JP7324790B2 - paint composition - Google Patents

Description

The present invention relates to coating compositions, and in particular to solvent-based coating compositions for forming urea resins.

Polyurethane resin compositions are excellent in physical properties such as abrasion resistance, bendability, flexibility, softness, workability, adhesiveness, and chemical resistance, and are also excellent in suitability for various processing methods. It is widely used as a coating material for parts, clothing, furniture, home appliances, daily goods, construction, civil engineering, and automobile parts, as a resin component for inks, adhesives, paints, etc., or as various molded products such as films and sheets. there is

In the field of coating materials and paints, it is required to further improve the strength and durability of the resulting paint film (coating). However, although coating films obtained from conventional polyurethane resins are excellent in flexibility, it has been difficult to satisfy the quality requirements in fields where strength (tensile strength) is required.

Urea bonds (formed by the reaction of polyamine compounds and polyisocyanate compounds) are more reactive than urethane bonds, so curing time can be shortened. have. Therefore, applications of resins having urea bonds are expected also in the fields of coating materials and paints.

However, since the reaction speed (curing speed) of the polyamine compound and the polyisocyanate compound is extremely high, it is difficult to carry out the reaction with a conventional mixing device. For this reason, this reaction is carried out using special equipment such as an impingement mixing gun, and it is extremely difficult to apply it industrially.

Various studies have been made to control the reaction rate.
For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2002-80555) describes a liquid A containing an organic polyisocyanate and a liquid B containing a polyoxyalkylene polyamine having an average molecular weight of 200 to 10000 and an alkyl group-substituted aromatic polyamine. A two-component curing resin is described which is reacted.

In addition, studies have also been conducted focusing on the fact that the use of an aromatic polyamine compound lengthens the reaction time to some extent, that is, the pot life (also referred to as pot life) can be lengthened compared to the case of using an aliphatic polyamine compound. For example, Patent Document 2 (JP-A-2009-242600) describes a urea-urethane resin composition comprising a terminal isocyanate prepolymer, an aromatic amine, hydrophilic silica and a curing accelerator.

JP-A-2002-80555 Japanese Patent Application Laid-Open No. 2009-242600

However, it is necessary to further investigate the control of the rate of the urea bond formation reaction, and there is also a problem that the obtained coating film does not meet the required physical properties such as elongation rate and mechanical strength. . For example, when an aromatic amine compound as disclosed in Patent Document 2 is used, there is a problem that the obtained coating film has poor weather resistance and cannot be used for exterior applications.

An object of the present invention is to provide a coating composition which can be cured at a lower rate and which can form a coating film having good weather resistance.

The present disclosure provides the following [1] to [7].
[1]
A coating composition comprising a main agent (I) and a curing agent (II),
The main agent (I) contains a polyamine compound (A),
The curing agent (II) contains a polyisocyanate compound (B),
At least one of the main agent (I) and the curing agent (II) contains a carbonyl compound (C),
The polyamine compound (A) is at least one selected from aliphatic polyamine compounds and alicyclic polyamine compounds and includes a polyamine compound (A1) having at least one of a primary amino group and a secondary amino group. ,
paint composition.
[2]
The coating composition according to [1], wherein the polyamine compound (A1) is an aliphatic polyamine compound.
[3]
The coating composition according to [1] or [2], wherein the polyisocyanate compound (B) is at least one selected from aliphatic isocyanate compounds and alicyclic isocyanate compounds.
[4]
The coating composition according to any one of [1] to [3], wherein the carbonyl compound (C) is at least one selected from ester compounds, ketone compounds and amide compounds.
[5]
The carbonyl compound (C) includes a cyclic ester compound, a cyclic ketone compound, a cyclic amide compound, a chain ester compound having two or more carbonyl groups, a chain ketone compound having two or more carbonyl groups, and two or more carbonyl groups. The coating composition according to any one of [1] to [4], which is at least one selected from chain amide compounds having
[6]
The coating composition according to any one of [1] to [5], wherein the carbonyl compound (C) is a compound having two or more α-hydrogens.
[7]
[ 1] The coating composition according to any one of [6].

The present invention provides a coating composition that can be cured at a lower rate and that is capable of forming a coating with good weather resistance.

The coating composition of the present disclosure is a two-component curable coating composition containing main agent (I) and curing agent (II). In the coating composition of the present disclosure,
The main agent (I) contains a polyamine compound (A),
Curing agent (II) contains a polyisocyanate compound (B),
At least one of the main agent (I) and the curing agent (II) contains a carbonyl compound (C),
The polyamine compound (A) is at least one selected from aliphatic polyamine compounds and alicyclic polyamine compounds and includes a polyamine compound (A1) having at least one of a primary amino group and a secondary amino group.

By containing the carbonyl compound (C), the coating composition of the present disclosure can suppress the reaction rate between the polyamine compound (A) and the polyisocyanate compound (B). Moreover, by using at least one selected from aliphatic polyamine compounds and alicyclic polyamine compounds as the polyamine compound (A), the coating composition of the present disclosure can form a coating film with good weather resistance. On the other hand, usually when an aliphatic polyamine compound or an alicyclic polyamine compound is used, the reaction between the polyamine compound and the isocyanate compound tends to be faster, making it difficult to control the reaction. However, in the coating composition of the present disclosure, by containing the carbonyl compound (C), it is possible to control the reaction rate even when using an aliphatic polyamine compound or an alicyclic polyamine compound.
Although this should not be construed as being limited to a specific theory, it is presumed as follows. The nucleophilicity of the amino group is considered to be the dominant factor in the reaction rate of the reaction between the polyamine compound and the isocyanate compound (reaction to form a urea group). This is also supported by the fact that the urea group-forming reaction proceeds significantly faster when an aliphatic amine having an electron-donating group is used than when an aromatic amine having an electron-withdrawing group is used. Therefore, it is important how to control the nucleophilicity of the amino group. In the coating composition of the present disclosure, the amino group of the highly nucleophilic polyamine compound (A1) also interacts with the carbonyl compound (C) in some way, and as a result, the polyamine compound (A) and the polyisocyanate compound It is considered that the reaction with (B) is less likely to occur.

[Polyamine compound (A)]
Polyamine compound (A) is a compound having two or more amino groups. The polyamine compound (A) contains at least one polyamine compound (A1) selected from aliphatic polyamine compounds and alicyclic polyamine compounds.

In one embodiment, two or more amino groups are present at the molecular ends of polyamine compound (A).

(Polyamine compound (A1))
The polyamine compound (A1) has at least one group selected from a primary amino group (R--NH ₂ ) and a secondary amino group (R--NH--R) as an amino group. Here, each R is independently a monovalent organic group.

The polyamine compound (A1) preferably has two or more primary amino groups and/or secondary amino groups as amino groups. For example, the amino group of the polyamine compound (A1) may have 2 or more primary amino groups, or 2 or more secondary amino groups, and is a primary amino group and a secondary amino group, The total may be 2 or more.

An aliphatic polyamine compound is a polyamine compound that does not have a ring structure in its molecular structure.
Examples of aliphatic polyamine compounds include alkylenepolyamine compounds, polyalkylenepolyamine compounds, and other aliphatic polyamine compounds.

Examples of alkylenepolyamine compounds include H ₂ N—R ¹ —NH ₂ and R ² HN—R ¹ —NHR ² (wherein R ¹ is substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms). a divalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted, and R ² is a monovalent hydrocarbon group).
More specifically, the alkylenepolyamine compounds include methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane. , 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane and the like.

A polyalkylene polyamine compound has a molecular structure in which primary, secondary or tertiary amino groups are linked via alkylene chains such as methylene chains, ethylene chains, propylene chains and butylene chains.
Examples of polyalkylenepolyamine compounds include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexamethylenetetramine.

Other aliphatic polyamine compounds include, for example, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2′-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3- aminoethyl)amine, bishexamethylenetriamine, aspartate amine represented by the following formula (11), and the like.

[In the above formula, R ⁶¹ is a divalent organic group having no ring structure, which may be branched or linear. The divalent organic group is preferably an aliphatic group, more preferably an alkylene group having 2 to 12 carbon atoms, still more preferably an alkylene group having 4 to 8 carbon atoms.
R ⁶² are the same or different organic groups having 1 to 20 carbon atoms and having no ring structure, preferably the same or different, branched or linear groups having 1 to 12 carbon atoms and more preferably the same or different, branched or linear alkyl groups having 1 to 8 carbon atoms. ]

Commercially available products may be used as the aspartic acid ester amine. Examples of commercially available products include Desmophen NH1220 (manufactured by Sumika Covestro Urethane Co., Ltd.) represented by the following formula.

In one embodiment, other aliphatic polyamine compounds include polyamine compounds having alkylene oxide groups such as polyoxypropylenediamine, trimethylolpropane poly(oxypropylene)triamine, glycerylpoly(oxypropylene)triamine, and the like.

In one embodiment, other aliphatic polyamine compounds include, for example, compounds represented by the following formula (12) or (13).

[In the above formulas (12) and (13), each symbol is as follows.
R ⁵ , R ^5′ and R ⁴³ are each independently a hydrogen atom or a monovalent hydrocarbon group (eg, methyl group, ethyl group, etc.). In one embodiment, ^R5 and ^R5' are hydrogen atoms.
R ³¹ is a divalent hydrocarbon group, preferably an alkylene group having 1 to 5 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ³¹ is more preferably an alkylene group having 1 to 3 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ³¹ is, for example, -CH(CH ₃ )CH ₂ -, -CH ₂ CH(CH ₃ )-.
n3 is 1-70, preferably 1-40.
R ³² is a divalent hydrocarbon group, preferably an alkylene group having 1 to 5 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ³² is more preferably an alkylene group having 1 to 3 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ³² is, for example, -CH(CH ₃ )CH ₂ -, -CH ₂ CH(CH ₃ )-.
Each R ⁴¹¹ is independently an alkylene group having 1 to 5 carbon atoms and may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ⁴¹¹ is more preferably an alkylene group having 1 to 3 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ⁴¹¹ is, for example, -CH(CH ₃ )CH ₂ -, -CH ₂ CH(CH ₃ )-.
R ⁴²¹ is an alkylene group having 1 to 5 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ⁴²¹ is more preferably an alkylene group having 1 to 3 carbon atoms, such as a methylene group.
Each R ⁴¹² is independently an alkylene group having 1 to 5 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ⁴¹² is more preferably an alkylene group having 1 to 3 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ⁴¹² is, for example, -CH(CH ₃ )CH ₂ -, -CH ₂ CH(CH ₃ )-.
R ⁴²² is an alkylene group having 1 to 5 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ⁴²² is more preferably an alkylene group having 1 to 3 carbon atoms, such as a methylene group.
Each R ⁴¹³ is independently an alkylene group having 1 to 5 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ⁴¹³ is more preferably an alkylene group having 1 to 3 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ⁴¹³ is, for example, -CH(CH ₃ )CH ₂ -, -CH ₂ CH(CH ₃ )-.
R ⁴²³ is an alkylene group having 0 to 5 carbon atoms, which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. R ⁴²³ is more preferably an alkylene group having 1 to 3 carbon atoms, such as a methylene group. In one embodiment, R ⁴²³ is a 0-carbon alkylene group, ie, a single bond.
n41 is 1-33, n42 is 1-33, and n43 is 1-33. The sum of n41, n42 and n43 is 3-99, preferably 5-85. ]

An alicyclic polyamine compound is a polyamine compound having an alicyclic structure in its molecular structure.

Examples of the alicyclic structure include structures containing 3- to 18-membered rings, specifically 4- to 12-membered rings. The alicyclic polyamine compound may be a monocyclic compound or a polycyclic compound. In addition, in the case of a polycyclic compound, the above-mentioned "ring structure" indicates the ring having the largest number of atoms. The alicyclic structure may be a structure having a substituent or a structure having no substituent.

In one embodiment, the number of carbon atoms in the alicyclic polyamine compound may be 3-80, or 6-24.

In one embodiment, the molecular weight of the alicyclic polyamine compound is, for example, 40-1,000, specifically 100-300.

Examples of alicyclic polyamine compounds include 1,4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, 4,4′-isopropylidenebiscyclohexylamine, 2,5(2,6)-bis(amino methyl)bicyclo[2.2.1]heptane (e.g., norbornadiamine), bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane (e.g., 4,4′-diaminodicyclohexylmethane, etc.), isophoronediamine, mensendiamine ( MDA), 1,4-bis-(8-aminopropyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2′-aminoethylpiperazine), 1-[2′-(2″ -aminoethylamino)ethyl]piperazine, 1,11-diazacycloeicosane, 1,15-diazacyclooctacosane and the like.

In one embodiment, as the alicyclic polyamine compound, an aspartic acid ester amine represented by the following formula (14) can be mentioned.

[In the above formula, R ^61′ is a divalent organic group, which may be branched or linear, and may have an alicyclic structure. The divalent organic group is preferably an aliphatic group, more preferably an alkylene group having 3 to 80 carbon atoms and/or a cycloalkylene group, still more preferably an alkylene group having 6 to 24 carbon atoms and/or or a cycloalkylene group.
R ^62′ is the same or different and an organic group having 1 to 20 carbon atoms, preferably the same or different and a branched or linear alkyl group having 1 to 12 carbon atoms. , more preferably the same or different, are branched or linear alkyl groups having 1 to 8 carbon atoms, and may have an alicyclic structure.
However, at least one of R ^61′ and R ^62′ has a ring structure, preferably R ^61′ has a ring structure. ]

The alkylene group and/or cycloalkylene group represents an alkylene group, a cycloalkylene group, or a combination of an alkylene group and a cycloalkylene group.

Commercially available products may be used as the aspartic acid ester amine. Commercially available products include, for example,
Desmophen NH1420:

Desmophen NH1520:

(both of which are manufactured by Sumika Covestro Urethane Co., Ltd.).

In one embodiment, polyamine compound (A1) is an aliphatic polyamine compound.

In one embodiment, the polyamine compound (A1) is an alicyclic polyamine compound.

In one embodiment, the coating composition of the present disclosure contains an aliphatic polyamine compound and an alicyclic polyamine compound as the polyamine compound (A1). By including these compounds, the reaction rate of the resulting coating composition can be further suppressed. Moreover, the durability of the resulting coating film can be further improved.

In one embodiment, the content of the alicyclic polyamine compound is 0 to 99 parts by mass, preferably 20 to 90 parts by mass, more preferably 100 parts by mass of the total polyamine compound (A). 20 to 80 parts by mass.

In one embodiment, the content of the alicyclic polyamine compound is 40 to 90 parts by mass with respect to the total of 100 parts by mass of the polyamine compound (A).

The weight average molecular weight of the polyamine compound (A1) is, for example, 150 to 10,000, specifically 200 to 10,000, 220 to 4,000. When the weight average molecular weight of the polyamine compound (A1) is within the above range, the reaction rate of the obtained coating composition can be further suppressed. Moreover, the durability of the resulting coating film can be further improved. In the present disclosure, the weight average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography (GPC).

In one embodiment, the polyamine compound (A1) has a weight average molecular weight of, for example, 1,000 to 10,000, more specifically 1,500 to 4,000. Having such a weight average molecular weight is advantageous from the viewpoint of suppressing the reaction rate.

In one embodiment, the polyamine compound (A) has 20 to 80 parts by mass of the polyamine compound (A1) with respect to 100 parts by mass of the polyamine compound (A).

In one embodiment, polyamine compound (A) comprises only polyamine compound (A1).

(Other polyamine compounds)
The polyamine compound (A) may further contain an aromatic polyamine compound within a range that does not impair the effects of the present invention. Here, the aromatic polyamine compound is a polyamine compound having an aromatic ring in its molecular structure. Inclusion of an aromatic polyamine compound makes it easier to control the urea group formation reaction.

Examples of aromatic polyamine compounds include bis(aminoalkyl)benzene, bis(aminoalkyl)naphthalene, aromatic polyamine compounds having two or more primary amino groups bonded to a benzene ring, and other aromatic polyamines. compounds and the like.

Examples of aromatic polyamine compounds include, but are not limited to, bis(cyanoethyl)diethylenetriamine, o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, phenylenediamine, naphthylenediamine, amine, diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 2, 2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl , 3,3′-dimethoxy-4,4′-diaminobiphenyl, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, polytetramethylene oxide-di-p-aminobenzoate and the like.

The aromatic polyamine compound may be contained in an amount of 0.5 to 70 parts by mass, 1 to 70 parts by mass, or 1 to 50 parts by mass with respect to the total 100 parts by mass of the polyamine compound (A). part may be contained, and 1 to 30 parts by mass may be contained. By including the aromatic polyamine compound within the above range, there is an advantage that the urea resin forming reaction can be more easily controlled.

[Other amine compounds]
The coating composition of the present disclosure (specifically, main agent (I)) may contain an amine compound having one amino group within a range that does not impair the effects of the present invention.
Examples of the amine compound include, but are not limited to, dipropylamine, dibutylamine, diisobutylamine, N-methylhexylamine, di-N-octylamine, tetra(aminomethyl)methane, aspartic acid, and the like. .

[Polyisocyanate compound (B)]
Polyisocyanate compound (B) is a compound having two or more isocyanate groups, and is not particularly limited as long as it does not depart from the scope of the present invention.

The polyisocyanate compound (B) is, for example, at least one selected from aliphatic isocyanates, alicyclic isocyanates and aromatic isocyanates.

Polyisocyanate compounds (B) include alicyclic isocyanates having free isocyanate groups, such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), and trimethylhexamethylene diisocyanate; Alicyclic isocyanates such as pentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), norbornane diisocyanate methyl; xylylene diisocyanate (XDI), 2,4-tolylene diisocyanate (TDI) , 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), metaxylylene diisocyanate (MXDI) and other aromatic isocyanates; Examples include:

The polyisocyanate compound (B) is preferably at least one selected from aliphatic isocyanates and alicyclic isocyanates, more preferably aliphatic isocyanates. Since the polyisocyanate compound has lower reactivity than the aromatic isocyanate compound, the reaction rate of urea group formation can be suppressed.
A preferred aliphatic isocyanate is hexamethylene diisocyanate (HDI) and a preferred cycloaliphatic isocyanate is isophorone diisocyanate (IPDI).

If desired, the isocyanate groups may be modified without departing from the scope of the present invention, and the isocyanate groups contained in the polyisocyanate compound (B) may cause a cross-linking reaction. Since the multimeric polyisocyanate compound is trifunctional or higher, at least one of a plurality of isocyanate groups may be modified, and at least two isocyanate groups may cause a cross-linking reaction.

These polyisocyanate compounds (B) may be used alone or in combination of two or more.

The content of the polyisocyanate compound (B) is the equivalent ratio of the amino groups of the polyamine compound (A) to the isocyanate groups of the polyisocyanate compound (B) (for example, NCO/NH ₂ in the case of secondary amines). is preferably in the range of 0.5 to 2.0, more preferably in the range of 0.8 to 1.2. In addition, the amino group used for the calculation of the above equivalent ratio indicates the amino group present at the end of the molecule. When the equivalent ratio is within the above range, there is an advantage that the water resistance of the coating film formed is improved.

[Carbonyl compound (C)]
A carbonyl compound (C) is a compound having a carbonyl group. By using the carbonyl compound (C), it is possible to suppress gelling immediately after mixing the main agent and the curing agent, and it is possible to suppress the reaction rate of the coating composition.

The carbonyl compound (C) is preferably at least one selected from ester compounds, ketone compounds and amide compounds.

Examples of the ester compounds include butyl acetate, isobutyl acetate, tert-butyl acetate, dimethyl succinate, diethyl succinate, dimethyl glutarate, dimethyl adipate, methoxypropyl acetate (PMA), propylene glycol monomethyl ether propionate ( methotate), ethyl 3-ethoxypropionate (EEP), butyl cellosolve acetate, 3-methoxy-3-methyl-1-butyl acetate (e.g. Solfit AC), butyl carbitol acetate, methyl acetoacetate, ethyl acetoacetate , diethyl malonate, dimethyl malonate, γ-butyrolactone, ε-caprolactone, γ-decalactone and the like. The ester compounds may be used alone or as a mixture of two or more.

Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, tert-butyl methyl ketone, isopropyl ketone, isopropyl methyl ketone, diisopropyl ketone, 2-heptanone, acetylacetone, 2,3-butanedione, cyclohexanone, 2-methyl cyclohexanone, 2,6-dimethylcyclohexanone, 3,3-dimethylcyclohexanone, fenchone, cyclobutanone, cyclopentanone, isophorone and the like. The ketone compound may be used alone or as a mixture of two or more.

Examples of the amide compound include 2-pyrrolidone, N-methylpyrrolidone (NMP), N-ethylmaleimide and the like. The amide compound may be used alone or as a mixture of two or more.

In one embodiment, the carbonyl compound (C) includes a cyclic ester compound, a cyclic ketone compound, a cyclic amide compound, a chain ester compound having two or more carbonyl groups, a chain ketone compound having two or more carbonyl groups, and two It is preferably at least one selected from the above chain amide compounds having a carbonyl group.

A cyclic ester compound is a compound having a ring structure, preferably containing an ester bond within the ring structure.
Cyclic ester compounds include, for example, compounds having 4 to 15 carbon atoms, specifically 4 to 10 carbon atoms.
Examples of the cyclic ester compounds include γ-butyrolactone, ε-caprolactone, γ-decalactone and the like.

A cyclic ketone compound is a compound having a ring structure, and preferably a carbon atom constituting a carbonyl group is included in the atoms constituting the ring structure.
Cyclic ketone compounds include, for example, compounds having 4 to 15 carbon atoms, specifically 4 to 10 carbon atoms.
Examples of the cyclic ketone compound include cyclobutanone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, 3,3-dimethylcyclohexanone, fenchone, and isophorone.

A cyclic amide compound is a compound having a ring structure, and preferably carbon atoms and nitrogen atoms contained in the amide group are included in atoms constituting the ring structure.
Cyclic amide compounds include, for example, compounds having 4 to 15 carbon atoms, specifically 4 to 10 carbon atoms.
Examples of the cyclic amide compounds include N-methylpyrrolidone (NMP) and N-ethylmaleimide.

When the carbonyl compound (C) is a compound having a ring structure, the ring structure may be monocyclic or polycyclic. The ring structure may be, for example, a 4- to 12-membered ring, specifically a 5- to 9-membered ring. When the cyclic ketone compound is a polycyclic compound, the above-mentioned "ring structure" indicates the ring having the largest number of atoms.

The ring structure may have a substituent. Examples of substituents include alkyl groups having 1 to 12 carbon atoms, preferably alkyl groups having 1 to 8 carbon atoms.

Chain ester compounds having two or more carbonyl groups preferably have 5 to 40 carbon atoms, more preferably 5 to 16 carbon atoms. The chain structure may be linear or may have a branched structure. In a chain ester compound having two or more carbonyl groups, the carbonyl groups may be a carbonyl group and an ester group, or two or more ester groups. The compound preferably contains 2 to 4, more preferably 2, carbonyl groups.

Examples of the chain ester compound having two or more carbonyl groups include oxo acid esters such as methyl acetoacetate and ethyl acetoacetate; diethyl malonate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate and the like. and dibasic acid esters of.

Chain ketone compounds having two or more carbonyl groups preferably have 4 to 40 carbon atoms, more preferably 4 to 16 carbon atoms. The compound preferably contains 2 to 4, more preferably 2, carbonyl groups. The chain structure may be linear or may have a branched structure.
Examples of chain ketone compounds having two or more carbonyl groups include acetylacetone and 2,3-butanedione.

A chain amide compound having two or more carbonyl groups preferably has 4 to 40 carbon atoms, more preferably 4 to 16 carbon atoms. The compound preferably contains 2 to 4, more preferably 2, carbonyl groups. The chain structure may be linear or may have a branched structure.

In one embodiment, the carbonyl compound (C) is a compound having two or more α-hydrogens. By including the number of α-hydrogens as described above, it is believed that electron donation is more likely to be received and that this can contribute to the suppression of the reaction rate of urea group formation. In the present disclosure, α-hydrogen means a hydrogen atom bonded to the first carbon atom (referred to as α-carbon) adjacent to the carbonyl group.

In one embodiment, the carbonyl compound (C) is a cyclic ester compound, a cyclic ketone compound, a cyclic amide compound, a chain ester compound having two or more carbonyl groups, a chain ketone compound having two or more carbonyl groups, or two It is preferably a chain amide compound having the above carbonyl group and a compound having two or more α-hydrogens.
Examples of such compounds include γ-butyrolactone, ε-caprolactone, γ-decalactone, cyclobutanone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, 3,3-dimethylcyclohexanone, isophorone, and the like. cyclic ketone compounds, cyclic amide compounds such as 2-pyrrolidone and N-methylpyrrolidone (NMP); oxo acid esters such as methyl acetoacetate and ethyl acetoacetate; diethyl malonate, dimethyl malonate, dimethyl succinate, diethyl succinate dibasic acid esters such as acetylacetone, diketone compounds such as 2,3-butanedione, and the like.

In one embodiment, the carbonyl compound (C) is a cyclic ketone compound or a cyclic amide compound and has two or more α-hydrogens.

In one embodiment, the carbonyl compound (C) is preferably a compound having 3 or more α-hydrogens, more preferably 4 or more. By using such a compound, the reaction rate of the resulting coating composition can be further suppressed.
Examples of such compounds include cyclic ketone compounds such as cyclobutanone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3,3-dimethylcyclohexanone and isophorone; oxo acid esters such as methyl acetoacetate and ethyl acetoacetate; dibasic acid esters such as dimethyl succinate, dimethyl glutarate, and dimethyl adipate; and diketone compounds such as acetylacetone and 2,3-butanedione.

The carbonyl compound (C) is preferably a cyclic ketone compound such as cyclobutanone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, 3,3-dimethylcyclohexanone, isophorone; oxo acid esters such as ethyl acetate; dibasic acid esters such as dimethyl succinate, dimethyl glutarate and dimethyl adipate; monoketone compounds; diketone compounds such as acetylacetone and 2,3-butanedione, more preferably Mention may be made of cyclohexanone, cyclopentanone, acetylacetone.

In one embodiment, the content of the carbonyl compound (C) is 1 to 900 parts by mass with respect to 100 parts by mass of the solid content of the polyamine compound (A) and the solid content of the polyisocyanate compound (B). , preferably 1 to 250 parts by mass, more preferably 5 to 120 parts by mass, even more preferably 20 to 120 parts by mass, and particularly preferably 20 to 110 parts by mass. By being within the above range, the reaction rate of the coating composition can be further suppressed, and the resulting coating film can have a desired thickness.

In one embodiment, the content of the carbonyl compound (C) is 45 to 120 parts by mass with respect to the total amount of 100 parts by mass of the solid content of the polyamine compound (A) and the solid content of the polyisocyanate compound (B). It may be 80 to 110 parts by mass.

[Other ingredients]
The coating composition of the present disclosure may optionally contain other components in addition to the above components.
Other components include, for example, pigments, resin particles, resin components, dispersants, curing catalysts, viscosity agents, film-forming aids, and additives commonly used in coating compositions (e.g., UV absorbers, light stabilizers, oxidation inhibitors, antifoaming agents, surface conditioners, pinhole inhibitors, rust inhibitors, etc.) and the like.

In one embodiment, the coating composition of the present disclosure contains a polyol compound as the resin component. The polyol compound is not particularly limited as long as it is a compound containing two or more hydroxyl groups per molecule. Examples of polyol compounds include ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, glycerin, trimethylolethane, trimethylolpropane, polyethylene glycol, polypropylene glycol, and polyepoxypolyol. , polycarbonate polyols, polyester polyols, polyether polyols, polyesteramide polyols, acrylic polyols, polyurethane polyols, or mixtures thereof.

Polyol compounds include castor oil polyol (e.g. URIC series manufactured by Ito Oil Co., Ltd.), acrylic polyol (e.g. Acrydic series manufactured by DIC), polyester polyol (e.g. Polylight series manufactured by DIC), polycarbonate diol (e.g. Asahi Kasei Co., Ltd. (manufactured by Duranol series) may be used.

Polyol compounds may be used alone or in combination of two or more.

The above other components can be added to the main agent (I) and/or the curing agent (II) in an amount within a range that does not impair the physical properties of the coating composition of the present disclosure.

In one embodiment, only the main agent (I) contains the carbonyl compound (C).

In one embodiment, only curing agent (II) contains carbonyl compound (C).

In one embodiment, the main agent (I) and curing agent (II) contain a carbonyl compound (C).

[Method for producing paint composition]
The coating composition of the present disclosure is a two-component curing type having main agent (I) and curing agent (II).
The main agent (I) and curing agent (II) can be prepared by mixing the components contained therein by methods known to those skilled in the art. For example, a method commonly used by those skilled in the art, such as kneading and mixing means using a kneader or rolls, or dispersing and mixing means using a sand grind mill, disper, or the like, can be used.

The main agent (I) and the curing agent (II) may be mixed before use and applied by a normal application method. For example, commonly used coating methods such as immersion, brush, roller, roll coater, air spray, airless spray, curtain flow coater, roller curtain coater and die coater can be used.
Alternatively, the main agent (I) and the hardening agent (II) may be separately fed to the gun using a two-liquid mixing gun, and the two may be mixed at the tip of the gun.
The coating method can be appropriately selected according to the object to be coated.

A coating film, film, or sheet can be formed on the substrate by applying the coating composition of the present disclosure onto the substrate and curing the substrate.
For example, by discharging the coating composition from a spray device, it can be applied to an object to be coated to form a coating film. A coating composition may be cast on the release-treated film or sheet, dried and cured to form a film or sheet.

Materials to be coated include, for example, metal substrates, plastic substrates, composite substrates thereof, wood, glass, cloth, concrete, and ceramic materials.
Examples of metal substrates include metals such as iron, steel, copper, aluminum, tin, and zinc, and alloys containing these metals. The metal substrate may be plated with zinc, copper, chromium, or the like, or may be surface-treated with a surface treatment agent such as chromic acid, zinc phosphate, or zirconium salt. Furthermore, a primer coating may be applied thereon.
Examples of plastic substrates include polypropylene resins, polycarbonate resins, urethane resins, polyester resins, polystyrene resins, ABS resins, vinyl chloride resins, and polyamide resins. These plastic substrates may be coated with a primer.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these. "Parts" and "%" in the examples are based on mass unless otherwise specified.

(Example 1)
<Manufacturing of main agent>
83.4 parts by mass of JEFFAMINE D-2000 was used as the main component as the polyamine compound (A1-1). In addition, the detail of each used component is mentioned later (the same applies below).

<Production of curing agent>
16.6 parts by mass of Coronate HX as the polyisocyanate compound (B1) and 42.9 parts by mass of butyl acetate as the carbonyl compound (C1) were mixed with a disper and stirred until uniform to obtain a curing agent.

<Manufacture of paint composition>
83.4 parts by mass of the main agent and 59.5 parts by mass of the curing agent were mixed with a disper and stirred until uniform to obtain a coating composition.

(Examples 2 to 22, Comparative Examples 1 to 3)
A coating composition was prepared in the same manner as in Example 1 except that the types and amounts of each component were set to the types and amounts shown in Tables 1 to 3. The composition and various characteristic values are shown in Tables 1-3. In addition, in the contents and ratios in the table, (A) shall be read as (A) and (a) for examples containing other polyamines.

[Polyamine compound (A)]
(Polyamine compound (A1))
(A1-1) JEFFAMINE D-2000, manufactured by HUNTSMAN, primary aliphatic polyamine compound (polyoxypropylenediamine); solid content concentration: 100% by mass, weight average molecular weight: 2,000, amine equivalent: 1,000
(A1-2) JEFFAMINE D-230, manufactured by HUNTSMAN, aliphatic primary polyamine compound (polyoxypropylenediamine); solid content concentration: 100% by mass, weight average molecular weight: 230, amine equivalent: 115
(A1-3) JEFFAMINE T-403, manufactured by HUNTSMAN, primary aliphatic polyamine compound (polyoxypropylene triamine); solid content concentration: 100 mass%, weight average molecular weight: 440, amine equivalent: 147
(A1-4) Desmophen NH1220, manufactured by Sumika Covestro Urethane Co., Ltd., aliphatic secondary polyamine (aspartic acid ester amine); solid content concentration: 100% by mass, weight average molecular weight: 461, amine equivalent: 234
(A2-1) Daitoclar I-2237, manufactured by Daito Sangyo Co., Ltd., alicyclic primary polyamine compound; solid content concentration: 100 mass%, weight average molecular weight: 170, amine equivalent: 105
(A2-2) Desmophen NH1420, manufactured by Sumika Covestrourethane Co., Ltd., alicyclic secondary polyamine (aspartic acid ester amine); solid content concentration: 100% by mass, weight average molecular weight: 555, amine equivalent: 276
(Other polyamine compounds)
(a1-1) Iharakyuamine MT, manufactured by Kumiai Chemical Industry Co., Ltd., aromatic primary polyamine compound (3,3′-dichloro-4,4′-diaminodiphenylmethane); solid content concentration: 100% by mass, weight average molecular weight : 267, amine equivalent: 134
(a1-2): Elastomer 650P, manufactured by Kumiai Chemical Industry Co., Ltd., aromatic primary polyamine compound (polytetramethylene oxide-di-p-aminobenzoate); solid content concentration: 100% by mass, weight average molecular weight: 888, amine Equivalent: 444

[Polyisocyanate compound (B)]
(B1) Coronate HX, manufactured by Tosoh Corporation, aliphatic isocyanate compound (isocyanurate form of HDI (hexamethylene diisocyanate)); solid content concentration: 100% by mass, NCO content: 21% by mass
(B2) Desmodur N3400, manufactured by Sumika Covestro Urethane Co., Ltd., aliphatic isocyanate compound (uretdione form of HDI (hexamethylene diisocyanate)); solid content concentration: 100% by mass, NCO content: 21.8% by mass
(B3) Millionate MT, manufactured by Tosoh Corporation, aromatic isocyanate compound (MDI (diphenylmethane diisocyanate)); solid content concentration: 100% by mass, NCO content: 33.6% by mass

[Carbonyl compound (C)]
(C1): Butyl acetate, manufactured by Daicel Chemical Industries, Ltd., chain ester compound; number of carbonyl groups: 1, number of α-hydrogens: 3
(C2): DBE (dibasic acid ester (containing 20% by mass of dimethyl succinate, 60% by mass of dimethyl glutarate and 17.5% by mass of dimethyl adipate)), manufactured by Shoei Chemical Industry Co., Ltd., chain ester compound; Number of carbonyl groups: 2, Number of α-hydrogens: 4
(C3): methyl isobutyl ketone, manufactured by Mitsubishi Chemical Corporation, chain ketone compound; number of carbonyl groups: 1, number of α-hydrogens: 5
(C4): Cyclohexanone, manufactured by Mitsubishi Chemical Corporation, cyclic ketone compound; number of carbonyl groups: 1, number of α-hydrogens: 4
(C5): 2,6-dimethylcyclohexanone, manufactured by Tokyo Chemical Industry Co., Ltd., cyclic ketone compound; number of carbonyl groups: 1, number of α hydrogens: 2
(C6): N-methylpyrrolidone, manufactured by Mitsubishi Chemical Corporation, cyclic amide compound; number of carbonyl groups: 1, number of α-hydrogens: 2

[Other ingredients]
Solvent (c1): T-SOL 100, manufactured by Exxon Chemical Co., aromatic compound Solvent (c2): Isobutanol, manufactured by Mitsubishi Chemical Corporation, alcohol compound

[Evaluation item]
(Gelling time)
The main agent and the curing agent were mixed, stirred with a disper for 1 minute, and allowed to stand after the stirring was completed. At the same time as the stirring was completed, a stopwatch was started to measure the time, and the time required for the mixture of the main agent and the curing agent (coating composition) to completely lose its fluidity was measured and taken as the gelation time. In addition, "60<" in the table indicates the case where the fluidity of the mixture did not disappear even after 60 minutes. The paint temperature was 23°C.
○: The gelation time is 3 minutes or more.
Δ: The gelling time is less than 3 minutes.
x: gelled at the end of stirring.

<Production of test plate>
The coating composition was applied to a polypropylene plate having a thickness of 2 mm and a size of 100×200 mm using a 15 mil applicator and dried at 100° C. for 1 hour to obtain a test plate.

(Weather resistance evaluation) A test plate was subjected to an accelerated weather resistance test for 500 hours using a Sunshine Weather Meter S80 (manufactured by Suga Test Instruments Co., Ltd.), which is a sunshine carbon arc lamp type accelerated weather resistance tester specified in JIS B 7753. went. Operating conditions are as follows Irradiance: 255 W/m ²
Black panel temperature: 63°C
Water injection time: 18 minutes out of 120 minutes The appearance of the coating film on each test plate after the accelerated weather resistance test was visually observed to evaluate the weather resistance. Evaluation criteria are as follows. A score of 3 or more was regarded as passing.
5 points: No abnormality.
4 points: A slight reduction in gloss is observed.
3 points: Decrease in gloss is observed.
2 points: Decrease in gloss and yellowing are observed.
1 point: Remarkable loss of gloss and yellowing are observed.

The examples yielded coating compositions with longer gel times and slower curing rates with good weatherability.

In Comparative Example 1, when the carbonyl compound (C) was not added and the main agent and the curing agent were mixed, gelation occurred immediately after mixing.
In Comparative Examples 2 and 3, an attempt was made to adjust the gelation time using an aromatic polyamine compound without adding the carbonyl compound (C). In Comparative Example 2, when the main agent and the curing agent were mixed, gelation occurred immediately after mixing, and in Comparative Example 3, a larger amount of the aromatic polyamine compound was added, but the gelling time was not sufficiently long.

By using the coating composition of the present invention, it is possible to control the reaction rate between the main agent and the curing agent, and to form a coating film with good weather resistance.

Claims (6)

A coating composition comprising a main agent (I) and a curing agent (II),
The main agent (I) contains a polyamine compound (A),
The curing agent (II) contains a polyisocyanate compound (B),
At least one of the main agent (I) and the curing agent (II) contains a carbonyl compound (C),
The polyamine compound (A) is at least one selected from aliphatic polyamine compounds and alicyclic polyamine compounds and includes a polyamine compound (A1) having at least one of a primary amino group and a secondary amino group. ,
The carbonyl compound (C) includes a cyclic ester compound, a cyclic ketone compound, a chain ester compound having two or more carbonyl groups, a chain ketone compound having two or more carbonyl groups, and a chain amide having two or more carbonyl groups. including at least one selected from compounds,
When the carbonyl compound (C) contains a chain ester compound having two or more carbonyl groups, the chain ester compound having two or more carbonyl groups is at least selected from oxo acid esters and dibasic acid esters. 1 type as an essential ingredient ,
paint composition. The coating composition according to claim 1, wherein the polyamine compound (A1) is an aliphatic polyamine compound. The coating composition according to claim 1 or 2, wherein the polyisocyanate compound (B) is at least one selected from aliphatic isocyanate compounds and alicyclic isocyanate compounds. The coating composition according to any one of claims 1 to 3, wherein the carbonyl compound (C) is at least one selected from an ester compound, a ketone compound and an amide compound. The coating composition according to any one of claims 1 to 4, wherein the carbonyl compound (C) is a compound having two or more α-hydrogens. The content of the carbonyl compound (C) is 1 to 900 parts by mass with respect to 100 parts by mass of the total amount of the solid content of the polyamine compound (A) and the solid content of the polyisocyanate compound (B). Item 6. The coating composition according to any one of items 1 to 5.