JP2019183014A - Coating composition and coated film - Google Patents

Abstract

To provide a coating composition excellent in glossiness, hardness, weather resistance, and water vapor barrier property when made as a coated film, and the coated film by curing the coating composition.SOLUTION: A coating composition contains an isocyanate component containing at least one compound of triisocyanate represented by the general formula (I), and a polyisocyanate compound derived from the triisocyanate, and fluorine-containing polyol having a hydroxyl value of 10 mgKOH/g to 200 mgKOH/g. The coated film is manufactured by curing the coating composition.SELECTED DRAWING: None

Description

  The present invention relates to a coating composition and a coating film.

  Conventionally, paints made of fluorine-containing polyols are known as paint resins having excellent weather resistance, and are used as topcoats for structures, building exteriors, aircraft, windmills, plastics, and the like. As a curing agent for the fluorine-containing polyol, a polyisocyanate compound is used (see, for example, Patent Document 1).

2. Description of the Related Art In recent years, technological development for reducing the viscosity of polyisocyanates used as curing agents has been actively carried out due to an increase in global environmental protection. It is because the usage-amount of the organic solvent used for a coating composition can be reduced by making polyisocyanate low viscosity (for example, refer patent document 2, 3).
As a technique for reducing the viscosity of the curing agent, a technique using a low-viscosity triisocyanate compound alone (for example, see Patent Documents 4 to 6), or a technique for converting a part of these triisocyanate compounds to isocyanurate (for example, Patent Document 7) is known. When these techniques are used, a material satisfying low viscosity and a certain degree of drying has been obtained.

JP 2011-256257 A Japanese Patent No. 3055197 JP 05-222007 A Japanese Examined Patent Publication No. 63-015264 JP-A-53-135931 Japanese Patent Laid-Open No. 60-045461 Japanese Patent Application Laid-Open No. 10-077882

  In the polyisocyanate disclosed in Patent Documents 2 and 3, when improving the weather resistance of the coating resin and reducing the viscosity of the isocyanate at the same time, a bifunctional polyisocyanate is present in the structure, and the crosslinking density As a result, it was difficult to achieve the above problem. Moreover, in patent documents 4-6, no mention is made about the coating composition containing a triisocyanate compound and a fluorine-containing polyol.

  The present invention has been made in view of the above circumstances, and is a coating composition excellent in gloss, hardness, weather resistance and water vapor barrier properties when formed into a coating film, and a coating obtained by curing the coating composition. Providing a membrane.

That is, the present invention includes the following aspects.
The coating composition which concerns on 1st aspect of this invention is an isocyanate component containing at least any one compound among the triisocyanate shown by the following general formula (I), and the polyisocyanate compound induced | guided | derived from the said triisocyanate, And a fluorine-containing polyol having a hydroxyl value of 10 mgKOH / g or more and 200 mgKOH / g or less.

(In the general formula (I), a plurality of Y ^{1 s} each independently contains a single bond or one or more selected from the group consisting of an ester group and an ether group. A plurality of Y ¹ may be the same or different, and R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. )

In the coating composition according to the first aspect, the isocyanate component may have a viscosity at 25 degrees of 5 mPa · s to 100 mPa · s.
In the coating composition according to the first aspect, the isocyanate group content of the isocyanate component may be 40% by mass or more.

  The coating film which concerns on the 2nd aspect of this invention hardens the coating composition which concerns on the said 1st aspect.

  According to the coating composition of the said aspect, the coating film which is excellent in glossiness, hardness, a weather resistance, and water vapor | steam barrier property is obtained. The coating film of the said aspect is excellent in glossiness, hardness, a weather resistance, and water vapor | steam barrier property.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

In this specification, “polyisocyanate” refers to a polymer in which a plurality of monomers having one or more isocyanate groups (—NCO) are bonded.
In this specification, “polyol” refers to a compound having two or more hydroxy groups (—OH).

≪Paint composition≫
The coating composition of this embodiment contains an isocyanate component as a curing agent and a resin component containing a fluorine component as a main component.
The isocyanate component is at least one of a triisocyanate represented by the following general formula (I) (hereinafter sometimes referred to as “triisocyanate (I)”) and a polyisocyanate compound derived from the triisocyanate. Of the compound.
Moreover, the resin component containing a fluorine component includes a fluorine-containing polyol having a hydroxyl value of 10 mgKOH / g or more and 200 mgKOH / g or less.

(In the general formula (I), a plurality of Y ^{1 s} each independently contains a single bond or one or more selected from the group consisting of an ester group and an ether group. A plurality of Y ¹ may be the same or different, and R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. )

Since the coating composition of the present embodiment has the above configuration, a coating film having excellent gloss, hardness, weather resistance, and water vapor barrier properties can be obtained.
Subsequently, each component of the coating composition of this embodiment is demonstrated in detail below.

<Isocyanate component>
The isocyanate component includes at least one of triisocyanate (I) and a polyisocyanate compound derived from the triisocyanate (I) (hereinafter sometimes simply referred to as “polyisocyanate compound”). .
The isocyanate component may contain only triisocyanate (I) or a polyisocyanate compound, and may contain both triisocyanate (I) and a polyisocyanate compound.
The isocyanate component may contain one type of triisocyanate (I) or polyisocyanate compound alone, or may contain two or more types of triisocyanate (I) or polyisocyanate compounds in combination.

[Triisocyanate (I)]
Triisocyanate (I) is a compound represented by the following general formula (I).

(Y ¹ )
In general formula (I), a plurality of Y ¹ are each independently a single bond or a divalent group having 1 to 20 carbon atoms that may contain one or more selected from the group consisting of an ester group and an ether group. It is a hydrocarbon group. A plurality of Y ¹ may be the same or different.

The divalent hydrocarbon group having 1 to 20 carbon atoms that does not include an ester group and an ether group in Y ¹ may be an aliphatic group or an aromatic group. The aliphatic group may be linear, branched or cyclic.
Examples of the linear or branched aliphatic group include alkanediyl groups (alkylene groups) and alkylidene groups.
Examples of the cyclic aliphatic group include a cycloalkylene group.
Examples of the aromatic group include an arylene group such as a phenylene group.
Among these, an alkylene group is preferable as the divalent hydrocarbon group having 1 to 20 carbon atoms.
Examples of the alkylene group include a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, and an octamethylene group.
Among these, the alkylene group is preferably a tetramethylene group.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms and including at least one selected from the group consisting of an ester group and an ether group in Y ¹ include a group represented by the following general formula (II) ( Hereinafter, “may be referred to as“ group (II) ””).
_{- (CH 2) n1 -X- (} CH 2) n2 - ··· (II)

In the group (II), a bond opposite to X in — (CH ₂ ) _n1 — is bonded to C in the general formula (I), and a bond opposite to X in — (CH ₂ ) _n2 —. Is bonded to the NCO in the general formula (I). N1 and n2 are integers satisfying 1 ≦ n1 + n2 ≦ 20. That is, both n1 and n2 do not become 0, and n2 on the side bonded to the NCO is preferably 1 or more.
Among these, n1 and n2 are each independently preferably an integer of 0 or more and 20 or less, more preferably an integer of 0 or more and 4 or less, and further preferably an integer of 0 or more and 2 or less.
As a combination of n1 and n2, for example, a combination of n1 = 0 and n2 = 2, a combination of n1 = 2 and n2 = 2 is preferable.
In the group (II), X is preferably an ester group.

In addition, when at least ^one of the plurality of Y ¹ has one or more of the group consisting of an aliphatic group and an aromatic group, the isocyanate component can be made to have a lower viscosity, and the isocyanate component can be cured in the coating composition. The weather resistance of the coating film produced by using it as an agent can be made better.
In addition, when at least ^one of the plurality of Y ¹ has an ester group or an ether group, the heat resistance of the isocyanate component can be further improved.
Further, when at least ^one of the plurality of Y ¹ has an ester group, the heat resistance of the isocyanate component can be further improved.
Further, when at least ^one of the plurality of Y ¹ has an ether group, the hydrolysis resistance of the isocyanate component can be further improved.

(R ¹ )
R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group of R ^1, is not particularly limited, an alkyl group, an alkenyl group, an alkynyl group. Among these, as R ¹ , a hydrogen atom is preferable.

Specifically, preferred triisocyanate (I) is, for example, 4-isocyanatomethyl-1,8-octamethylene diisocyanate (hereinafter referred to as “NTI”) disclosed in Japanese Patent Publication No. 63-015264 (Patent Document 4). Molecular weight 251), 1,3,6-hexamethylene triisocyanate (hereinafter referred to as “HTI”) disclosed in JP-A-57-198760 (reference document 1) 209), bis (2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter sometimes referred to as “GTI”, molecular weight 311) disclosed in JP-B-4-001033 (reference 2), Lysine triisocyanate (hereinafter referred to as “LTI”) disclosed in JP-A-53-135931 (Patent Document 5) Sometimes referred to, molecular weight 267), and the like. These triisocyanates may be used alone or in combination of two or more.
Among these, NTI, GTI or LTI is preferable, and NTI or LTI is more preferable from the viewpoint of further improving the reactivity of the isocyanate group.

[Method for producing triisocyanate (I)]
Triisocyanate (I) can be obtained by converting an amino acid derivative, an amine such as an ether amine or an alkyltriamine into an isocyanate. As the amino acid derivative, for example, 2,5-diaminovaleric acid, 2,6-diaminohexanoic acid, aspartic acid, glutamic acid and the like can be used. Since these amino acids are diamine monocarboxylic acids or monoamine dicarboxylic acids, the carboxyl group is esterified with an alkanolamine such as ethanolamine. Thereby, the triamine which has an ester group obtained can be made into the triisocyanate containing an ester group by phosgenation etc.

Examples of the ether amine include Mitsui Chemicals Fine's trade name “D403”, which is a polyoxyalkylene triamine. This is a triamine and can be made into a triisocyanate containing an ether group by phosgenation of an amine or the like.
Examples of the alkyltriamine include triisocyanatononane (4-aminomethyl-1,8-octanediamine). This is a triamine and can be made into a triisocyanate containing only hydrocarbons by phosgenation of the amine.

[Polyisocyanate compound]
The polyisocyanate compound is derived from the triisocyanate (I). That is, the polyisocyanate compound is a reaction product obtained by a polymerization reaction using the triisocyanate (I) as a monomer.
In addition, the polyisocyanate compound can have various functional groups such as isocyanurate group, biuret group, allophanate group, uretdione group, iminodioxadiazinedione group, and urethane group.

  In general, the “isocyanurate group” is a functional group obtained by reacting three isocyanate groups, and is a group represented by the following formula (III).

  In general, the “biuret group” is a functional group obtained by reacting three isocyanate groups with a biuret agent, and is a group represented by the following formula (IV).

  In general, an “allophanate group” is a functional group obtained by reacting two isocyanate groups with one hydroxyl group, and is a group represented by the following formula (V).

  In general, the “uretdione group” is a functional group obtained by reacting two isocyanate groups, and is a group represented by the following formula (VI).

  In general, the “iminooxadiazinedione group” is a functional group obtained by reacting three isocyanate groups, and is a group represented by the following formula (VII).

  In general, the “urethane group” is a functional group obtained by reacting one isocyanate group and one hydroxyl group, and is a group represented by the following formula (VIII).

[Production method of polyisocyanate compound]
The polyisocyanate compound can be obtained by subjecting triisocyanate (I) to a polymerization reaction using a known catalyst or by heating. After completion of the reaction, the unreacted triisocyanate (I) may be removed, or the unreacted triisocyanate (I) may be used as it is as an isocyanate component without being removed.

For example, when producing a polyisocyanate compound from volatile diisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentane diisocyanate, toluene diisocyanate, and isophorone diisocyanate, it is necessary to remove unreacted diisocyanate. At this time, the content of the diisocyanate contained in the polyisocyanate compound derived from the diisocyanate can be less than 2% by mass relative to the total mass of the product, and is preferably less than 1% by mass.
On the other hand, when the polyisocyanate compound derived from triisocyanate (I) is used as it is without removing the unreacted triisocyanate (I), the unreacted triisocyanate (I) has an isocyanate group. Since it has three, it can maintain, without reducing the crosslinking | crosslinked ability with the polyol of this isocyanate component.
Moreover, when removing unreacted triisocyanate (I) from the obtained polyisocyanate compound, the polyisocyanate compound can be separated from the product by a thin film distillation method or a solvent extraction method.

[Other isocyanate compounds]
The isocyanate component may further contain other isocyanate compounds in addition to the triisocyanate (I) and the polyisocyanate compound.
Examples of other isocyanate compounds include diisocyanate and polyisocyanate compounds derived from the diisocyanate.
Examples of the diisocyanate include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.

  Examples of the aliphatic diisocyanate include tetramethylene diisocyanate (TMDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane-1,6-diisocyanate, and 2-methylpentane-1. , 5-diisocyanate (MPDI), lysine diisocyanate (LDI), and the like.

  Examples of the alicyclic diisocyanate include 1,3-bis (isocyanatomethyl) -cyclohexane (1,3-H6-XDI), 3 (4) -isocyanatomethyl-1-methyl-cyclohexyl isocyanate (IMCI). ), Isophorone diisocyanate (IPDI), bis (isocyanatomethyl) -norbornane (NBDI), 4,4′-dicyclohexylmethane diisocyanate (H12MDI), and the like.

Examples of the aromatic diisocyanate include 1,3-bis (isocyanatomethyl) -benzene, 1,3-bis (2-isocyanatopropyl-2) benzene and the like.
These diisocyanates may be used alone or in combination of two or more.

  Among these, HDI or IPDI is preferable as the diisocyanate because of weather resistance and industrial availability.

The polyisocyanate compound derived from diisocyanate is obtained by polymerizing the diisocyanate using a catalyst or heating. Moreover, the polyisocyanate compound derived from diisocyanate can have various functional groups such as isocyanurate group, biuret group, allophanate group, uretdione group, iminodioxadiazinedione group, and urethane group in the molecule.
Among them, the polyisocyanate compound derived from diisocyanate preferably has an isocyanurate group from the viewpoint of weather resistance.

[Physical properties of isocyanate component]
Next, the physical properties of the isocyanate component will be described in detail below.

(Viscosity at 25 ° C.)
The viscosity at 25 ° C. of the isocyanate component is not particularly limited, but is preferably 5 mPa · s or more and 2000 mPa · s or less, more preferably 5 mPa · s or more and 1800 mPa · sm or less, and more preferably 5 mPa · s or more and 100 mPa · s or less. It is more preferably s or less, and even more preferably 5 mPa · s or more and 80 mPa · s or less. There exists a tendency for sclerosis | hardenability to be more excellent by making the viscosity in 25 degreeC of an isocyanate component more than the said lower limit. On the other hand, there exists a tendency for workability | operativity to be more excellent by making the viscosity in 25 degreeC of an isocyanate component below into the said upper limit.
The viscosity can be measured using an E-type viscometer (manufactured by Tokimec).

(Isocyanate group content)
The lower limit of the isocyanate group content of the isocyanate component (hereinafter may be referred to as “NCO content”) can be 30% by mass in a state that does not substantially contain a solvent or diisocyanate, and is 35% by mass. % Is preferable, and 40 mass is more preferable.
On the other hand, the upper limit of the NCO content can be 60% by mass in a state in which substantially no solvent or diisocyanate is contained, preferably 57% by mass, and more preferably 55% by mass.
That is, the NCO content can be 30% by mass or more and 60% by mass or less, and is preferably 35% by mass or more and 57% by mass or less, and is preferably 40% by mass or more and 55% by mass in a state that substantially contains no solvent or diisocyanate. % Or less is more preferable.
When the NCO content is within the above range, an isocyanate component having more sufficient crosslinkability can be obtained.
In addition, in this specification, "the state which does not contain a solvent and diisocyanate substantially" means the state whose content of a solvent or diisocyanate is less than 1 mass% with respect to the total mass of an isocyanate component. .

(Functional number of isocyanate groups)
The number of functional groups of the isocyanate group of the isocyanate component is preferably 2 or more and 12 or less. When the number of functional groups of the isocyanate group is greater than or equal to the above lower limit, it has more sufficient crosslinkability. On the other hand, it can be set as the viscosity which can achieve the viscosity reduction of an isocyanate component because the number of functional groups of an isocyanate group is below the said upper limit.

[Other compounds]
The isocyanate component can contain other compounds. Examples of other compounds include unsaturated bond-containing compounds, inert compounds, metal atoms, basic amino compounds, carbon dioxide, and halogen atoms. These other compounds may be used alone or in combination of two or more.

The lower limit of the content of the other compound in the isocyanate component is preferably 1.0 mass ppm, based on the total mass of the compound having an isocyanate group such as the triisocyanate (I) or the polyisocyanate compound. 0.0 mass ppm is more preferable, 5.0 mass ppm is further more preferable, and 10 mass ppm is especially preferable.
On the other hand, the upper limit of the content of the other compounds is preferably 1.0 × 10 ⁴ mass ppm, more preferably 5.0 × 10 ³ mass ppm, and 3.0 × 10 ⁴ relative to the mass of the isocyanate component. ³ mass ppm is more preferable, and 1.0 × 10 ³ mass ppm is particularly preferable.
That is, the content of the other compounds is preferably 1.0 mass ppm or more and 1.0 × 10 ⁴ mass ppm or less, more preferably 3.0 mass ppm or more and 5.0 × 10 ³ mass based on the mass of the isocyanate component. ppm or less is more preferable, 5.0 mass ppm or more and 3.0 × 10 ³ mass ppm or less is more preferable, and 10 mass ppm or more and 1.0 × 10 ³ mass ppm or less is particularly preferable.
When content of the said other compound exists in the said range, the coloring prevention at the time of long-term storage of an isocyanate component and long-term storage stability improve more.

(Unsaturated bond-containing compound)
As the unsaturated bond-containing compound, a compound having a carbon-carbon unsaturated bond, a carbon-nitrogen unsaturated bond, or a carbon-oxygen unsaturated bond is preferable. Among these, from the viewpoint of the stability of the compound, the unsaturated group-containing compound is preferably a compound having a double bond, such as a carbon-carbon double bond (C = C) or a carbon-oxygen double bond ( More preferred are compounds having C = O). Moreover, it is preferable that the carbon atom which comprises this compound has couple | bonded with three or more atoms.
In general, the carbon-carbon double bond may be a carbon-carbon double bond constituting an aromatic ring, but the unsaturated bond-containing compound contained in the isocyanate component has an unsaturated bond: It does not contain carbon-carbon double bonds constituting the aromatic ring.
Examples of the compound having a double bond between carbon and oxygen include carbonic acid derivatives. Examples of the carbonic acid derivative include urea compounds, carbonic acid esters, N-unsubstituted carbamic acid esters, N-substituted carbamic acid esters, and the like.

(Inactive compounds)
Inactive compounds are classified into the following compounds A to G.
The hydrocarbon compounds are compounds A and B, the ether compounds and sulfide compounds are the following compounds C to E, the halogenated hydrocarbon compounds are the following compounds F, silicon-containing hydrocarbon compounds, silicon-containing ether compounds and silicon-containing sulfide compounds. Are classified into the following compounds G, respectively. In addition, the compound A-compound G mentioned here does not contain an unsaturated bond other than an aromatic ring, and the compound which has an above-mentioned unsaturated bond is not contained.
Compound A: An aliphatic hydrocarbon compound having a linear, branched or cyclic structure.
Compound B: An aromatic hydrocarbon compound which may be substituted with an aliphatic hydrocarbon group.
Compound C: A compound having an ether bond or sulfide bond and an aliphatic saturated hydrocarbon group, wherein the same or different aliphatic saturated hydrocarbon compounds are bonded via an ether bond or a sulfide bond.
Compound D: A compound having an ether bond or a sulfide bond and an aromatic hydrocarbon group, wherein the same or different aromatic hydrocarbon compounds are bonded via an ether bond or a sulfide bond.
Compound E: A compound having an ether bond or sulfide bond, an aliphatic saturated hydrocarbon group, and an aromatic hydrocarbon group.
Compound F: A halide in which at least one hydrogen atom constituting an aliphatic saturated hydrocarbon compound or at least one hydrogen atom constituting an aromatic hydrocarbon compound is substituted with a halogen atom.
Compound G: A compound in which some or all of the carbon atoms of the compounds A to E are substituted with silicon atoms.

(Metal atom)
The metal atom may exist as a metal ion or may exist as a metal atom alone. One type of metal atom may be included alone, or a combination of two or more types of metal atoms may be included. As a metal atom, the metal atom which can take the valence of 2 valence or more and 4 valence or less is preferable, and iron, cobalt, nickel, zinc, tin, copper, or titanium is more preferable.

(Basic amino compounds)
A basic amino compound is a derivative of ammonia, a compound in which one hydrogen is substituted with an alkyl group or an aryl group (primary), a compound in which two hydrogens are substituted (secondary), and all three are substituted. Compound (tertiary). Among these, as the basic amino compound, a secondary or tertiary amino compound is preferable, and an aliphatic amine, an aromatic amine, a heterocyclic amine, or a basic amino acid is more preferable.

(carbon dioxide)
Carbon dioxide may be dissolved in the isocyanate component at normal pressure, or may be dissolved in a pressurized state in a pressure vessel. Since the use of carbon dioxide containing water may cause hydrolysis of the isocyanate component, the amount of water contained in carbon dioxide is preferably managed as necessary.

(Halogen atom)
The halogen atom may be present as a halide ion or may be present as a halide. One type of halogen atom may be included alone, or a combination of two or more types of halogen atoms may be included. Although it does not specifically limit as a halogen atom, Chlorine or a bromine is preferable and a chlorine ion, a bromine ion, hydrolyzable chlorine, or a hydrolyzable bromine is more preferable. Examples of hydrolyzed chlorine include carbamoyl chloride compounds in which hydrogen chloride is added to an isocyanate group. Examples of hydrolyzable bromine include carbamoyl bromide compounds in which hydrogen bromide is added to an isocyanate group.
The halogen atom content in the isocyanate component is preferably 1.0 × 10 ² mass ppm or less with respect to the total mass of the composition from the viewpoint of preventing coloring.

<Resin component>
The resin component contains a fluorine component and a compound having two or more active hydrogen-containing groups having reactivity with an isocyanate group in the molecule. Examples of the compound having two or more active hydrogen-containing groups in the molecule include polyols, polyamines, polythiols, and the like, and includes at least a polyol. That is, the coating composition of the present embodiment contains at least a fluorine-containing polyol as a resin component (main agent).

[Fluorine-containing polyol]
In the present specification, the “fluorine-containing polyol” means a polyol containing fluorine in the molecule. Examples of the fluorine-containing polyol include fluoroolefins, cyclovinyl ethers, and hydroxyalkyl vinyl ethers disclosed in JP-A-57-34107 (Reference 3), JP-A-61-275111 (Reference 4), and the like. And copolymers such as monocarboxylic acid vinyl ester.
More specific examples of the fluorine-containing polyol include, for example, Lumiflon LF100, LF200, LF400, LF600, LF800, FE800, FE4400, FD1000, Zaffle GK500, GK510, GK550 from Daikin Chemical Industries, Ltd. GK570, GK580, Central Glass's Cefral Coat 703, 705, DIC's Fluonate K-700, K-702, K-704, K-705, K-707, WZQ-660, etc. Can be mentioned. These fluorine-containing polyols may be used individually by 1 type, and may be used in combination of 2 or more type.

[Hydroxyl value and acid value of polyol]
The lower limit of the hydroxyl value of the polyol is preferably 10 mgKOH / g, more preferably 20 mgKOH / g, and even more preferably 30 mgKOH / g.
The upper limit of the hydroxyl value of the polyol is preferably 200 mgKOH / g, more preferably 180 mgKOH / g, and even more preferably 160 mgKOH / g.
That is, the hydroxyl value of the polyol is preferably from 10 mgKOH / g to 200 mgKOH / g, more preferably from 20 mgKOH / g to 180 mgKOH / g, and even more preferably from 30 mgKOH / g to 160 mgKOH / g.
When the hydroxyl value of the polyol is within the above range, the workability of the coating composition of the present embodiment, and the gloss, hardness, weather resistance and water vapor barrier properties of the coating film using the coating composition are better. It becomes a thing.
That is, the coating composition of this embodiment contains the above isocyanate component and a fluorine-containing polyol having a hydroxyl value of 10 mgKOH / g or more and 200 mgKOH / g or less.
The acid value of the polyol is preferably 0 mgKOH / g or more and 30 mgKOH / g or less.
The hydroxyl value and acid value can be measured according to JIS K1557.

[NCO / OH]
The molar ratio (NCO / OH) of the isocyanate group of the isocyanate component to the hydroxyl group of the polyol is preferably from 0.2 to 5.0, more preferably from 0.4 to 3.0, and from 0.5 to 2.0. The following is more preferable.
When NCO / OH is at least the above lower limit value, a tougher coating film tends to be obtained. On the other hand, when NCO / OH is not more than the above upper limit value, the smoothness of the coating film tends to be further improved.

[Other polyols]
In addition to the fluorine-containing polyol, the coating composition of the present embodiment may contain other polyol as a resin component (main agent). Examples of other polyols include polyester polyols, polyether polyols, acrylic polyols, and polyolefin polyols.

(Polyester polyol)
The polyester polyol can be obtained, for example, by subjecting a dibasic acid alone or a mixture of two or more kinds to a polyhydric alcohol alone or a mixture of two or more kinds.
Examples of the dibasic acid include succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, carboxylic acids such as isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, and pentaerythritol. , 2-methylolpropanediol, ethoxylated trimethylolpropane and the like.

As a specific method for producing the polyester polyol, for example, the condensation reaction can be carried out by mixing the above components and heating at about 160 ° C. or higher and 220 ° C. or lower.
Alternatively, for example, polycaprolactones obtained by ring-opening polymerization of lactones such as ε-caprolactone using a polyhydric alcohol can also be used as the polyester polyol.
The polyester polyol obtained by the above-described production method can be modified using aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, compounds obtained from these, and the like. Especially, it is preferable to modify the polyester polyol using aliphatic diisocyanate, alicyclic diisocyanate, and a compound obtained therefrom from the viewpoints of weather resistance and yellowing resistance of the resulting coating film.

  When the coating composition of the present embodiment contains a solvent having a high water content, a part of the carboxylic acid derived from the dibasic acid in the polyester polyol is left and neutralized with a base such as amine or ammonia. By doing so, the polyester polyol can be made into a water-soluble or water-dispersible resin.

(Polyether polyol)
The polyether polyol can be obtained using, for example, any one of the following methods (1) to (3).
(1) A method of obtaining a polyether polyol by randomly or block-adding an alkylene oxide alone or a mixture to a polyvalent hydroxy compound alone or a mixture using a catalyst.
Examples of the catalyst include hydroxides (lithium, sodium, potassium, etc.), strong basic catalysts (alcolate, alkylamine, etc.), complex metal cyanide complexes (metal porphyrin, hexacyanocobaltate zinc complex, etc.) and the like. It is done.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.
(2) A method of obtaining a polyether polyol by reacting an alkylene oxide with a polyamine compound.
As said polyamine compound, ethylenediamine etc. are mentioned, for example.
As said alkylene oxide, the thing similar to what was illustrated by (1) is mentioned.
(3) A method of obtaining so-called polymer polyols by polymerizing acrylamide or the like using the polyether polyols obtained in (1) or (2) as a medium.

Examples of the polyvalent hydroxy compound include those shown in the following (i) to (vi).
(I) diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like;
(Ii) sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and rhamnitol;
(Iii) monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribodesource;
(Iv) disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose;
(V) trisaccharides such as raffinose, gentianose, and meletitose;
(Vi) Tetrasaccharides such as stachyose.

(Acrylic polyol)
The acrylic polyol, for example, polymerizes only a polymerizable monomer having one or more active hydrogens in one molecule, or a polymerizable monomer having one or more active hydrogens in one molecule, and the polymerizable monomer It can be obtained by copolymerizing with other copolymerizable monomers.

Examples of the polymerizable monomer having one or more active hydrogens in one molecule include the following (i) to (vi). These may be used alone or in combination of two or more.
(I) Acrylic acid esters having active hydrogen such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate;
(Ii) Methacrylic acid having active hydrogen such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate Esters;
(Iii) (meth) acrylic acid esters having polyvalent active hydrogen such as (meth) acrylic acid monoesters of triols such as glycerin and trimethylolpropane;
(Iv) Monoethers of polyether polyols and (meth) acrylic acid esters having active hydrogen as described above Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, and polybutylene glycol. ;
(V) an adduct of glycidyl (meth) acrylate and a monobasic acid (for example, acetic acid, propionic acid, p-tert-butylbenzoic acid, etc.);
(Vi) Adducts obtained by ring-opening polymerization of lactones to active hydrogens of (meth) acrylic acid esters having the above active hydrogens. Examples of the lactones include ε-caprolactam and γ-valerolactone. Is mentioned.

Examples of other monomers copolymerizable with the polymerizable monomer include those shown in the following (i) to (iv). These may be used alone or in combination of two or more.
(I) Methyl acrylate, ethyl acrylate, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid-2-ethylhexyl, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, methacrylic acid-n-butyl, methacrylic acid (Meth) acrylic acid esters such as isobutyl, methacrylic acid-n-hexyl, cyclohexyl methacrylate, lauryl methacrylate, glycidyl methacrylate;
(Ii) Acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc.), unsaturated amides (unsaturated carboxylic acids such as acrylamide, N-methylolacrylamide, diacetone acrylamide);
(Iii) vinyl monomers having a hydrolyzable silyl group such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ- (meth) acrylopropyltrimethoxysilane;
(Iv) Other polymerizable monomers such as styrene, vinyl toluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.

  As a specific method for producing an acrylic polyol, for example, the above monomers are solution-polymerized in the presence of a known radical polymerization initiator such as a peroxide or an azo compound, and diluted with an organic solvent or the like as necessary. As a result, an acrylic polyol can be obtained.

  When the coating composition of the present embodiment contains a solvent having a large amount of water, it can be produced by a known method such as solution polymerization of the above monomers and conversion to an aqueous layer or emulsion polymerization. In that case, it is possible to impart water solubility or water dispersibility to the acrylic polyol by neutralizing an acidic moiety such as a carboxylic acid-containing monomer such as acrylic acid or methacrylic acid or a sulfonic acid-containing monomer with an amine or ammonia. it can.

(Polyolefin polyol)
Examples of the polyolefin polyol include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene having two or more hydroxyl groups, polyisoprene having two or more hydroxyl groups, and hydrogenated polyisoprene having two or more hydroxyl groups.

<Other additives>
In addition to the isocyanate component and the fluorine-containing polyol, the coating composition of the present embodiment may contain a melamine-based curing agent such as a complete alkyl type, a methylol type alkyl, or an imino group type alkyl as necessary. .

Moreover, all of the said isocyanate component, the said fluorine-containing polyol, and the coating composition of this embodiment may contain the organic solvent.
Although it does not specifically limit as an organic solvent, It is preferable that it does not have a functional group which reacts with a hydroxyl group and an isocyanate group, and it is preferable that it is fully compatible with an isocyanate component. Examples of such organic solvents include, but are not limited to, ester compounds, ether compounds, ketone compounds, aromatic compounds, ethylene glycol dialkyl ether compounds, and polyethylene glycol dicarboxylates that are generally used as coating solvents. Compounds, hydrocarbon solvents, aromatic solvents and the like.

  The isocyanate component, the fluorine-containing polyol, and the coating composition of the present embodiment are all catalysts for accelerating curing within a range that does not impair the desired effect of the present embodiment, depending on the purpose and application. Various additives used in the technical field such as pigments, leveling agents, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, surfactants, coating surface hydrophilic agents, etc. may be mixed and used. it can.

[Curing promotion catalyst]
Examples of the curing accelerating catalyst include, but are not limited to, metal salts and tertiary amines.
Examples of the metal salt include dibutyltin dilaurate, tin 2-ethylhexanoate, zinc 2-ethylhexanoate, and a cobalt salt.
Tertiary amines include, for example, triethylamine, pyridine, methylpyridine, benzyldimethylamine, N, N-dimethylcyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N, N′-endoethylenepiperazine, N, N ′. -Dimethyl piperazine etc. are mentioned.

[Pigment]
Examples of the pigment include titanium oxide, carbon black, indigo, quinacridone, and pearl mica.

[Leveling agent]
The leveling agent is not particularly limited, and examples thereof include silicone, aerosil, wax, stearate, polysiloxane and the like.

[Antioxidants, UV absorbers and light stabilizers]
Antioxidants, ultraviolet absorbers and light stabilizers include, for example, phosphoric acid or phosphorous acid aliphatic, aromatic or alkyl group-substituted aromatic esters, hypophosphorous acid derivatives, phosphorus compounds, phenol derivatives (especially hindered Phenolic compounds), compounds containing sulfur, tin compounds and the like. These may be contained alone or in combination of two or more.
Examples of the phosphorus compound include phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, dialkylbisphenol A diphosphite, and the like.
Examples of the sulfur-containing compound include thioether compounds, dithioacid salt compounds, mercaptobenzimidazole compounds, thiocarbanilide compounds, and thiodipropionic acid esters.
Examples of the tin compound include tin malate and dibutyltin monoxide.

[Plasticizer]
Although it does not specifically limit as a plasticizer, For example, phthalic acid esters, phosphoric acid esters, fatty acid esters, pyromellitic acid ester, epoxy plasticizer, polyether plasticizer, liquid rubber, non-aromatic paraffin oil Etc.
Examples of the phthalic acid esters include dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, and diisononyl phthalate.
Examples of phosphoric acid esters include tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimethylhexyl phosphate, tris-chloroethyl phosphate, tris-dichloropropyl phosphate, and the like.
Examples of fatty acid esters include trimellitic acid octyl ester, trimellitic acid isodecyl ester, trimellitic acid esters, dipentaerythritol esters, dioctyl adipate, dimethyl adipate, di-2-ethylhexyl azelate, dioctyl azelate. , Dioctyl sebacate, di-2-ethylhexyl sebacate, methylacetyl lysinate and the like.
Examples of the pyromellitic acid ester include pyromellitic acid octyl ester.
Examples of the epoxy plasticizer include epoxidized soybean oil, epoxidized linseed oil, and epoxidized fatty acid alkyl ester.
Examples of the polyether plasticizer include adipic acid ether ester and polyether.
Examples of the liquid rubber include liquid NBR, liquid acrylic rubber, and liquid polybutadiene.

[Surfactant]
Examples of the surfactant include known anionic surfactants, cationic surfactants, and amphoteric surfactants.

[Coating surface hydrophilic agent]
Examples of the coating surface hydrophilic agent include silicate compounds, silica hydrophilic agents, fluorine hydrophilic agents, titanium oxide photocatalysts, quaternary ammonium salt-containing polymers, and the like.

<Method for producing coating composition>
The coating composition of this embodiment can be manufactured using the following method.
For example, first, the fluorine-containing polyol or a solvent dilution thereof, if necessary, other resins, curing accelerators, pigments, leveling agents, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, The said isocyanate component is added as a hardening | curing agent to what added additives, such as surfactant. Next, if necessary, a solvent is further added to adjust the viscosity. Subsequently, a coating composition can be obtained by stirring using hand stirring or stirring equipment, such as a mazeller.

<Uses>
The coating composition of the present embodiment can be used as a coating such as roll coating, curtain flow coating, spray coating, bell coating, and electrostatic coating. Moreover, for example, it can be used as a primer or a top intermediate coating material for materials such as metal (steel plate, surface-treated steel plate, etc.), plastic, wood, film, inorganic material and the like. Further, for example, it is also useful as a paint for imparting heat resistance, cosmetic properties (surface smoothness, sharpness) and the like to pre-coated metals including rust-proof steel plates, automobile coating, and the like. In addition, it is also useful as a raw material for urethane such as adhesives, pressure-sensitive adhesives, elastomers, foams, and surface treatment agents.

≪Coating film≫
The coating film of this embodiment is formed by curing the coating composition according to the above embodiment.
The coating film of this embodiment is excellent in gloss, hardness, weather resistance, and water vapor | steam barrier property by including the said coating composition.

The coating film of the present embodiment is obtained by coating the coating composition on an object to be coated using a known coating method such as roll coating, curtain flow coating, spray coating, bell coating, or electrostatic coating. It can be manufactured by curing.
Examples of the object to be coated include the same materials as those exemplified in the above “<Usage>”.

  Hereinafter, the present embodiment will be described more specifically with specific examples and comparative examples. However, the present embodiment is not limited to the following examples and comparative examples unless they exceed the gist of the present embodiment. Absent. The physical properties of the polyisocyanate compositions in Examples and Comparative Examples were measured as follows. Unless otherwise specified, “parts” and “%” mean “parts by mass” and “mass%”.

<Method of measuring physical properties>
[Physical Property 1] Viscosity The viscosity of each isocyanate component was measured at 25 ° C. using an E-type viscometer (manufactured by Tokimec). In the measurement, a standard rotor (1 ° 34 ′ × R24) was used. The number of revolutions is as follows.
100 rpm (when less than 128 mPa · s)
50 rpm (128 mPa · s or more and less than 256 mPa · s)
20 rpm (256 mPa · s or more and less than 640 mPa · s)
10 rpm (in the case of 640 mPa · s or more and less than 1280 mPa · s)
5 rpm (in the case of 1280 mPa · s or more and less than 2560 mPa · s)

[Physical Property 2] Isocyanate Group (NCO) Content The isocyanate group (NCO) content (mass%) was determined by neutralizing the isocyanate group in the measurement sample with an excess of 2N amine and back titrating with 1N hydrochloric acid.

[Physical Property 3] Conversion Rate The “conversion rate” here means the mass ratio of the polyisocyanate compound produced by the polymerization reaction with respect to the mass of the charged isocyanate monomer such as triisocyanate or diisocyanate. The conversion was calculated as follows. First, using the synthesized polyisocyanate compound as a sample, measurement was performed by gel permeation chromatography (GPC) under the following apparatus and conditions, and the polystyrene-based number average was calculated. Molecular weight was obtained. In GPC measurement, the number average molecular weight of the polyisocyanate compound was defined as an area ratio of a peak having a number average molecular weight larger than that of an isocyanate monomer such as unreacted triisocyanate or diisocyanate.

(Measurement condition)
Equipment: “HLC-8120GPC” (trade name) manufactured by Tosoh Corporation
Column: "TSKgel SuperH1000" (product name) x 1 manufactured by Tosoh Corporation
"TSKgel SuperH2000" (trade name) x 1
“TSKgel SuperH3000” (trade name) × 1 Carrier: Tetrahydrofuran Detection method: Differential refractometer Sample concentration: 5 wt / vol%
Outflow amount: 0.6 mL / min
Column temperature: 30 ° C

<Evaluation method>
[Evaluation 1] Gloss of coating film A coated plate in which an aluminum plate was painted in white was prepared in advance. After coating each coating composition obtained in Examples and Comparative Examples on the coated plate so as to have a dry film thickness of 40 μm, the coating composition was cured at 23 ° C. and 50% RH for one week to obtain a coating film. It was. The gloss of the prepared coating film was measured using a gloss meter (Glossometer UGV-6P, manufactured by Suga Test Instruments Co., Ltd.) under the condition of a reflection angle of 60 °. As the evaluation criteria, ◎ if the gloss value is 85% or more, ◯ if it is 80% or more and less than 85%, Δ if it is 75% or more and less than 80%, and × if it is less than 75%.

[Evaluation 2] Coating Film Hardness Each coating composition obtained in Examples and Comparative Examples was coated on a glass plate to a dry film thickness of 40 μm, and then cured at 23 ° C. and 50% RH for 1 week. To obtain a coating film. The produced coating film was measured with a Koenig hardness meter (manufactured by BYK Chemie), and the hardness of the coating film was evaluated. As evaluation criteria, ◎ if the number of measurements was 90 times or more, ◯ if it was 70 times or more and less than 90 times, Δ if it was 50 times or more and less than 70 times, and x if it was less than 50 times.

[Evaluation 3] Weather resistance of coating film A coated plate in which an aluminum plate was painted in white was prepared in advance. After coating each coating composition obtained in Examples and Comparative Examples on the coated plate so as to have a dry film thickness of 40 μm, the coating composition was cured at 23 ° C. and 50% RH for one week to obtain a coating film. It was. The produced coating film was measured under the following conditions using a Sansha Ink Senon Weather Meter (manufactured by Suga Test Instruments), and the weather resistance of the coating film was evaluated.

(Measurement condition)
Operation cycle: Drying / spraying = 102 minutes / 18 minutes cycle operation Drying black panel temperature: 63 degrees Humidity condition: 50%
Layer temperature during spraying: 28 ° C
Light intensity: 180 W / m ²

  As evaluation criteria, ◎ if the gloss retention after 8000 h is 90% or more, ◎ if 80% or more, Δ if 50% or more, and x if less than 50%.

[Evaluation 4] Water vapor barrier property of coating film Each coating composition obtained in Examples and Comparative Examples was coated on an aluminum foil to a thickness of 25 μm, and then at 23 ° C. and 50% RH for 1 week. It was allowed to stand and harden to obtain a coating film. The prepared coating film is peeled off from the aluminum foil and used as a sample. Based on JIS Z0208 (moisture-proof packaging material moisture permeability test method), measurement is performed under condition B (temperature 40 degrees, humidity 90 RH%), and the water vapor barrier property of the coating film Evaluated. As evaluation criteria, if the water vapor permeation amount 500 g / mm less than ² ◎, 500g / mm ² or more 750 g / mm ² than if 〇, if 750 g / ^{mm 2} or more 1000 g / mm less than ² △, × if 1000 g / mm ² or more It was.

<Synthesis of Triisocyanate (I) and Polyisocyanate Compound>
Synthesis Example 1 Synthesis of Isocyanate Component L-1 (NTI) 4-Aminomethyl-1,8-octamethylenediamine (hereinafter simply referred to as “4-aminomethyl-1,8-octamethylenediamine”) was placed in a four-necked flask equipped with a stirrer, a thermometer, and a gas introduction tube. 1060 g (sometimes referred to as “triamine”) was dissolved in 1500 g of methanol, and 1800 mL of 35% concentrated hydrochloric acid was gradually added dropwise thereto while cooling. Methanol and water were removed under reduced pressure, and the mixture was concentrated and dried under the conditions of 60 ° C. and 5 mmHg for 24 hours. As a result, white solid triamine hydrochloride was obtained. 650 g of the resulting triamine hydrochloride was suspended as a fine powder in 5000 g of o-dichlorobenzene, and the temperature of the reaction solution was increased while stirring. When the temperature reached 100 ° C., phosgene was started to be blown at a rate of 200 g / hour, and the temperature was further raised and maintained at 180 ° C., and phosgene was continuously blown for 12 hours. Dissolved phosgene and the solvent were distilled off under reduced pressure, followed by vacuum distillation to obtain colorless and transparent 4-isocyanatomethyl-1,8-octamethylene having a boiling point of 161 ° C./1.2 mmHg or more and 163 ° C./1.2 mmHg or less. 420 g of diisocyanate (hereinafter sometimes referred to as “NTI”) was obtained. The viscosity of the obtained NTI was 8 mPa · s / 25 ° C., and the NCO content was 50.0 mass%. The obtained NTI was designated as isocyanate component L-1.

[Synthesis Example 2] Synthesis of isocyanate component L-2 (LTI) In a four-necked flask equipped with a stirrer, a thermometer and a gas introduction tube, ethanol amine 122.2 g, o-dichlorobenzene 100 mL, and toluene 420 mL Then, ice-cooled hydrogen chloride gas was introduced to convert ethanolamine into hydrochloride. Next, 182.5 g of lysine hydrochloride was added, the reaction solution was heated to 80 ° C., ethanolamine hydrochloride was dissolved, and hydrogen chloride gas was introduced to form lysine dihydrochloride. Further, hydrogen chloride gas was passed at a rate of 20 mL / min to 30 mL / min, the reaction solution was heated to 116 ° C., and this temperature was maintained until no water distilled off. The resulting reaction mixture was recrystallized in a mixed solution of methanol and ethanol to obtain 165 g of lysine β-aminoethyl ester trihydrochloride. 100 g of this lysine β-aminoethyl ester trihydrochloride was suspended as fine powder in 1200 mL of o-dichlorobenzene, and the temperature of the reaction solution was raised while stirring. When the temperature reached 120 ° C., phosgene was blown in at a rate of 0.4 mol / hour, maintained for 10 hours, and then heated to 150 ° C. The suspension was almost dissolved. After cooling, the mixture was filtered, and the dissolved phosgene and the solvent were distilled off under reduced pressure, followed by vacuum distillation, whereby a colorless transparent lysine triisocyanate (hereinafter referred to as “boiling point” 155 ° C./0.022 mmHg to 157 ° C./0.022 mmHg). 80.4 g was obtained (sometimes referred to as “LTI”). The viscosity of the obtained LTI was 20 mPa · s / 25 ° C., and the NCO content was 47.1% by mass. The obtained LTI was designated as isocyanate component L-2.

[Synthesis Example 3] Synthesis of Isocyanate Component L-3 A four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen blowing tube was placed in a nitrogen atmosphere, and 100 g of NTI and 2-ethyl-1 were used as monomers. -The hexanol 0.5g was prepared and temperature was hold | maintained at 80 degreeC for 2 hours. Thereafter, 0.01 g of isocyanurate-forming catalyst benzyltrimethylammonium capric acid was added to carry out an isocyanurate-forming reaction. When the conversion reached 42%, 0.05 g of dibutyl phosphoric acid was added to stop the reaction. The reaction solution was further maintained at 120 ° C. for 15 minutes to obtain an isocyanate component L-3. The viscosity of the isocyanate component L-3 was 85 mPa · s / 25 ° C., and the NCO content was 42.3 mass%.

[Synthesis Example 4] Synthesis of Isocyanate Component L-4 In the same apparatus as in Synthesis Example 3, 100 g of NTI and 0.6 g of methanol were charged as monomers, and the temperature was maintained at 80 ° C. for 2 hours. Thereafter, 0.1 g of isocyanurate-forming catalyst tetramethylammonium capric acid was added to carry out an isocyanurate-forming reaction. When the conversion rate reached 48%, 0.03 g of dibutyl phosphoric acid was added to stop the reaction. The reaction solution was further maintained at 120 ° C. for 15 minutes to obtain an isocyanate component L-4. The viscosity of the isocyanate component L-4 was 80 mPa · s / 25 ° C., and the NCO content was 42.0 mass%.

[Synthesis Example 5] Synthesis of Isocyanate Component L-5 In the same apparatus as in Synthesis Example 3, 100 g of NTI, 23 g of trimethyl phosphoric acid, 23 g of methyl cellosolve acetate, and 0.74 g of water were charged as monomers at a temperature of 90 ° C. Hold for 1 hour. Thereafter, the temperature was maintained at 160 ° C. for 2 hours to obtain an isocyanate component L-5. The viscosity of the resulting isocyanate component L-5 was 26 mPa · s / 25 ° C., and the NCO content was 44.8% by mass.

[Synthesis Example 6] Synthesis of Isocyanate Component L-6 In the same apparatus as in Synthesis Example 3, 100 g of LTI, 20 g of trimethyl phosphoric acid, 20 g of methyl cellosolve acetate, and 0.56 g of water were charged at a temperature of 90 ° C. Hold for 1 hour. Thereafter, the temperature was set to 160 ° C. and maintained for 2 hours to obtain an isocyanate component L-6. The viscosity of the resulting isocyanate component L-6 was 33 mPa · s / 25 ° C., and the NCO content was 43.4% by mass.

[Synthesis Example 7] Synthesis of Isocyanate Component Q-1 In the same apparatus as in Synthesis Example 3, 100 g of HDI and 4 g of isobutanol were charged as monomers, and the temperature was maintained at 80 ° C. for 2 hours. Thereafter, 0.1 g of isocyanurate-forming catalyst tetramethylammonium capric acid was added to carry out an isocyanurate-forming reaction. When the conversion rate reached 30%, 0.03 g of dibutyl phosphoric acid was added to stop the reaction. The reaction solution was further maintained at 120 ° C. for 15 minutes, and the resulting reaction solution was fed to a thin film evaporator to remove unreacted HDI, thereby obtaining an isocyanate component Q-1. The obtained isocyanate component Q-1 had a viscosity of 300 mPa · s / 25 ° C. and an NCO content of 20.0% by mass.

[Synthesis Example 8] Synthesis of Isocyanate Component Q-2 In the same apparatus as in Synthesis Example 3, 100 g of HDI and 0.1 g of isobutanol were charged as monomers, and the temperature was maintained at 80 ° C. for 2 hours. Thereafter, 0.4 g of isocyanurate-forming catalyst tetramethylammonium capric acid was added to carry out an isocyanurate-forming reaction. When the conversion reached 45%, 0.3 g of dibutyl phosphoric acid was added to stop the reaction. The reaction solution was further maintained at 120 ° C. for 15 minutes. The obtained reaction liquid was fed to a thin film evaporator, and unreacted HDI was removed to obtain an isocyanate component Q-2. The obtained isocyanate component Q-2 had a viscosity of 2500 mPa · s / 25 ° C. and an NCO content of 21.5% by mass.

[Example 1] Production of coating composition A-1 Fluorine-containing polyol (manufactured by Daikin Corporation, trade name “Zeffle GK570”, resin concentration 65%, hydroxyl value 60 mgKOH / g), obtained in Synthesis Example 1 The isocyanate component L-1 was used so that the isocyanate group / hydroxyl molar ratio was 1.0. Furthermore, it adjusted so that solid content might be 40 mass% with butyl acetate, and coating composition A-1 was obtained. The resulting coating composition was subjected to various evaluations using the methods described above. As a result, the gloss was ◎, the hardness was ◎, the weather resistance was ◎, and the water vapor barrier property of the coating film was ◎. The evaluation results are shown in Table 1.

[Examples 2 to 6] Production of coating compositions A-2 to A-6 A coating composition A-2 was prepared in the same manner as in Example 1 except that the isocyanate components of the type shown in Table 1 were used. -A-6 was produced. Various evaluation was performed about the obtained coating composition using the method of the said description. The evaluation results are shown in Table 1.

Comparative Example 1 Production of Coating Composition B-1 Same as Example 1 except that HDI (viscosity is 3 mPa · s / 25 ° C., NCO content is 50.0 mass%) was used as the isocyanate component. The coating composition B-1 was produced using the method described above. Various evaluation was performed about the obtained coating composition using the method of the said description. The evaluation results are shown in Table 1.

[Comparative Examples 2-3] Production of Coating Compositions B-2 to B-3 A coating composition B-2 was prepared in the same manner as in Example 1 except that the isocyanate components of the type shown in Table 1 were used. -B-3 was manufactured. Various evaluation was performed about the obtained coating composition using the method of the said description. The evaluation results are shown in Table 1.

From Table 1, the coating composition A-1-A-6 which mix | blended the isocyanate component containing at least any one compound among the polyisocyanate compound induced | guided | derived from triisocyanate (I) and triisocyanate (I) (Example) In 1-6), the blended isocyanate component had a low viscosity of 8 mPa · s or more and 85 mPa · s or less, and the gloss, hardness, weather resistance, and water vapor barrier properties were all good when used as a coating film.
Also, coating compositions A-1 and A-2 (Examples 1 and 2) containing an isocyanate component containing only triisocyanate (I) are polyisocyanate compounds derived from triisocyanate (I) and triisocyanate ( The NCO content was particularly high at 47% by mass or more, compared with the coating compositions A-3 to A-6 (Examples 3 to 6) in which the isocyanate component containing both of I) was blended.
Moreover, coating composition A-1, A-2, A-5, and A-6 which mix | blended the isocyanate component whose NCO content is 43.4 mass% or more are the isocyanate components whose NCO content is less than the above. The weather resistance was particularly better than the blended coating compositions A-3 and A-4.

  The coating composition of the present embodiment can be used as a coating such as roll coating, curtain flow coating, spray coating, bell coating, and electrostatic coating. The coating composition of the present embodiment can be used as a primer or a top intermediate coating for materials such as metals, plastics, wood, films, and inorganic materials. The coating composition of the present embodiment is also useful as a coating that imparts heat resistance, cosmetics (surface smoothness, sharpness), etc. to pre-coated metals including rust-proof steel plates, automobile coating, and the like. The coating composition of this embodiment is also useful as a urethane raw material for adhesives, pressure-sensitive adhesives, elastomers, foams, surface treatment agents and the like.

Claims (4)

An isocyanate component containing at least one of the triisocyanate represented by the following general formula (I) and a polyisocyanate compound derived from the triisocyanate;
A fluorine-containing polyol having a hydroxyl value of 10 mgKOH / g or more and 200 mgKOH / g or less,
A coating composition comprising:

(In the general formula (I), a plurality of Y ^{1 s} each independently contains a single bond or one or more selected from the group consisting of an ester group and an ether group. A plurality of Y ¹ may be the same or different from each other, and R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. )   The coating composition according to claim 1, wherein the isocyanate component has a viscosity at 25 degrees of 5 mPa · s to 100 mPa · s.   The coating composition according to claim 1 or 2, wherein an isocyanate group content of the isocyanate component is 40% by mass or more.   The coating film formed by hardening | curing the coating composition of Claims 1-3.