urethane bond. In addition, the isocyanate group contained in the polyisocyanate and the tertiary amine compound represented by the formula (5) (hereinafter also simply referred to as "tertiary amine compound" or "tertiary amine". Active hydrogen) reacts to form urethane bonds or urea bonds.

In addition, the urethane prepolymer used in the present embodiment is a urethane having an isocyanate group derived from a polyisocyanate in order to react with water (any polyamine compound not including a tertiary amine may be used) as described above. Ester prepolymer.

(polyisocyanate)

The polyisocyanate is used to produce a urethane prepolymer, which is represented by the following formula (1).

Formula (1): O=C=N-R ¹ -N=C=O

In formula (1), R ¹ is represented by -R ² -R ³ -R ⁴ -, R ² is a single bond or an alkylene group, and R ³ is a group represented by the following formula,

wherein, in the formula, R ⁵ , R ⁶ and R ⁷ are independently a hydrogen atom or an alkyl group.

R ⁴ is a single bond, an alkylene group or a group represented by the following formula.

In the formula, the bonding site on the left is bonded to ^R3 .

R ¹ is preferably

Among them, R ⁵ , R ⁶ and R ⁷ in the formula are independently a hydrogen atom or a methyl group, and more preferably, all of R ⁵ , R ⁶ and R ⁷ in the formula are a hydrogen atom or a methyl group.

In addition, the bicyclic structure which has a cyclohexane structure is also included as a cyclohexane ring structure. In addition, a plurality of cyclohexane ring structures may be contained in the polyisocyanate.

(Type of polyisocyanate)

The polyisocyanate is not particularly limited as long as it is a polyisocyanate represented by the formula (1) having one or more cyclohexane rings and two or more isocyanate groups, and examples thereof include isophorone diisocyanate, 1 ,3-bis(isocyanate methyl)cyclohexane, 1,4-bis(isocyanate methyl)cyclohexane, 1,3-diisocyanate cyclohexane, 1,4-diisocyanate cyclohexane, 3-isocyanate -Methyl-3,5,5-trimethylcyclohexylisocyanate, dicyclohexylmethane 4,4'-diisocyanate, etc. Polyisocyanates not included in the formula (1), that is, dimers such as uretdione structures, trimers such as isocyanurate structures, and adducts using polyfunctional polyols can also be used The polyisocyanate etc. which have 3 or more isocyanate groups in 1 molecule are used together with the polyisocyanate represented by formula (1).

A polyisocyanate may be used individually by 1 type, and may use 2 or more types together.

Among the above, the polyisocyanate is preferably at least one compound selected from the group consisting of isophorone diisocyanate and dicyclohexylmethane 4,4'-diisocyanate.

(The input amount of polyisocyanate)

In the production of the urethane prepolymer described later, with respect to the polyisocyanate, polyol, two or more kinds of diols, and tertiary amine compounds and/or used in the production of the urethane prepolymer The total amount of the salts thereof is preferably 31 to 70 mass %, and more preferably 40 to 65 mass %, and the input amount of the polyisocyanate is preferably 31 to 70 mass %.

That is, in the urethane prepolymer used in the present embodiment, the amount (in terms of mass) of the polyisocyanate-derived structural unit in the urethane prepolymer is preferably 31 to 70%, and more preferably 40 to 65%.

In the present embodiment, when the “triol or higher polyol containing no benzene ring and nitrogen atom” described later is used in the production of the urethane prepolymer, the benzene ring and nitrogen atom are not contained. The input amount of the triol or more polyols is included in the above total amount.

(Polyol)

The polyol is used to manufacture the urethane prepolymer, which is represented by the following formula (2).

Formula (2):

或-R¹³-CO-。In formula (2), n is an integer, R ⁸ is represented by -R ⁹ -R ¹⁰ -R ¹¹ -, R ⁹ is a single bond,

or -R ¹³ -CO-.

中，右侧的键合位与R¹⁰键合，在-R¹³-CO-中，右侧的键合位与R¹⁰键合，exist

In, the bonding site ^on the right is bonded to R10, in ^-R13 -CO-, the bonding site ^on the right is bonded to R10,

并且R¹⁸为直链或支链的亚烷基，x为1～5的整数，1为2～4的整数，Wherein, R ¹² is a straight-chain or branched alkylene group, and R ¹³ is -R ¹⁸ -O- or

and R ¹⁸ is a linear or branched alkylene group, x is an integer of 1-5, 1 is an integer of 2-4,

In -R ¹⁸ -O-, the bonding site on the right is bonded to CO,

中，右侧的键合位与CO键合。exist

, the bonding site on the right is bonded to CO.

R ¹⁰ is a group represented by the following formula,

R ¹¹ is

single bond,

或-CO-R¹³-，

or -CO-R ¹³ -,

where, except for single bonds, the bonding site ^on the left is bonded to R10,

并且R¹⁵及R¹⁶独立地为氢原子、烷基、卤代烷基或苯基，R¹⁷为氢原子、烷基或苯基，R¹⁸为直链或支链的亚烷基，x为1～5的整数，1为2～4的整数，R ¹² is straight-chain or branched alkylene, R ¹³ is -R ¹⁸ -O- or

And R ¹⁵ and R ¹⁶ are independently a hydrogen atom, an alkyl group, a haloalkyl group or a phenyl group, R ¹⁷ is a hydrogen atom, an alkyl group or a phenyl group, R ¹⁸ is a straight-chain or branched-chain alkylene group, and x is 1- 5 is an integer, 1 is an integer from 2 to 4,

In -R ¹⁸ -O-, the bonding site on the right is bonded to CO,

中，右侧的键合位与CO键合。exist

, the bonding site on the right is bonded to CO.

R ¹⁴ is a hydrogen atom, an alkyl group, a phenyl group,

Wherein, R ¹⁸ is a linear or branched alkylene group, and 1 is an integer of 2-4.

In the above formula (2), R ⁸ is preferably

(右侧的键合位与0H键合)、

(the bonding position on the right is bonded to 0H),

R ¹² is preferably ethylene or isopropylidene. R ¹⁴ is preferably a hydrogen atom, methyl, isopropyl or phenyl. R ¹⁵ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a phenyl group. R ¹⁶ is preferably a hydrogen atom, methyl, ethyl, trifluoromethyl or phenyl. R ¹⁷ is preferably a hydrogen atom, methyl, isopropyl or phenyl.

(type of polyol)

The polyhydric alcohol is not particularly limited as long as it is a polyhydric alcohol represented by formula (2) having one or more benzene rings and two or more hydroxyl groups and no nitrogen atom, and examples thereof include resorcinol, 2- Aromatic polyols such as methyl resorcinol, bisphenol A, bisphenol S, bisphenol F; 2 moles of bisphenol A-ethylene oxide adduct, 4 moles of bisphenol A-ethylene oxide addition compound, 6 moles of bisphenol A-ethylene oxide adduct, 10 moles of bisphenol A-ethylene oxide adduct, 2 moles of bisphenol A-propylene oxide adduct, bisphenol A-propylene oxide 4 moles of adducts, 6 moles of bisphenol A-propylene oxide adducts, 10 moles of bisphenol A-propylene oxide adducts and other polyether polyols with benzene rings; using phthalic acid, isophthalic acid Aromatic polycarboxylic acids such as formic acid, terephthalic acid, trimellitic acid and ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2-methylpropylene glycol, neopentyl glycol, Polyester polyols with benzene rings obtained by polycondensation of polyols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methylpentanediol; Polycarbonate polyols having a benzene ring obtained by transesterification of vinyl esters with polyols such as bisphenol A.

A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

Among the above, the polyol is preferably a polyether polyol having a benzene ring.

(The input amount of polyol)

In the production of the urethane prepolymer described later, with respect to the polyisocyanate, polyol, two or more kinds of diols, and tertiary amine compounds and/or used in the production of the urethane prepolymer The total amount of the salts and the input amount of the polyol can be, for example, usually 1 to 35% by mass, and more preferably 3 to 25% by mass. That is, in the urethane prepolymer used in the present embodiment, the amount (in terms of mass) of the structural unit derived from the polyol of the formula (2) is usually 1 to 35 in the urethane prepolymer. %, preferably 3 to 25%.

In the present embodiment, when the “triol or higher polyol containing no benzene ring and nitrogen atom” described later is used in the production of the urethane prepolymer, the benzene ring and nitrogen atom are not contained. The input amount of triol or more polyols is included in the above total amount.

(diol)

The diols represented by the formulae (3) and (4) are used in the production of the above-mentioned urethane prepolymer. In addition, two or more types of compounds selected from the diols represented by formula (3) and (4) are used for manufacture of this urethane prepolymer.

Formula (3): HO-R ¹⁹ -H (3)

In formula (3), R ¹⁹ is

where the bonding site on the left side of each is bonded to OH,

或金刚烷环，R²¹为亚烷基，m为2～4的整数，n为整数。R ²⁰ is independently alkylene,

or an adamantane ring, R ²¹ is an alkylene group, m is an integer of 2 to 4, and n is an integer.

Formula (4): HO-R ²² -OH (4)

In formula (4), R ²² is

金刚烷环、alkylene,

adamantane ring,

However, y is 2 or 3, and z is an integer of 1-6.

As at least two kinds of diols used in the production of the urethane prepolymer, it is preferable to use 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, and it is more preferable to use a diol having a weight average molecular weight of 600 or less. Diol (C-1) represented by the weight average molecular weight of more than 600, and diol (C-2) represented by the formula (4) and represented by the weight average molecular weight of 600 or less.

In addition, as a diol (C-1), the diol in the range whose weight average molecular weight is 800 or more and 4000 or less is more preferable. As the diol (C-2), a diol having a weight average molecular weight of 60 or more and 400 or less is more preferable.

Unless otherwise specified, the weight average molecular weight of each component in the present embodiment is a value obtained in terms of polystyrene by measuring by GPC (gel permeation chromatography).

(Specific compounds of diols (C-1) and (C-2))

As diol (C-1), polyether diol, polyester diol, polycarbonate diol, etc. can be used, for example.

As said polyether glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol (polytetramethylene ether glycol) etc. are mentioned, for example. Polyether diols are produced by addition-polymerizing alkylene oxides such as ethylene oxide and propylene oxide under a basic catalyst, for example.

As the above-mentioned polyester diol, for example, aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid, unsaturated carboxylic acids such as sebacic acid, etc., as acid species, and alcohols can be mentioned. ethylene glycol, propylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol Diol, 1,10-decanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, cyclohexyldimethanol, 1,3-adamantine Polyester diol produced by esterification of alkanediol or the like.

As said polycarbonate diol, the polycarbonate diol manufactured by ring-opening polymerization of cyclic esters, such as ε-caprolactone, is mentioned, for example, and specifically, dimethyl carbonate, carbonic acid can be mentioned. Polycarbonate diol produced by reacting diethyl ester, diphenyl carbonate, and the like with alcohols exemplified in the above-mentioned polyester diol.

Examples of the diol (C-2) include ethylene glycol (62.07 g/mol), propylene glycol (76.09 g/mol), 1,5-pentanediol (104.15 g/mol), 1,6-hexanediol Diol (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, Alkyl glycols such as 5-pentanediol (118.17g/mol), 1,4-cyclohexyldimethanol (146.14g/mol), 1,3-adamantanediol (168.23g/mol); diethylenediol Alcohol (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), dipropylene glycol (134.17g/mol) and other polyalkylene glycols; dimethylolpropionic acid (134g/mol) and the like.

As diol (C-1), polyether diols, such as polyethylene glycol, polypropylene glycol, and polybutylene glycol, are preferable. As diol (C-2), polyalkylene glycol is preferable.

(the input amount of diol)

In the production of the urethane prepolymer, the amount of polyisocyanate, polyol, two or more diols, and tertiary amine compounds and/or salts thereof used in the production of The total amount of the two or more diols to be added is usually, for example, 2 to 60% by mass, preferably 4 to 55% by mass, and more preferably 7 to 50% by mass. That is, in the urethane prepolymer used in the present embodiment, the amount (in terms of mass) of structural units derived from two or more diols is usually 2 to 60% in the urethane prepolymer , preferably 4 to 55%, more preferably 7 to 50%.

In addition, in the manufacture of the urethane prepolymer, with respect to the polyisocyanate, the polyhydric alcohol, two or more kinds of diols, and the tertiary amine compound and/or used in the manufacture of the urethane prepolymer The total amount of the salts can be usually, for example, 1 to 50 mass %, preferably 3 to 40 mass %, and more preferably 5 to 30 mass %, when the diol (C-1) is used in the input amount.

That is, in the urethane prepolymer used in this embodiment, the presence amount (in terms of mass) of the structural unit of the diol (C-1) is usually 1 to 50% in the urethane prepolymer , preferably 3 to 40%, more preferably 5 to 30%.

In addition, in the production of the urethane prepolymer, with respect to the polyisocyanate, polyol, two or more kinds of diols, and tertiary amine compounds and/or used in the production of the urethane prepolymer The total amount of the salts can be, for example, usually 1 to 25% by mass, preferably 1 to 20% by mass, and more preferably 2 to 15% by mass, when the diol (C-2) is used in an input amount.

That is, in the urethane prepolymer used in this embodiment, the presence amount (in terms of mass) of the structural unit of the diol (C-2) is usually 1 to 25% in the urethane prepolymer , preferably 1 to 20%, more preferably 2 to 15%.

When the "triol or higher polyol containing no benzene ring and nitrogen atom" described later is used in the production of the urethane prepolymer of one aspect of the present invention, the benzene ring and nitrogen atom are not contained The input amount of triol or more polyols is included in the above total amount.

(tertiary amine compound or its salt)

A tertiary amine compound and/or its salt is used for manufacture of the said urethane prepolymer, and it is represented by the following formula (5).

Formula (5):

In the formula, R ²³ is alkyl, aminoalkyl, hydroxyalkyl,

R ²⁴ is hydroxyalkyl, aminoalkyl or N-alkylaminoalkyl.

The aminoalkyl group in R ²³ is preferably -(CH ₂ ) ₂ -NH ₂ or -(CH ₂ ) ₃ -NH ₂ . The aminoalkyl group in R ²⁴ is preferably —(CH ₂ ) ₂ —NH ₂ . The hydroxyalkyl group in R ²³ and R ²⁴ is preferably —(CH ₂ ) ₂ —OH. The N-alkylaminoalkyl group in R ²⁴ is preferably —(CH ₂ ) ₂ —NH—CH ₃ .

A urethane prepolymer into which a group derived from a tertiary amine compound and/or a salt thereof is introduced is obtained by reacting the active hydrogen of the tertiary amine compound and its salt with the above-mentioned polyisocyanate.

In addition, the tertiary amine compound and/or its salt contains two or more active hydrogens, for example, it is preferable to contain two or more substituents which have an active hydrogen, such as an amino group, a hydroxyl group, and an N-alkylamino group. Moreover, as N-alkylamino group, 2-methylamino group is preferable.

(The input amount of the tertiary amine compound and/or its salt)

In the production of the urethane prepolymer described later, with respect to the polyisocyanate, polyol, two or more kinds of diols, and tertiary amine compounds and/or used in the production of the urethane prepolymer The total amount of its salts, the input amount of the tertiary amine compound and/or its salts can be usually, for example, 1 to 20% by mass, preferably 2 to 15% by mass.

That is, in the urethane prepolymer used in the present embodiment, the amount (in terms of mass) of the structural unit derived from the tertiary amine compound of the formula (5) and/or its salt is present in the urethane prepolymer Among them, it is usually 1 to 20%, preferably 2 to 15%.

When the "triol or higher polyol containing no benzene ring and nitrogen atom" described later is used in the production of the urethane prepolymer of one aspect of the present invention, the benzene ring and nitrogen atom are not contained The input amount of triol or more polyols is included in the above total amount.

(Types of tertiary amine compounds)

The tertiary amine compound is not particularly limited as long as it is a tertiary amine having two or more active hydrogens, and examples thereof include N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N- N-aminoalkyldialkanolamines such as tert-butyldiethanolamine, N-(3-aminopropyl)diethanolamine; triethanolamine, N,N,N',N'-tetrakis(2-hydroxyethyl)ethyl Diamine, bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane, 1-bis(2-hydroxyethyl)amino 2-propanol and other optionally substituted trialkanolamines; 2,2' -Diamino-N-methyldiethylamine, N,N',N"-trimethyldiethylenetriamine, tris(2-aminoethyl)amine and other tertiary amines. These tertiary amines can be combined with formic acid, Organic acids such as acetic acid, and inorganic acids such as hydrochloric acid and sulfuric acid are used in the form of salts, and those obtained by quaternizing with an alkylating agent such as dimethyl sulfate, diethyl sulfate, and methyl iodide can also be used. As the tertiary amine compound, N-aminoalkyl dialkanolamine is preferable, and N-methyldiethanolamine is particularly preferable.

The cationic group-containing urethane resin of the present embodiment is a urethane 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. Examples of the acid used at this time include organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, malic acid, malonic acid, and adipic acid; methanesulfonic acid, ethanesulfonic acid, Organic acids such as organic sulfonic acid such as trifluoromethanesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, bromic acid, and phosphoric acid. These acids may be used individually by 1 type, and may use 2 or more types together.

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 sulfates such as dimethyl sulfate and diethyl sulfate; methyl chloride, benzyl chloride, methyl bromide, benzyl bromide, Halogenated alkanes such as methyl iodide; carbonates such as dimethyl carbonate and diethyl carbonate. These quaternizing agents may be used individually by 1 type, and may use 2 or more types together. In addition, an acid and a quaternizing agent may be used in combination as a neutralizing agent.

In addition, in this specification, these acids and quaternizing agents may be called ionizing agents.

In the present specification, "alkyl" or "alkyl" contained in haloalkyl, aminoalkyl, hydroxyalkyl, N-alkylaminoalkyl, etc. is not particularly limited, and is usually an alkane having 20 or less carbon atoms. The group may be an alkyl group having 12 or less carbon atoms or an alkyl group having 6 or less carbon atoms. Typically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, 3-methylpentyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.

The "alkylene group" is also not particularly limited, but 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, Isohexyl, 3-methylpentylene, heptylene, octylene, nonylylene, decylene, undecylene, dodecylene and the like.

Incidentally, the haloalkyl group includes a haloalkyl group in which one or more hydrogen atoms in the above-mentioned alkyl group are substituted by a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

(Other components that can be used in the production of urethane prepolymers)

In the production of the urethane prepolymer of the present embodiment, other components other than those described above may be used. Examples of other components include polyisocyanates other than the above-mentioned polyisocyanates, polyols other than the above-mentioned polyols and the above-mentioned diols that do not contain a benzene ring and nitrogen atom, organic solvents, and polyamine compounds other than the above-mentioned tertiary amine compounds. , ionizing agents, acids, organometallic compounds, etc.

(polyisocyanates other than polyisocyanates)

Although it does not specifically limit as polyisocyanate other than the said polyisocyanate, For example, 1, 4- tetramethylene diisocyanate, (2, 6- diisocyanato) ethyl hexanoate, 1, 6- Hexamethylene diisocyanate, 1,12-dodeca methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or 2,4,4-trimethylhexamethylene diisocyanate Aliphatic diisocyanates such as; isophenylene 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, 4,4'-diisocyanate-3,3'-dimethyl Aromatic diisocyanates such as biphenyl, 3-methyl-diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, tetramethylxylylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2-isocyanato(2,6-diisocyanato)ethylhexanoate, etc. Aliphatic triisocyanates; aromatic triisocyanates such as triphenylmethane triisocyanate, tris(isocyanate phenyl) phosphorothioate, and the like. Polyisocyanates other than the above-mentioned polyisocyanates may be dimers such as uretdione structures, trimers such as isocyanurate structures, or may be adducts using polyfunctional polyols. A polyisocyanate having three or more isocyanate groups in one molecule.

Among them, aromatic polyisocyanates such as aromatic diisocyanates and aromatic triisocyanates are preferably used, and aromatic diisocyanates are more preferably used. The content of the other components and the amount of the structure derived from the other components in the urethane prepolymer can be appropriately set by those skilled in the art within a range that does not inhibit the effects of the present invention.

(Polyols other than the polyols represented by the above formula (2) and the diols represented by the above formulas (3) and (4))

As the polyol other than the polyol represented by the above formula (2) and the diol represented by the above formula (3) and (4), a triol or higher polyol containing no benzene ring and nitrogen atom can be used, For example, trimethylolpropane, pentaerythritol, etc. are mentioned.

Among triol or more polyols that do not contain a benzene ring and nitrogen atom, trimethylolpropane (TMP) is preferable. When a triol or higher polyol containing no benzene ring and nitrogen atom is used for the production of a urethane prepolymer, compared to the polyisocyanate, polyvalent polyol used in the production of the urethane prepolymer The total amount of alcohol, two or more diols, tertiary amine compounds and/or their salts, and polyols containing no benzene rings and nitrogen atoms of triols or more, the input amount of the polyols is preferably 0.5 to 18% by mass, More preferably, it is 3 to 15 mass %. That is, in the urethane prepolymer used in the present embodiment, the amount (in terms of mass) of the structural unit derived from a triol or higher polyol that does not contain a benzene ring and a nitrogen atom is present in the urethane prepolymer. The content is usually 0.5 to 18%, preferably 3 to 15%.

The urethane prepolymer and the cationic group-containing polyurethane resin according to the present embodiment preferably have a branched structure. As a method of introducing a branched structure, the method of using a triol or more polyol containing no benzene ring and nitrogen atom as described above is mentioned, but it is not limited to this method.

In the production of a urethane prepolymer and/or the production of a cationic group-containing urethane resin, an organic solvent can be used. The organic solvent is used as a solvent for reacting the above-mentioned components. The organic solvent is not particularly limited, and examples thereof include ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester-based solvents such as ethyl acetate and butyl acetate; tetrahydrofuran, 1,4-dioxane, etc. Ether-based solvents such as alkane; nitrile-based solvents such as acetonitrile and acrylonitrile; acrylate-based solvents such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate; dimethylformamide, dimethyl ethyl acetate, etc. Amide-based solvents such as amides, N-methylpyrrolidone, N-ethylpyrrolidone, etc.; sulfoxide-based solvents such as dimethyl sulfoxide.

From the viewpoint of reducing the load on the environment, these organic solvents can be removed by vacuum distillation if necessary after production of the urethane prepolymer or the cationic group-containing urethane resin.

The composite and the aqueous resin composition of the present embodiment can be produced by the following method.

A urethane prepolymer having an isocyanate group at a terminal is produced by dissolving and reacting a polyisocyanate, a polyol, two or more diols, a tertiary amine compound, and/or a salt thereof in an organic solvent.

In addition, as an organic solvent, arbitrary organic solvents, such as acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, and butyl acetate, can be used.

Next, after adding an unsaturated polymerizable monomer to the urethane prepolymer having an isocyanate group at the terminal to prepare a uniform solution, the urethane prepolymer having an isocyanate group at the terminal is ionized with an ionizing agent. Part or all of the tertiary amine is ionized, and water is added to emulsify it, and if necessary, a polyamine compound is added to perform a chain extension reaction, whereby a cationic group-containing polyurethane resin can be produced.

In addition, when the unsaturated polymerizable monomer does not contain an active hydrogen group in the molecule, other components (polyisocyanates, polyols, two or more diols, tertiary amine compounds and/or salts thereof, etc.) are mixed. In this case, unsaturated polymerizable monomers may also be mixed.

Furthermore, at the same time as the chain extension or after the reaction, an unsaturated polymerizable monomer is polymerized to generate an unsaturated polymerizable monomer polymer, and then the organic solvent is distilled off under reduced pressure, whereby an embodiment comprising the present invention can be produced. The composite water-based resin composition.

In addition, in this specification, a "composite" means a composite polymer emulsion of a cationic group-containing polyurethane resin and an unsaturated polymerizable monomer polymer. More specifically, it refers to a composite polymer emulsion obtained by emulsification of an unsaturated polymerizable monomer polymer using a cationic group-containing polyurethane resin as an emulsifier.

When producing the composite according to one aspect of the present invention, it is preferable to adjust the total mass (Y _M ) of each component used in the production of the urethane prepolymer and the mass (Y M ) of the above-mentioned unsaturated polymerizable monomer. The ratio [X _M /Y _M ] of X _M ) is in the range of 20/80 to 60/40, and more preferably [X _M /Y _M ] is adjusted to be in the range of 30/70 to 60/40.

(polyamine compound)

It does not specifically limit as a polyamine compound which is a chain extender used in manufacture of the said cationic group-containing polyurethane resin, For example, ethylenediamine, 1,2-propylenediamine, 1,6 can be used - Hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethyldiamine, 3,3'-dimethyl-4 ,4'-dicyclohexylmethyldiamine, 1,4-cyclohexanediamine, 1,3-bisaminomethylcyclohexane, 2-aminoethylaminopropyltrimethoxysilane; N-hydroxymethyl Aminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; Diethylenetriamine, Dipropylene Triamine, triethylenetetramine; hydrazine, 1,6-hexamethylene dihydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophenylene Dicarboxylic acid dihydrazide; β-semicarbazide propionyl hydrazide, 3-semicarbazide propylcarbazate, semicarbazide-3-semicarbazide methyl-3,5,5-trimethylcyclohexane, etc. Among them, hydrazine or ethylenediamine is preferably used.

When a chain extender is used, the input amount of the polyamine compound is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

Furthermore, in the aqueous resin composition which concerns on one aspect of this invention, various additives generally used can be used as needed. Examples of such additives include weather-resistant agents, antibacterial agents, antifungal agents, pigments, fillers, rust inhibitors, dyes, film-forming aids, inorganic cross-linking agents, and organic cross-linking agents (eg, blocked isocyanate-based cross-linking agents). linking agent, epoxy-based cross-linking agent, carbodiimide-based cross-linking agent, oxazoline-based cross-linking agent, melamine-based cross-linking agent, etc.), silane coupling agent, anti-blocking agent, viscosity modifier, fluid Leveling agent, defoaming agent, dispersion stabilizer, light stabilizer, antioxidant, ultraviolet absorber, inorganic filler, organic filler, plasticizer, lubricant, antistatic agent, etc.

In addition, the aqueous resin composition according to the present embodiment can be widely used as a general coating material, and is particularly suitable for use as a coating material such as a metal surface treatment agent.

The aqueous resin composition according to the present embodiment preferably contains the above-mentioned complex as an active ingredient corresponding to various uses such as paint.

Example

Hereinafter, the composite according to the present embodiment and the aqueous resin composition and paint containing the composite will be described in detail using examples. However, the present invention is not limited to this example.

Before preparing the coatings of Examples and Comparative Examples, the synthesis methods of various composites used in the preparation of various coatings are shown below.

<Synthesis example 1>

37.8 g of bisphenol A-polyoxyethylene 2-mol adduct (Newpol BPE-20T, manufactured by Sanyo Chemical Industry Co., Ltd.), 40.3 g of polyethylene glycol (PEG2000, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), diethylene glycol ( Diethylene glycol, manufactured by Nippon Shokubai Corporation) 17.6 g, N-methyldiethanolamine (amino alcohol MDA, manufactured by Nippon Emulsifier) 17.6 g, isophorone diisocyanate (Desmodur I, manufactured by Bayer Corporation) 138.7 g, 168 g of methyl methacrylate (manufactured by Kanto Chemical Co., Ltd.) was added to 150 g of methyl ethyl ketone, and dissolved sufficiently. After making this mixed solution react at 50 degreeC for about 5 hours, it was confirmed to contain 3 mass % or less of isocyanate groups. Next, the solution was cooled to 45°C, and 10 g of dimethyl sulfate was added. Next, 1500 g of water was added, and 1.3 g of potassium persulfate was added, and the reaction was carried out at 75° C. for 3 hours. Then, methyl ethyl ketone was removed by vacuum distillation at 50° C. to obtain 25% of non-volatile components (including complexes). Waterborne resin composition. In addition, regarding the content rate of isocyanate groups, according to JIS K7301:1995, 2 g of the reaction solution was dissolved in dimethylformamide, 10 ml of n-dibutylamine-toluene solution was added, bromophenol blue was used as an indicator, and 0.5 mol/L hydrochloric acid solution was titrated and calculated using the following formula.

【Number 1】

(wherein, A refers to the volume of hydrochloric acid solution required for titration for the amount (mass) of isocyanate used when preparing a predetermined amount of reaction solution, B refers to the volume of hydrochloric acid solution required to titrate the reaction solution, f refers to "1", N refers to the molar concentration of the standard solution of hydrochloric acid, and S refers to the mass of the reaction solution.)

<Synthesis Examples 2 to 45>

Except making each component and input amount (mass %) shown in Table 1 and Table 2, the same method as that of Synthesis Example 1 was carried out to obtain 25% of non-volatile components (including complexes) of Synthesis Examples 2 to 45. Waterborne resin composition.

<Synthesis Example 46>

A non-volatile component containing 25% was obtained by the same method as in Synthesis Example 1, except that 10 g of 85% phosphoric acid was used in place of 10 g of dimethyl sulfate, using the components and the input amounts (mass %) shown in Table 2. The aqueous resin composition of Synthesis Example 46 (comprising a complex).

<Synthesis Example 47>

Using the respective components and input amounts (mass %) shown in Table 2, except that 4 g of formic acid was used instead of 10 g of dimethyl sulfate, a nonvolatile component containing 25% (including Composite) of the aqueous resin composition of Synthesis Example 47.

<Comparative Synthesis Examples 1 to 4>

The aqueous solutions of Comparative Synthesis Examples 1 to 4 containing 25% of nonvolatile components (including complexes) were obtained in the same manner as in Synthesis Example 1, except that the components and the input amounts (mass %) shown in Table 3 were used. resin composition.

Each component described in Tables 1 to 3 is shown below. In addition, the input amount (mass %) of each component used for manufacture of the urethane prepolymer described in Tables 1 to 3 is based on the total amount of each component (A) to (E) below. calculate.

<Polyisocyanate (A; some of the following are polyisocyanates having a cyclohexane ring structure)>

A1: Isophorone diisocyanate (Desmodur I, manufactured by Bayer AG)

A2: Dicyclohexylmethane 4,4'-diisocyanate (Desmodur W, manufactured by Bayer Corporation)

A3: 1,3-bis(isocyanate methyl)cyclohexane (Takenate 600, manufactured by Mitsui Chemicals Co., Ltd.)

A4: Hexamethylene diisocyanate (50M-HDI, manufactured by Asahi Kasei Corporation)

<Polyol (B)>

B1: Bisphenol A-polyoxyethylene 2-mol adduct (Newpol BPE20T, manufactured by Sanyo Chemical Industry Co., Ltd.)

B2: Aromatic dibasic acid polyester polyol (Teslarc (TL series) 2508-70, manufactured by Hitachi Chemical Co., Ltd.)

B3: Polycarbonate diol (Nippollan 981, manufactured by Tosoh Corporation)

<Diol (C; some of the following are diols containing no benzene ring and nitrogen atom)>

C1: Polyethylene glycol (PEG2000, Mw2000, manufactured by Sanyo Chemical Industry Co., Ltd.)

C2: Polyethylene glycol (PEG400, Mw400, manufactured by Sanyo Chemical Industry Co., Ltd.)

C3: Polyethylene glycol (PEG1000, Mw1000, manufactured by Sanyo Chemical Industry Co., Ltd.)

C4: Polyethylene glycol (PEG4000, Mw4000, manufactured by Sanyo Chemical Industry 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 Shokubai Co., Ltd.)

C8: Diethylene glycol (diethylene glycol, Mw106, manufactured by Nippon Shokubai Co., Ltd.)

<Tertiary amine (D)>

D1: N-methyldiethanolamine (amino alcohol MDA, manufactured by Nippon Emulsifier Co., Ltd.)

<Others (triol or higher polyols containing no benzene ring and nitrogen atom) (E)>

E1: Trimethylolpropane (TMP, manufactured by Perstorp)

<Unsaturated polymerizable monomer (X)>

x1: Methyl methacrylate (manufactured by Kanto Chemical Co., Ltd.)

x2: Butyl acrylate (manufactured by Kanto Chemical Co., Ltd.)

x3: methyl methacrylate + styrene (manufactured by Kanto Chemical Co., Ltd.) [mass ratio 1:1]

<Test material (metal material)>

The following metallic materials were used in the test materials.

GI: Hot dip galvanized steel sheet (thickness: 0.6 mm, coating weight: 50 g/m ² on one side)

EG: Electro-galvanized steel sheet (thickness: 0.6 mm, coating weight: 20 g/m ² on one side)

GL: Fused 55% aluminum-zinc alloy plated steel sheet (plate thickness: 0.4 mm, plating adhesion amount: 75 g/m ² on one side)

<Preparation of paint>

To 100 parts by mass of each aqueous resin composition of the synthesis example and the comparative synthesis example, 186 parts by mass of water, 20 parts by mass of colloidal silica, 10 parts by mass of 75% phosphoric acid, and a silane coupling agent (KBM-403, Shin-Etsu Silicon) were added. Ketone Co., Ltd.) 10 parts by mass were mixed well to prepare paints of Examples and Comparative Examples, respectively.

＜Surface treatment＞

Using an alkali degreaser [a solution prepared by mixing FINE CLEANER E6406 (manufactured by Pakase Seiki Co., Ltd., Japan) with water in an amount of 20 g/L] and spraying it at 60°C for 10 seconds, various samples were tested. Material was degreased. After that, water washing was performed by spraying water for 10 seconds. Various paints were applied to the various test materials after washing with water by bar coating, and then dried at 150°C (PMT: the highest plate temperature of the test material during firing) to form coatings with a film thickness of 2 μm. membrane.

<Evaluation test>

(corrosion resistance)

Various corrosion resistance tests were performed with respect to the various treated boards (No. 1-53) surface-treated as mentioned above. The evaluation method and evaluation criteria are as follows.

・Flat part corrosion resistance test

Based on the salt spray test method (JIS-Z-2371:2015), the area ratio (%) of the generated white rust was obtained after neutral salt water spray for 120 hours, and the flat surface corrosion resistance was evaluated according to the following criteria. In addition, in this evaluation, C or more was made into pass.

A: Less than 5%

B: 5% or more and less than 10%

C: 10% or more and less than 30%

D: 30% or more

・Corrosion resistance test of processing part

After extruding the various treated plates to 6 mm using a cupping tester, the area of the white rust generated was determined after being sprayed with neutral salt water for 72 hours based on the salt spray test method (JIS-Z-2371:2015). Ratio (%), the corrosion resistance of the processed part was evaluated according to the following criteria. In addition, in this evaluation, C or more was made into pass.

AA: less than 5%

A: 5% or more and less than 10%

B: 10% or more and less than 20%

C: 20% or more and less than 30%

D: 30% or more

·Corrosion resistance test of alkali degreasing part

The treated plate was sprayed with an alkali degreaser (same as the alkali degreaser used for the surface treatment) for 2 minutes, washed with water, and dried. Then, based on the salt spray test method (JIS-Z-2371:2015), after performing neutral salt water spray for 72 hours, the area ratio (%) of the generated white rust was determined, and the alkali resistance was evaluated according to the following criteria. In addition, in this evaluation, C or more was made into pass.

A: Less than 5%

B: 5% or more and less than 10%

C: 10% or more and less than 30%

D: 30% or more

(Heat discoloration resistance test (heat resistance))

The treated plate was heated in an oven at 200° C. for 1 hour, the color difference (ΔE) before and after heating was determined using a color difference meter (manufactured by Nippon Denshoku Corporation), and the heat resistance was evaluated based on the following evaluation criteria. In this evaluation, C or more was made pass.

A: △E is less than 2

B: ΔE is 2 or more and less than 3

C: ΔE is 3 or more and less than 5

D: △E is 5 or more

(Solvent resistance test)

The gauze impregnated with methyl ethyl ketone (MEK) was pressed against various treatment plates with a load of 1 kg, and after sliding it back and forth 10 times, the color difference (ΔE) before and after sliding was obtained using a color difference meter, and the evaluation was based on the following evaluation criteria. Solvent resistance. In this evaluation, C or more was made pass.

A: △E is less than 0.5

B: ΔE is 0.5 or more and less than 1

C: ΔE is 1 or more and less than 2

D: ΔE is 2 or more

＜Evaluation results＞

The results of the above evaluation tests are shown in Tables 4 to 6 below.

Table 4

table 5

Table 6

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,

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,

wherein the left bonding site is bonded to R³Bonding is carried out on the raw materials,

formula (2):

in the formula (2), n is an integer,

R⁸with-R⁹-R¹⁰-R¹¹To represent (a) a (b) to (a),

R⁹is a single bond,

or-R¹³-CO-，

In that

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

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

In the middle, the bonding site on the right side is bonded with CO,

R¹⁰is a group of the formula,

R¹¹is composed of

A single bond, a,

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

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

In the middle, the bonding site on the right side is bonded with CO,

R¹⁴is a hydrogen atom, an alkyl group, a phenyl group,

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

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,

An adamantane ring,

Wherein y is 2 or 3, z is an integer of 1 to 6,

formula (5):

in the formula, R²³Is alkyl, aminoalkyl, hydroxyalkyl,

-C(CH₂OH)₃Or

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.