JP6267958B2 - Polyisocyanate composition, coating composition, and cured product - Google Patents

Description

  The present invention relates to a polyisocyanate composition, a coating composition, and a cured product.

  Polyurethane resins using polyisocyanate compositions obtained from aliphatic diisocyanates and alicyclic diisocyanates as curing agents have excellent weather resistance, chemical resistance, abrasion resistance, etc. Widely used as an agent.

  However, when a polyisocyanate composition obtained from an aliphatic diisocyanate is used alone, sufficient drying properties may not be obtained. In addition, when a polyisocyanate composition obtained from an alicyclic diisocyanate is used alone, the reactivity may be low and a sufficient crosslinked coating film may not be obtained.

  In order to solve these problems, a polyisocyanate composition containing an aliphatic diisocyanate and an alicyclic diisocyanate has been proposed.

  As an example of mixing two kinds of polyisocyanates having different properties, a polyisocyanate composition in which an aliphatic polyisocyanate and an alicyclic polyisocyanate are mixed (for example, see Patent Document 1 and Patent Document 2) is disclosed.

  The polyisocyanate composition described in Patent Document 1 is excellent in terms of crosslinkability and quick drying. Moreover, since the polyisocyanate composition described in Patent Document 2 uses an aliphatic polyisocyanate having a high allophanate group / isocyanurate ratio, it is excellent in terms of low viscosity.

  Moreover, the polyisocyanate composition which the specific ratio contains the uretdione dimer obtained by copolymerization of aliphatic diisocyanate and alicyclic diisocyanate is also disclosed (for example, refer patent document 3).

Japanese Translation of National Publication No. 06-510087 International Publication Number WO2008 / 142848 Japanese Patent Laid-Open No. 04-298522

  However, the polyisocyanate composition described in Patent Document 1 has a problem that the viscosity increases and the amount of solvent used increases. Moreover, since the polyisocyanate composition described in Patent Document 2 has a large amount of modification of allophanate groups, there is a problem in that the average number of functional groups of the polyisocyanate composition is low and the crosslinkability and adhesion are poor. Furthermore, the polyisocyanate composition described in Patent Document 3 has a problem that the storage stability of the polyisocyanate composition is poor.

  The present invention has been made in view of the above problems, and can provide a coating composition having a low viscosity, excellent adhesion and quick drying, and excellent storage stability. It aims at providing the coating composition containing an isocyanate composition and the hardened | cured material which consists of this coating composition.

  As a result of intensive studies, the present inventors have found that the above problems can be achieved by using a polyisocyanate containing a specific structure, and have completed the present invention.

That is, the present invention is as follows.
[1]
A polyisocyanate composition comprising an alicyclic polyisocyanate consisting of aliphatic polyisocyanates and alicyclic diisocyanates units consisting of fat-aliphatic diisocyanate units,
The molar ratio of the aliphatic diisocyanate unit / the alicyclic diisocyanate unit in the polyisocyanate composition is 95/5 to 50/50,
The polyisocyanate composition comprises a polyisocyanate having an isocyanurate group;
The content of the isocyanurate group is 100 mol% in total of the isocyanurate group, allophanate group, burette group, urethane group, uretdione group, iminooxadiazinedione group, and urea group in the polyisocyanate composition. , 60 mol% or more,
The polyisocyanate composition comprises a uretdione dimer and a polyisocyanate having an allophanate group;
The content of the uretdione dimer is 1 to 35% by mass,
And the molar ratio of allophanate group / isocyanurate group is from 1/99 to 50/50,
The polyisocyanate composition whose viscosity in 25 degreeC is 100-10000 mPa * s.
[2]
The polyisocyanate having an isocyanurate group includes an isocyanurate trimer;
The polyisocyanate composition according to [1], wherein the content of the isocyanurate trimer is 55 to 95% by mass.
[3]
The polyisocyanate composition according to [1] or [2] above, wherein the average number of functional groups of the isocyanate group of the polyisocyanate composition is 2.5 to 4.0.
[4]
The aliphatic polyisocyanate includes an aliphatic polyisocyanate having a uretdione dimer and an allophanate group,
The content of the uretdione dimer is 1 to 50% by mass with respect to the total amount of the aliphatic polyisocyanate,
And the molar ratio of allophanate group / isocyanurate group is from 1/99 to 50/50,
The polyisocyanate composition according to any one of [1] to [3] above.
[5]
The polyisocyanate composition according to any one of [1] to [4] , wherein the aliphatic polyisocyanate has a viscosity at 25 ° C. of 150 to 800 mPa · s.
[6]
A coating composition comprising an active hydrogen compound and the polyisocyanate composition according to any one of [1] to [5] .
[7]
Hardened | cured material obtained using the coating composition of previous clause [6] .

  According to the present invention, a polyisocyanate composition having low viscosity, excellent adhesion and quick drying, and excellent storage stability, a coating composition obtained from the polyisocyanate composition, And a cured product comprising the coating composition.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.

[Diisocyanate unit]
In the present embodiment, the “diisocyanate unit” refers to a diisocyanate constituting a polyisocyanate.

[Aliphatic diisocyanate]
The “aliphatic diisocyanate” used in the present embodiment refers to a diisocyanate compound that does not contain an aromatic ring in its structure. Although it does not specifically limit as aliphatic diisocyanate, A C4-C30 thing is preferable, for example, tetramethylene-1, 4- diisocyanate, pentamethylene 1, 5- diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, Examples include lysine diisocyanate. Among these, hexamethylene diisocyanate (hereinafter also referred to as “HDI”) is preferable from the viewpoint of weather resistance and availability. An aliphatic diisocyanate may be used individually by 1 type, or may use 2 or more types together.

[Alicyclic diisocyanate]
The “alicyclic diisocyanate” used in the present embodiment refers to a diisocyanate compound having a cyclic aliphatic group in the molecule. Although it does not specifically limit as alicyclic diisocyanate, For example, isophorone diisocyanate (henceforth "IPDI"), hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1, 4- diisocyanate cyclohexane etc. are mentioned. Among these, IPDI, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are preferable from the viewpoint of availability, and IPDI is more preferable from the viewpoint of quick drying of the coating film and high hardness. An alicyclic diisocyanate may be used individually by 1 type, or may use 2 or more types together.

[Polyisocyanate composition]
The polyisocyanate composition of this embodiment is
Polyisocyanate composition comprising a copolymerized polyisocyanate comprising an aliphatic diisocyanate unit and an alicyclic diisocyanate unit, and / or an aliphatic polyisocyanate comprising an aliphatic diisocyanate unit and an alicyclic polyisocyanate comprising an alicyclic diisocyanate unit A thing,
The molar ratio of the aliphatic diisocyanate unit / the alicyclic diisocyanate unit in the polyisocyanate composition is 95/5 to 50/50,
The polyisocyanate composition comprises a polyisocyanate having an isocyanurate group;
The content of the isocyanurate group is 100 mol% in total of the isocyanurate group, allophanate group, burette group, urethane group, uretdione group, iminooxadiazinedione group, and urea group in the polyisocyanate composition. , 60 mol% or more,
The viscosity at 25 ° C. is 100 to 10,000 mPa · s.

The polyisocyanate composition of this embodiment is
(1) copolymerized polyisocyanate;
(2) Aliphatic polyisocyanates and alicyclic polyisocyanates;
(3) copolymerized polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate;
(4) copolymerized polyisocyanate and aliphatic polyisocyanate; or
(5) copolymerized polyisocyanate and alicyclic polyisocyanate;
Embodiments.

[Copolymerized polyisocyanate]
The copolymerized polyisocyanate is a polyisocyanate containing an aliphatic diisocyanate unit and an alicyclic diisocyanate unit, and can have functional groups such as a biuret group, an isocyanurate group, a urethane group, an allophanate group, and a uretdione group. Copolymerized polyisocyanate may be used individually by 1 type, or may use 2 or more types together.

  The content of biuret type polyisocyanate in the copolymerized polyisocyanate is preferably 0.5% by mass or less. When the content of the biuret type polyisocyanate is 0.5% by mass or less, the storage stability tends to be further improved.

  The total content of aliphatic and alicyclic diisocyanates in the copolymerized polyisocyanate is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% or less. . When the total content of aliphatic and alicyclic diisocyanates is 1% by mass or less, curability tends to be further improved. Moreover, the lower limit of the total content of the aliphatic and alicyclic diisocyanates is not particularly limited, but it is preferably as small as possible, more preferably 0% by mass.

[Aliphatic polyisocyanate]
The aliphatic polyisocyanate is a polyisocyanate containing an aliphatic diisocyanate unit and not containing an alicyclic diisocyanate unit, and has a functional group such as a biuret group, an isocyanurate group, a urethane group, an allophanate group, or a uretdione group. it can. An aliphatic polyisocyanate may be used individually by 1 type, or may use 2 or more types together.

  The viscosity of the aliphatic polyisocyanate at 25 ° C. is preferably 150 to 800 mPa · s. The upper limit of the viscosity at 25 ° C. of the aliphatic polyisocyanate is preferably 800 mPa · s, more preferably 700 mPa · s, and further preferably 600 mPa · s in terms of curability and workability. In addition, the lower limit of the viscosity at 25 ° C. of the aliphatic polyisocyanate is preferably 150 mPa · s, more preferably 200 mPa · s, and further preferably 250 mPa · s from the viewpoint of storage stability. The viscosity can be measured by the method described in the examples.

  The content of the uretdione dimer in the aliphatic polyisocyanate is preferably 1 to 50% by mass. The upper limit of the content of the uretdione dimer in the aliphatic polyisocyanate is preferably 50% by mass, more preferably 40% by mass, and even more preferably 30% by mass in terms of storage stability. . The lower limit of the content of the uretdione dimer in the aliphatic polyisocyanate is preferably 5% by mass, more preferably 8% by mass, and further preferably 10% by mass in terms of viscosity. .

  The molar ratio of allophanate group / isocyanurate group in the aliphatic polyisocyanate is preferably 1/99 to 50/50. The lower limit of the allophanate group in the aliphatic polyisocyanate is preferably 1%, more preferably 3%, still more preferably 5%, and even more preferably 8% in terms of low viscosity. Particularly preferably, it is 16%. The upper limit of the allophanate group in the aliphatic polyisocyanate is preferably 50%, more preferably 45%, still more preferably 40%, and still more preferably 35% in terms of hardness. Particularly preferably, it is 30%.

  The content of biuret type polyisocyanate in the aliphatic polyisocyanate is preferably 0.5% by mass or less. When the content of the biuret type polyisocyanate is 0.5% by mass or less, the storage stability tends to be further improved.

  The content of the aliphatic diisocyanate in the aliphatic polyisocyanate is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% or less. When the content of the aliphatic diisocyanate is 1% by mass or less, the curability tends to be further improved. Moreover, the lower limit of the content of the aliphatic diisocyanate is not particularly limited, but it is preferably as small as possible, and more preferably 0% by mass.

[Alicyclic polyisocyanate]
The alicyclic polyisocyanate is a polyisocyanate containing an alicyclic diisocyanate unit and not containing an aliphatic diisocyanate unit, and has functional groups such as a biuret group, an isocyanurate group, a urethane group, an allophanate group, and a uretdione group. Can do. Among these, the alicyclic polyisocyanate preferably contains an alicyclic polyisocyanate containing an isocyanurate group. By including an alicyclic polyisocyanate containing an isocyanurate group, the hardness tends to be further improved. An alicyclic polyisocyanate may be used individually by 1 type, or may use 2 or more types together.

  The content of the alicyclic polyisocyanate containing an isocyanurate group is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol, based on the total alicyclic polyisocyanate. % Or more, particularly preferably 80 mol% or more. When the content of the alicyclic polyisocyanate containing an isocyanurate group is within the above range, the hardness tends to be further improved. Further, the upper limit of the content of the alicyclic polyisocyanate containing an isocyanurate group is preferably as high as possible, more preferably 98% by mass.

  The content of biuret type polyisocyanate in the alicyclic polyisocyanate is preferably 0.5% by mass or less. When the content of the biuret type polyisocyanate is 0.5% by mass or less, the storage stability tends to be further improved.

  The content of the alicyclic diisocyanate in the alicyclic polyisocyanate is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% or less. When the content of the alicyclic diisocyanate is 1% by mass or less, the curability tends to be further improved. Moreover, the lower limit of the content of the alicyclic diisocyanate is not particularly limited, but it is preferably as small as possible, and more preferably 0% by mass.

  The mass mixing ratio of the aliphatic polyisocyanate and the alicyclic polyisocyanate is preferably 90/10 to 50/50 in terms of adhesion. The lower limit of the mass mixing ratio of the aliphatic polyisocyanate and the alicyclic polyisocyanate is preferably 55% by mass, more preferably 60% by mass, still more preferably 65% by mass, and particularly preferably 70%. % By mass. The upper limit of the mass mixing ratio of the aliphatic polyisocyanate and the alicyclic polyisocyanate is preferably 90% by mass, more preferably 85% by mass, still more preferably 80% by mass, Preferably it is 75 mass%.

  The molar ratio (aliphatic diisocyanate unit / alicyclic diisocyanate unit) between the aliphatic diisocyanate unit and the alicyclic diisocyanate unit in the polyisocyanate composition is 95/5 to 50/50. The lower limit of the molar ratio of the aliphatic diisocyanate unit is 50 mol%, preferably 55 mol%, more preferably 60 mol%, still more preferably 65 mol%, particularly preferably 70 mol%. It is. When the lower limit of the molar ratio of the aliphatic diisocyanate unit is 50 mol% or more, the low viscosity and curability are further improved. The upper limit of the molar ratio of the aliphatic diisocyanate unit is 95 mol%, preferably 90 mol%, more preferably 85 mol%, still more preferably 80 mol%, and particularly preferably 75 mol%. Mol%. When the upper limit value of the molar ratio of the aliphatic diisocyanate unit is 95 mol% or more, the hardness and adhesion are further improved. In addition, the molar ratio of the aliphatic diisocyanate unit and the alicyclic diisocyanate unit in the polyisocyanate composition can be measured by the method described in the examples.

  The content of biuret type polyisocyanate in the polyisocyanate composition of the present embodiment is preferably 0.5% by mass or less. When the content of the biuret type polyisocyanate is 0.5% by mass or less, the storage stability tends to be further improved.

  The total content of aliphatic and alicyclic diisocyanates in the polyisocyanate composition of the present embodiment is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.3%. % Or less. When the total content of aliphatic and alicyclic diisocyanates is 1% by mass or less, curability tends to be further improved. Moreover, the lower limit of the total content of the aliphatic and alicyclic diisocyanates is not particularly limited, but it is preferably as small as possible, more preferably 0% by mass.

[Polyisocyanate having an isocyanurate group]
The polyisocyanate composition includes a polyisocyanate having an isocyanurate group. It is preferable that at least one selected from the group consisting of a copolymerized polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate contains a polyisocyanate having an isocyanurate group. The isocyanurate group refers to a group represented by the following formula (1).
(1)

  The isocyanurate group content in the polyisocyanate composition is a total of 100 isocyanurate groups, allophanate groups, burette groups, urethane groups, uretdione groups, iminooxadiazinedione groups, and urea groups in the polyisocyanate composition. It is 60 mol% or more with respect to mol%, preferably 65 mol% or more, more preferably 70 mol% or more. When the content of the isocyanurate group is 60 mol% or more, low viscosity and curability are further improved. The upper limit of the content of isocyanurate groups is not particularly limited, but isocyanurate groups, allophanate groups, burette groups, urethane groups, uretdione groups, iminooxadiazinedione groups, and urea in the polyisocyanate composition. It is preferably 90 mol% or less, more preferably 80 mol% or less, and still more preferably 75 mol% or less, with respect to the total amount of the base structural units of 100 mol%. When the upper limit of the content of the isocyanurate group is 90 mol% or less, the adhesion tends to be further improved. In addition, content of the isocyanurate group in a polyisocyanate composition can be measured by the method as described in an Example.

  The polyisocyanate having an isocyanurate group is not particularly limited, and examples thereof include isocyanurate trimers, pentamers, heptamers and higher isocyanurate multimers. Among these, from the viewpoint of curability, the polyisocyanate having an isocyanurate group preferably contains an isocyanurate trimer. The isocyanurate trimer is a structure composed of three molecules of aliphatic and / or alicyclic diisocyanate and having one isocyanurate group.

  The content of the isocyanurate trimer is preferably 55 to 95% by mass with respect to the total amount of the polyisocyanate composition. The lower limit of the content of the isocyanurate trimer is preferably 55% by mass, more preferably 60% by mass, still more preferably 65% by mass, and particularly preferably 70% by mass. When the lower limit value of the content of the isocyanurate trimer is within the above range, the curability tends to be further improved. Further, the upper limit of the content of the isocyanurate trimer is preferably 95% by mass, more preferably 90% by mass, and still more preferably 80% by mass. When the upper limit of the content of the isocyanurate trimer is within the above range, the adhesion tends to be further improved. In addition, content of an isocyanurate trimer can be measured by the method as described in an Example.

[Polyisocyanate having an allophanate group]
The polyisocyanate composition of the present embodiment, that is, at least one selected from the group consisting of copolymerized polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate may contain a polyisocyanate having an allophanate group.

The allophanate group is a group formed from an alcohol and an isocyanate group, and is represented by the following formula (2).
(2)

  In the polyisocyanate composition, the allophanate group / isocyanurate group molar ratio is preferably 1/99 to 50/50. The lower limit of the molar ratio of the allophanate group is preferably 1 mol%, more preferably 5 mol%, still more preferably 8 mol%, and particularly preferably 10 mol%. When the lower limit of the molar ratio of the allophanate group is 1 mol% or more, the viscosity tends to be further lowered. The upper limit of the molar ratio of allophanate groups is preferably 50 mol%, more preferably 40 mol%, still more preferably 30 mol%, still more preferably 20 mol%, particularly preferably. Is 15 mol%. When the upper limit of the molar ratio of the allophanate group is 50 mol% or less, the hardness tends to be further improved. The allophanate group / isocyanurate group molar ratio can be measured by the method described in Examples.

[Urethione dimer]
The polyisocyanate composition of the present embodiment, that is, at least one selected from the group consisting of copolymerized polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate may contain a uretdione dimer. The uretdione dimer is a compound composed of two diisocyanate molecules and is represented by the following formula (3).
(3)

  As for content of a uretdione dimer, 1-35 mass% is preferable with respect to the total amount of a polyisocyanate composition. The lower limit of the content of the uretdione dimer is preferably 1% by mass, more preferably 2% by mass, still more preferably 5% by mass, and particularly preferably 8% by mass. When the lower limit of the content of the uretdione dimer is 1% by mass or more, the viscosity is further lowered and the curability tends to be further improved. The upper limit of the content of the uretdione dimer is preferably 35% by mass, more preferably 30% by mass, still more preferably 25% by mass, and particularly preferably 20% by mass. When the upper limit of the content of the uretdione dimer is 35% by mass or less, the storage stability tends to be further improved. In addition, content of a uretdione dimer can be measured by the method as described in an Example.

  The polyisocyanate of this embodiment preferably contains both a uretdione dimer and a polyisocyanate having an allophanate group from the viewpoint of further reducing the viscosity.

[Viscosity at 25 ° C]
The viscosity at 25 ° C. of the polyisocyanate composition of the present embodiment is 100 to 10,000 mPa · s. The lower limit of the viscosity at 25 ° C. is 100 mPa · s, preferably 500 mPa · s, more preferably 1000 mPa · s, still more preferably 1500 mPa · s, and particularly preferably 2000 mPa · s. When the lower limit of the viscosity at 25 ° C. is 100 mPa · s or more, the curability is further improved. The upper limit of the viscosity at 25 ° C. is 10,000 mPa · s, preferably 7000 mPa · s, more preferably 6000 mPa · s, still more preferably 5000 mPa · s, and particularly preferably 4000 mPa · s. is there. Workability improves more because the lower limit of the viscosity in 25 degreeC is 10000 mPa * s or less. The viscosity can be measured by the method described in the examples.

[Average number of functional groups of isocyanate groups]
As for the average functional group number of the isocyanate group of the polyisocyanate contained in the polyisocyanate composition of this embodiment, 2.5-4.0 are preferable. The lower limit of the average number of functional groups of the isocyanate group is preferably 2.5, more preferably 2.6, still more preferably 2.7, and particularly preferably 2.8. When the lower limit value of the average number of functional groups of the isocyanate group is 2.5 or more, the curability tends to be further improved. The upper limit of the average number of functional groups of the isocyanate group is preferably 4.0, more preferably 3.8, still more preferably 3.6, and particularly preferably 3.4. When the upper limit of the average number of functional groups of the isocyanate group is 4.0 or less, the viscosity tends to be further lowered. The average number of functional groups of the isocyanate group can be determined by the method described in the examples.

[Method for producing polyisocyanate composition]
Hereinafter, a specific manufacturing method is illustrated and the manufacturing method of a polyisocyanate composition is demonstrated.
Although it does not specifically limit as a manufacturing method of the polyisocyanate composition in this embodiment, For example, the following three methods are mentioned.
(I) A method of obtaining a polyisocyanate composition containing a copolymerized polyisocyanate using an aliphatic diisocyanate and an alicyclic diisocyanate as raw materials.
(Ii) A method of obtaining a polyisocyanate composition by mixing an aliphatic polyisocyanate made from an aliphatic diisocyanate and an alicyclic polyisocyanate made from an alicyclic diisocyanate.
(Iii) The copolymer polyisocyanate obtained in (i) above and at least one of the aliphatic polyisocyanate and alicyclic polyisocyanate obtained in (ii) above are mixed to obtain a polyisocyanate composition. Method.

  Among these, the method (ii) is preferable in terms of the simplicity of the production process and the ability to easily control the proportions of aliphatic and alicyclic, isocyanurate groups, uretdione groups, and allophanate groups. Hereinafter, each method will be described.

(I) Method of obtaining polyisocyanate composition containing copolymerized polyisocyanate using aliphatic diisocyanate and alicyclic diisocyanate as raw materials Copolymerized polyisocyanate was prepared by mixing aliphatic diisocyanate and alicyclic diisocyanate as raw materials. In the state, an isocyanurate reaction for forming an isocyanurate group, an uretodione reaction for forming a uretdione group, and / or an allophanate reaction for forming an allophanate group from an isocyanate group and an alcohol, etc. It can be obtained by removing the unreacted aliphatic diisocyanate and alicyclic diisocyanate after completion of the reaction. Hereinafter, a method for producing a copolymerized polyisocyanate having functional groups such as an isocyanurate group, an allophanate group, a uretdione group, a urethane group, and a biuret group will be described.

  The copolymerized polyisocyanate having an isocyanurate group can be produced by a known method. For example, it can be produced by multiplying an aliphatic diisocyanate and an alicyclic diisocyanate with an isocyanuration reaction catalyst.

  The isocyanuration reaction catalyst is not particularly limited, but generally has basicity. For example, 1) tetraalkylammonium such as tetramethylammonium, monoethyltrimethylammonium, diethyldimethylammonium, tetraethylammonium, tetrabutylammonium 2) Organic weak acid salts with acetic acid, capric acid, etc. 2) Hydroxyalkylammonium hydroxides such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxyethylammonium, acetic acid, caprin Organic weak acid salts with acids, etc. 3) Tin, zinc, lead of alkyl carboxylic acids such as acetic acid, caproic acid, octylic acid, myristic acid 4) Metal alcoholates such as sodium and potassium, 4) Metal alcoholates such as sodium and potassium, 5) Aminosilyl group-containing compounds such as hexamethyldisilazane, 6) Mannich bases, 7) Tertiary amines and epoxy compounds Combination use etc. are mentioned. Among these, 1), 2), and 3) are preferable from the viewpoint of catalyst efficiency, and the organic weak acid salt of 1) is particularly preferable.

  The addition amount of the isocyanurate reaction catalyst is preferably 10 to 1000 ppm based on the total amount of diisocyanate charged. The upper limit of the amount of addition of the isocyanurate reaction catalyst is preferably 1000 ppm, more preferably 500 ppm, and even more preferably 100 ppm from the viewpoint of simplicity of the production process. Moreover, the lower limit of the amount of addition of the isocyanurate-forming reaction catalyst is preferably 10 ppm from the viewpoint of reaction efficiency. In addition, the isocyanuration reaction temperature is preferably 50 to 120 ° C, and preferably 60 to 90 ° C in that the product is difficult to be colored.

  The isocyanuration reaction can be stopped by adding a reaction terminator as necessary when the conversion rate (mass ratio of polyisocyanate produced by the isocyanuration reaction to the charged diisocyanate) reaches a desired value. preferable. The conversion rate of the isocyanuration reaction is preferably 25% or less, more preferably 20% or less, from the viewpoint of low viscosity and curability. In order to obtain a copolymerized polyisocyanate having an isocyanurate group more efficiently, the progress of the reaction is preferably stopped at the initial stage. In particular, since cyclic initial trimerization of isocyanate groups has a very high initial reaction rate, it is preferable to appropriately select the reaction conditions, particularly the addition amount and addition method of the catalyst. As a method for adding the catalyst, for example, a method in which the catalyst is dividedly added at regular intervals is recommended.

  The reaction terminator is not particularly limited. For example, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid and other phosphoric acid compounds; phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid monoalkyl or dialkyl esters Halogenated acetic acid such as monochloroacetic acid; benzoyl chloride, sulfonic acid ester, sulfuric acid and the like. By using a reaction terminator, the storage stability of the resulting polyisocyanate tends to be further improved.

  The copolymerized polyisocyanate having an allophanate group can be produced by a known method. For example, it is produced by mixing an aliphatic diisocyanate and an alicyclic diisocyanate with an alcohol, and allophanating with an allophanate reaction catalyst. can do. In addition, it is also possible to use a reaction terminator similarly to the manufacturing method of the copolymerized polyisocyanate having an isocyanurate group.

  The alcohol is not particularly limited, but an alcohol formed only of carbon, hydrogen and oxygen is preferable, and a monoalcohol, a diol, a triol, a tetrahydric or higher alcohol, or a mixture of these alcohols is preferable. Further preferred. The molecular weight of the alcohol is not particularly limited, but a molecular weight of 200 or less is preferable. Examples of such alcohols include, but are not limited to, monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, and nonanol, ethylene glycol, 1,3-butanediol, and neopentyl glycol. And dialcohols such as 2-ethylhexanediol. Alcohol may be used individually by 1 type, or may use 2 or more types together.

  Although it does not specifically limit as an allophanatization reaction catalyst, For example, alkylcarboxylates, such as tin, lead, zinc, bismuth, zirconium, zirconyl, are mentioned. More specifically, organotin compounds such as tin 2-ethylhexanoate and dibutyltin dilaurate; organolead compounds such as lead 2-ethylhexanoate; organozinc compounds such as zinc 2-ethylhexanoate; 2-ethylhexane Examples thereof include bismuth acid, zirconium 2-ethylhexanoate, zirconyl 2-ethylhexanoate, and the like. The allophanatization reaction catalyst may be used alone or in combination of two or more.

  The equivalent ratio of the isocyanate group of aliphatic diisocyanate and alicyclic diisocyanate to the hydroxyl group of alcohol is preferably 10/1 to 1000/1, more preferably 100/1 to 1000/1. When the equivalent ratio is 10/1 or more, the average number of functional groups of the isocyanate group tends to increase. Moreover, it exists in the tendency for a viscosity to fall because an equivalent ratio is 1000/1 or less.

  Moreover, an isocyanurate formation reaction catalyst can also be used as an allophanatization reaction catalyst. When an allophanate reaction is performed using an isocyanurate reaction catalyst, an isocyanurate group is naturally generated. For this reason, it is preferable in terms of economic production that the isocyanurate reaction catalyst is used as the allophanate reaction catalyst and the allophanate reaction and the isocyanurate reaction are performed.

  The copolymerized polyisocyanate having a uretdione group can be produced by a known method, for example, by producing an aliphatic diisocyanate and an alicyclic diisocyanate using a uretdione-forming reaction catalyst or by heat-multimerization. Can do.

  Although it does not specifically limit as a uretdione-ized reaction catalyst, For example, the trialkyl phosphine which is a tertiary phosphine, such as tri-n-butylphosphine and tri-n-octylphosphine; Tris- (dimethylamino) phosphine, Tris- ( Tris (dialkylamino) phosphine such as diethylamino) phosphine; Cycloalkylphosphine such as cyclohexyl-di-n-hexylphosphine; Lewis acid such as boron trifluoride and zinc oxychloride. Many of the uretdioneation reaction catalysts can simultaneously promote the isocyanuration reaction. When a uretdione reaction catalyst is used, when the desired yield is reached, a quencher of the uretdione reaction catalyst such as phosphoric acid or methyl paratoluenesulfonate may be added to stop the uretdione reaction. preferable.

  In the case of obtaining a copolymer polyisocyanate having a uretdione group by heating an aliphatic diisocyanate and an alicyclic diisocyanate without using a uretdione-forming reaction catalyst, the heating temperature is preferably 120 ° C. or more, more preferably Is 150-170 ° C. The heating time is preferably 1 to 4 hours.

  The copolymerized polyisocyanate having a urethane group can be produced by a known method. For example, aliphatic diisocyanate and alicyclic diisocyanate and alcohol are mixed, and a urethanization reaction catalyst is added if necessary. It can manufacture by heating to 40-180 degreeC. As the alcohol, those similar to the above can be used.

  Although it does not specifically limit as a urethanation reaction catalyst, For example, a tin type compound, a zinc type compound, and an amine type compound is mentioned.

  The copolymer polyisocyanate having a biuret group can be produced by a known method. For example, aliphatic diisocyanate and alicyclic diisocyanate are mixed with water or a tertiary alcohol, and preferably 100 to 200 ° C. More preferably, it can be produced by heating at 140 to 180 ° C.

  The above isocyanurate reaction, allophanate reaction, and uretdione reaction can be performed sequentially or some of them can be performed in parallel. Preferably, the isocyanuration reaction and the allophanatization reaction are preceded in parallel, and then the uretdioneization reaction is performed. More preferably, the isocyanurate formation reaction and the allophanatization reaction are simultaneously performed using a common catalyst, and then the uretdione reaction by heating is performed. Thereby, a manufacturing process can be simplified more.

  Unreacted disoisocyanate can be removed from the reaction solution after completion of each reaction by thin-film distillation, extraction, or the like to obtain a polyisocyanate composition. It is preferable to remove unreacted diisocyanate from the viewpoint of safety.

(Ii) A method for obtaining a polyisocyanate composition by mixing an aliphatic polyisocyanate made from an aliphatic diisocyanate and an alicyclic polyisocyanate made from an alicyclic diisocyanate. The aliphatic polyisocyanate is isocyanurated. The reaction, uretdioneation reaction, and / or allophanatization reaction can be carried out in the presence of excess aliphatic diisocyanate, and after completion of the reaction, unreacted aliphatic diisocyanate can be removed. Aliphatic polyisocyanates having functional groups such as isocyanurate groups, allophanate groups, uretdione groups, urethane groups, biuret groups, and the like are produced by replacing aliphatic diisocyanates and alicyclic diisocyanates with aliphatic diisocyanates. It can manufacture by using group diisocyanate.

  The alicyclic polyisocyanate is subjected to isocyanuration reaction, uretdioneization reaction, and / or allophanate reaction in the presence of excess alicyclic diisocyanate, and after the reaction is completed, unreacted alicyclic diisocyanate is removed. Can be obtained. The production method of the alicyclic polyisocyanate having each functional group such as isocyanurate group, allophanate group, uretdione group, urethane group, biuret group is the production method of the above copolymer polyisocyanate. It can manufacture by using alicyclic diisocyanate instead of.

  In addition, the reaction temperature of the isocyanuration reaction is preferably 40 to 160 ° C, and more preferably 60 to 120 ° C in that the product is difficult to be colored.

  A polyisocyanate composition can be obtained by mixing the aliphatic polyisocyanate and the alicyclic polyisocyanate obtained as described above. The mass mixing ratio of the aliphatic polyisocyanate and the alicyclic polyisocyanate is preferably 90/10 to 50/50 in terms of adhesion. The lower limit of the mass mixing ratio of the aliphatic polyisocyanate and the alicyclic polyisocyanate is preferably 55% by mass, more preferably 60% by mass, still more preferably 65% by mass, and particularly preferably 70%. % By mass. The upper limit of the mass mixing ratio of the aliphatic polyisocyanate and the alicyclic polyisocyanate is preferably 90% by mass, more preferably 85% by mass, still more preferably 80% by mass, Preferably it is 75 mass%. In addition, although it does not specifically limit as a mixing method, For example, it can carry out by a conventionally well-known method.

(Iii) A polyisocyanate composition obtained by mixing the copolymerized polyisocyanate obtained by the method (i) with at least one of the aliphatic polyisocyanate and the alicyclic polyisocyanate obtained by the method (ii). In the method (iii), the copolymerized polyisocyanate obtained in the method (i) is mixed with at least one of the aliphatic polyisocyanate obtained in the method (ii) and the alicyclic polyisocyanate. It is a method to do.

  The blocked polyisocyanate composition can be obtained by blocking the isocyanate group of the polyisocyanate composition obtained by the production methods (i) to (iii) with a blocking agent. Although it does not specifically limit as a blocking agent which can be used here, The compound which has one active hydrogen in a molecule | numerator is mentioned. Specific examples thereof include alcohol compounds such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol; Mono- and dialkylphenols having an alkyl group having 4 or more carbon atoms as a substituent, such as n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, t-butylphenol, n-hexylphenol, 2- Monoalkylphenols such as ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol Alkylphenol compounds such as dialkylphenols such as di-t-butylphenol, di-sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di-n-nonylphenol; phenol, cresol, ethylphenol, styrenation Phenolic compounds such as phenol and hydroxybenzoic acid ester; active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; acetanilide and acetic acid Acid amide compounds such as amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam; acid imide compounds such as succinimide and maleic imide; imidazole Imidazole compounds such as 2-methylimidazole; urea compounds such as urea, thiourea, ethyleneurea; oxime compounds such as formal oxime, acetal oxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime; diphenylamine, aniline, Amine compounds such as carbazole, di-n-propylamine, diisopropylamine and isopropylethylamine; imine compounds such as ethyleneimine and polyethyleneimine; and pyrazole compounds such as pyrazole, 3-methylpyrazole and 3,5-dimethylpyrazole It is done.

  Among these, alcohol compounds, oxime compounds, acid amide compounds, active methylene compounds, and pyrazole compounds are preferable. As a blocking agent, it may be used individually by 1 type, or may use 2 or more types together.

[Coating composition]
The coating composition of this embodiment contains an active hydrogen compound and the polyisocyanate composition. The coating composition can be produced by mixing the polyisocyanate composition and an active hydrogen compound. When this coating composition is allowed to stand at room temperature or under heating for a certain period of time, the isocyanate group reacts with active hydrogen in the active hydrogen compound to form a cured product (cured composition).

  The active hydrogen compound (polyvalent active hydrogen compound) is a compound in which two or more active hydrogens are bonded in the molecule. Although it does not specifically limit as an active hydrogen compound, For example, a polyol, a polyamine, polythiol etc. are mentioned. Among these, a polyol is preferable.

  The polyol is not particularly limited, and examples thereof include polyester polyol, acrylic polyol, polyether polyol, polyolefin polyol, fluorine polyol, polycarbonate polyol, and epoxy polyol.

  The polyester polyol is not particularly limited. For example, a polyester polyol obtained by a condensation reaction of a dibasic acid and a polyhydric alcohol, and polycaprolactones obtained by ring-opening polymerization of a polyhydric alcohol and ε-caprolactone. Etc. Although it does not specifically limit as a dibasic acid, For example, it is 1 type chosen from the group which consists of carboxylic acids, such as a succinic acid, adipic acid, a sebacic acid, a dimer acid, a maleic anhydride, a phthalic anhydride, an isophthalic acid, a terephthalic acid The above is mentioned. The polyhydric alcohol is not particularly limited, and examples thereof include one or more selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, glycerin and the like.

  The acrylic polyol is not particularly limited. For example, a homopolymer of an ethylenically unsaturated bond-containing monomer having one or more kinds of hydroxyl groups, and an ethylenic group having one or more kinds of hydroxyl groups. Examples thereof include a copolymer of an unsaturated bond-containing monomer and one or more other ethylenically unsaturated bond-containing monomers copolymerizable therewith.

  The ethylenically unsaturated bond-containing monomer having a hydroxyl group is not particularly limited, and examples thereof include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and methacrylic acid. Hydroxybutyl etc. are mentioned. Of these, hydroxyethyl acrylate and hydroxyethyl methacrylate are preferred.

  Examples of other ethylenically unsaturated bond-containing monomers that can be copolymerized with an ethylenically unsaturated bond-containing monomer having a hydroxyl group include, but are not limited to, for example, methyl acrylate, ethyl acrylate, propyl acrylate Acrylates such as isopropyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, benzyl acrylate, and phenyl acrylate Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid -n-hexyl, cyclohexyl methacrylate, methacrylic acid-2-ethylhexyl, methacrylate Methacrylic acid esters such as lauryl laurate, benzyl methacrylate and phenyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid; acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone Unsaturated amides such as acrylamide, diacetone methacrylamide, maleic acid amide, maleimide; vinyl monomers such as glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate; and vinyl trimethoxysilane, vinyl And vinyl monomers having hydrolyzable silyl groups such as methyldimethoxysilane and γ- (meth) acryloxypropyltrimethoxysilane.

  The polyether polyols are not particularly limited. For example, polyether polyols obtained by adding an alkylene oxide to a polyvalent hydroxy compound using a hydroxide and / or a strong basic catalyst; ethylenediamines Polyether polyols obtained by reacting an alkylene oxide with a polyfunctional compound such as; and so-called polymer polyols obtained by polymerizing acrylamide or the like using these polyethers as a medium.

  The polyvalent hydroxy compound is not particularly limited, and examples thereof include diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like; erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, Sugar alcohol compounds such as galactitol, rhamnitol; monosaccharides such as arabinose, ribose, xylose, glucose, mannose, fructose, sorbose, rhamnose, rucose, fucose, ribosese; trehalose, sucrose, maltose, cellobiose, gentiobiose, lacto, melibiose And the like; disaccharides such as raffinose, gentianose, and meletitose; and tetrasaccharides such as stachyose.

  Examples of the alkylene oxide include one or more selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, and the like. Although it does not specifically limit as a hydroxide, For example, hydroxides, such as lithium, sodium, potassium, are mentioned. Further, the strong basic catalyst is not particularly limited, and examples thereof include alcoholate and alkylamine.

  The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

  It is preferable that the number of statistical hydroxyl groups (hereinafter, also referred to as “hydroxyl average functional group number”) possessed by one molecule of polyol is 2 or more. When the number of hydroxyl group average functional groups is 2 or more, the crosslinking density of the obtained coating film tends to be further improved.

  A fluorine polyol is a polyol containing fluorine in its molecule. Although it does not specifically limit as a fluoropolyol, For example, the fluoro olefin, cyclovinyl ether, hydroxyalkyl vinyl ether, monocarboxylic acid vinyl ester, etc. which are disclosed by Unexamined-Japanese-Patent No. 57-34107, Unexamined-Japanese-Patent No. 61-275311 etc. The copolymer of these is mentioned.

  The polycarbonate polyol is not particularly limited. For example, a low molecular carbonate compound such as a dialkyl carbonate such as dimethyl carbonate, an alkylene carbonate such as ethylene carbonate, a diaryl carbonate such as diphenyl carbonate, and the low molecular polyol used in the polyester polyol described above. Can be obtained by condensation polymerization.

  Although it does not specifically limit as an epoxy polyol, For example, a novolak type, (beta) -methyl epichloro type, a cyclic oxirane type, a glycidyl ether type, a glycol ether type, an epoxy type of an aliphatic unsaturated compound, an epoxidized fatty acid ester type, a polyvalent carboxyl Examples include acid ester type, aminoglycidyl type, halogenated type, and resorcin type epoxy polyol.

  Preferred polyols are acrylic polyols and polyester polyols, and more preferred are acrylic polyols.

  It is preferable that the resin solid content concentration of the polyol used is 60 to 100% by mass. The lower limit value of the resin solid content concentration of the polyol is preferably 60% by mass, more preferably 70% by mass, and further preferably 75% by mass. When the resin solid content concentration of the polyol is within the above range, VOC (volatile organic compound) tends to be further reduced.

  Moreover, it is preferable that the weight average molecular weights of a polyol are 500-10000. The lower limit of the weight average molecular weight of the polyol is preferably 500, more preferably 700, and even more preferably 1000 in terms of the adhesion of the cured composition. The upper limit of the weight average molecular weight of the polyol in terms of viscosity is preferably 10,000, more preferably 7000, and even more preferably 5000.

  The resin component hydroxyl value of the polyol is preferably 10 to 300 mg KOH / resin g. The lower limit value of the hydroxyl value of the resin content of the polyol in terms of the crosslinking density of the cured composition is preferably 10 mgKOH / resin g, more preferably 30 mgKOH / resin g. In terms of adhesion and impact resistance, the upper limit value of the resin hydroxyl value of the polyol is preferably 300 mgKOH / resin g, more preferably 200 mgKOH / resin g.

  In the coating composition of the present embodiment, the equivalent ratio of the isocyanate group of the polyisocyanate composition and the hydroxyl group of the polyol is preferably 5/1 to 1/5, more preferably 5/3 to 3/5, and further Preferably, it is 5/4 to 4/5.

  The polyamine that can be used as the active hydrogen compound is not particularly limited. For example, alkylenediamine such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, and the like. Polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine, etc. And aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

  Although it does not specifically limit as polythiol which can be used as an active hydrogen compound, For example, ethanedithiol, propanthidiol, butanedithiol, pentanedithiol, hexanedithiol, heptanedithiol, octanedithiol, nonanedithiol, decanedithiol, benzenedithiol, toluene- 1,2-benzenedithiol, toluene-3,4-dithiol, 3,6-dichloro-1,2-benzenedithiol, 1,5-naphthalenedithiol, benzenedimethanethiol, 4,4′-thiobisbenzenethiol, 2-di-n-butylamino-4,6-dimercapto-s-triazine, 5,5-bis (mercaptomethyl) -3,7-dithianonane-1,9-dithiol, dimercaptopropanol, dithioerythritol, di Lucaptoethyl sulfide, trithioglycerin, 1,3,5-triazine-2,4,6-trithiol 1,2,4-tris (mercaptomethyl) benzene, 2,4,6-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 2,4,6-tris (mercaptomethyl) mesitylene, tris (mercaptomethyl) isocyanurate, tris (3-mercaptopropyl) isocyanurate, 2,4,5- Examples thereof include polythiol compounds such as tris (mercaptomethyl) -1,3-dithiolane, 1,2,4,5-tetrakis (mercaptomethyl) benzene, tetramercaptobutane, and pentaerythrithiol.

  Further, the coating composition of the present embodiment includes an organic solvent, a curing accelerating catalyst, an antioxidant, an ultraviolet absorber, a light stabilizer, a pigment, a leveling agent, a plasticizer, and a surfactant, depending on the purpose and application. Various additives.

  Examples of the organic solvent include, but are not limited to, aliphatic hydrocarbon solvents such as hexane, heptane, and octane; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Ketone solvents; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, methyl lactate, and ethyl lactate; aromatic solvents such as toluene, xylene, diethylbenzene, mesitylene, anisole, benzyl alcohol, phenyl glycol, and chlorobenzene Solvent: ethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol Glycol solvents such as rumonomethyl ether acetate; Ether solvents such as diethyl ether, tetrahydrofuran and dioxane; Halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane and chloroform; Pyrrolidones such as N-methyl-2-pyrrolidone Amide solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; sulfoxide solvents such as dimethyl sulfoxide; lactone solvents such as γ-butyrolactone; amine solvents such as morpholine; A mixture is mentioned. In addition, these organic solvents may be used individually by 1 type, and may use 2 or more types together.

  Although it does not specifically limit as a hardening acceleration | stimulation catalyst, For example, tin-type compounds, such as dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin dineodecanoate, bis (2-ethylhexanoic acid) tin; 2-ethyl Zinc compounds such as zinc hexanoate and zinc naphthenate; titanium compounds such as titanium 2-ethylhexanoate and titanium diisopropoxybis (ethylacetonate); cobalt compounds such as cobalt 2-ethylhexanoate and cobalt naphthenate; 2 -Bismuth compounds such as bismuth ethylhexanoate and bismuth naphthenate; zirconium compounds such as zirconium tetraacetylacetonate, zirconyl 2-ethylhexanoate and zirconyl naphthenate; amine compounds and the like.

  Moreover, it does not specifically limit as antioxidant, For example, a hindered phenol type compound, a phosphorus compound, a sulfur type compound, etc. are mentioned.

  Although it does not specifically limit as a ultraviolet absorber, For example, a benzotriazole type compound, a triazine type compound, a benzophenone type compound etc. are mentioned.

  The light stabilizer is not particularly limited, and examples thereof include hindered amine compounds, benzotriazole compounds, triazine compounds, benzophenone compounds, and benzoate compounds.

  Although it does not specifically limit as a pigment, For example, titanium oxide, carbon black, indigo, pearl mica, aluminum, etc. are mentioned.

  Although it does not specifically limit as a leveling agent, For example, silicone oil etc. are mentioned.

  The plasticizer is not particularly limited, and examples thereof include phthalic acid esters, phosphoric acid compounds, and polyester compounds.

  Although it does not specifically limit as surfactant, For example, a well-known anionic surfactant, a cationic surfactant, an amphoteric surfactant, etc. are mentioned.

  The total resin solids concentration of the polyol and polyisocyanate composition in the coating composition of the present embodiment is preferably 50% by mass or more, more preferably 53% by mass, still more preferably 56% by mass or more, and particularly preferably. Is 60% by mass or more. The upper limit of the total resin solid content concentration is not particularly limited, but is preferably 70% by mass or less. When the total resin solid content concentration is within the above range, workability and high solidity tend to be further improved.

  When the coating composition of this embodiment is cured on various substrates, the adhesion of the substrate is significantly improved.

  The coating composition of the present embodiment includes a curable composition such as a coating composition, a pressure-sensitive adhesive composition, an adhesive composition, and a casting composition; various surface treatment compositions such as a fiber treatment agent; various elastomer compositions It can be suitably used as a crosslinking agent such as a product or a foam composition; a modifier; an additive.

  The method of using the coating composition is not particularly limited, and can be suitably used as a primer, intermediate coating, or top coating on various materials by roll coating, curtain flow coating, spray coating, electrostatic coating, bell coating, and the like. .

  In addition, the coating composition of the present embodiment is further applied to a pre-coated metal paint, an automobile paint, a plastic paint, a floor building paint, and the like, which includes a rust-proof steel plate, and has a cosmetic property, weather resistance, acid resistance, rust resistance, and chipping resistance. It is suitably used for imparting properties and adhesion.

  In particular, the coating composition of this embodiment has a strong coating film, high coating film hardness, good surface smoothness and chemical resistance, and excellent adhesion to an organic coating film. Therefore, it is useful as a top clear coat which is applied on a non-aqueous base coat containing a pigment and an aqueous base coat. The base coat and the top clear coat are preferably cured simultaneously.

  In addition, when used as a pressure-sensitive adhesive composition or an adhesive composition, it can be used as, for example, a coating solution diluted with various solvents because of its workability when applied to an adherend and ease of thinning. It is.

  Fields of use when used as an adhesive composition or an adhesive composition include automobiles, building materials or home appliances, woodworking, solar cell laminates, and the like. Among them, optical members for liquid crystal displays of home appliances such as televisions, personal computers, digital cameras, and mobile phones exhibit various functions. Therefore, it is necessary to laminate films and plates of various adherends. Since sufficient tackiness or adhesiveness is required between films and plates of various adherends, it is preferable as an example of use of the pressure-sensitive adhesive composition and adhesive composition of the present embodiment.

  The adherend to which the coating composition containing the polyisocyanate composition of the present embodiment can be used is not particularly limited. For example, various metals such as glass, aluminum, iron, galvanized steel, copper, and stainless steel, wood , Porous materials such as paper, mortar, stone, fluorine coated, urethane coated, acrylic urethane coated, etc., silicone-based, modified silicone-based, urethane-based sealing materials, vinyl chloride, natural rubber, Rubbers such as synthetic rubber, leathers such as natural leather and artificial leather, fibers such as plant-based, animal-based, carbon fiber and glass fiber, non-woven fabric, polyester, acrylic, polycarbonate, triacetyl cellulose, polyolefin and other resins Films and plates, UV curable acrylic resin layers, printing inks, UV inks and other inks And the like.

  Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to the following examples.

(Viscosity measurement)
The viscosity was measured at 25 ° C. using an E-type viscometer (VISICONIC ED type (trade name) manufactured by Tokimec). A standard rotor (1 ° 34 ′ × R24) was used as the rotor. The number of revolutions (r.p.m.) was as follows.
100r. p. m. (When the viscosity is less than 128 mPa · s)
50r. p. m. (When the viscosity is 128 mPa · s or more and less than 256 mPa · s)
20r. p. m. (When the viscosity is 256 mPa · s or more and less than 640 mPa · s)
10r. p. m. (When the viscosity is 640 mPa · s or more and less than 1280 mPa · s)
5r. p. m. (When the viscosity is 1280 mPa · s or more and less than 2560 mPa · s)
2.5r. p. m. (When the viscosity is 2560 mPa · s or more and less than 5120 mPa · s)
1.0r. p. m. (When the viscosity is 5120 mPa · s or more and less than 12800 mPa · s)
0.5r. p. m. (When the viscosity is 12800 mPa · s or more and less than 25600 mPa · s)

(Measurement of number average molecular weight)
The number average molecular weight of the polyisocyanate composition was measured as a number average molecular weight based on polystyrene by a gel permeation chromatograph (hereinafter also referred to as “GPC”) using the following apparatus.
Apparatus: Tosoh Corporation HLC-8120GPC (trade name)
Column: Tosoh Corporation TSKgel SuperH1000 (trade name) x 1
TSKgel SuperH2000 (trade name) x 1
TSKgel SuperH3000 (trade name) x 1 Carrier: Tetrahydrofuran Detection method: Differential refractometer

(Isocyanurate group content)
Isocyanurate group content (molar concentration) with respect to a total of 100 mol% of isocyanurate groups, allophanate groups, burette groups, urethane groups, uretdione groups, iminooxadiazinedione groups, and urea groups in the polyisocyanate composition is Using a Biospin Avance 600 (trade name) manufactured by Bruker, carbon thirteen nuclear magnetic resonance spectrum (13C-NMR) was obtained.

More specific description will be given below. The polyisocyanate composition was dissolved in deuterium chloroform at a concentration of 60% by mass to prepare an NMR measurement sample. The chemical shift standard was deuterochloroform signal of 77 ppm. The NMR measurement sample was measured by 13C-NMR, the area of the carbonyl carbon signal was determined, and the content of the isocyanurate group was calculated by the following formula.
Isocyanurate group content = (area near 149.0 ppm / 3) / (area near 149.0 ppm / 3 area near 154.4 ppm + area near 156.4 ppm / 2 + area near 155.9 ppm + 157.8 ppm Area / area around + 144.6ppm + area around 158.2ppm)

(Measurement of content of isocyanurate trimer)
GPC measurement similar to the number average molecular weight measurement was performed, and the peak area% corresponding to the molecular weight three times that of diisocyanate was calculated as the isocyanurate trimer content in the polyisocyanate composition from the following formula.
Isocyanurate trimer content (% by mass) = (peak area corresponding to molecular weight 3 times that of diisocyanate / total peak area) × 100

(Molar ratio of allophanate group / isocyanurate group)
The molar ratio of allophanate group / isocyanurate group was determined from measurement of proton nuclear magnetic resonance spectrum (1H-NMR) using FT-NMR DPX-400 (trade name) manufactured by Bruker.

More specific description will be given below. The polyisocyanate composition was dissolved in deuterium chloroform at a concentration of 10% by mass (0.03% by mass of tetramethylsilane was added to the polyisocyanate) to prepare an NMR measurement sample. As a chemical shift standard, the hydrogen signal of tetramethylsilane was set to 0 ppm. An NMR measurement sample was measured by 1H-NMR, and a signal of a hydrogen atom bonded to a nitrogen atom of an allophanate group near 8.5 ppm (1 mol hydrogen atom per 1 mol of the allophanate group) and an isocyanurate around 3.8 ppm The area ratio of the signal of the hydrogen atom of the methylene group adjacent to the nitrogen atom of the isocyanurate ring of the group (6 mol of hydrogen atom relative to 1 mol of isocyanurate group) is obtained, The ratio was calculated.
Molar ratio of allophanate group / isocyanurate group = (signal area around 8.5 ppm) / (signal area around 3.8 ppm / 6)

(Measurement of content of uretdione dimer)
GPC measurement similar to the number average molecular weight measurement was performed, and the peak area% corresponding to the molecular weight twice that of diisocyanate was calculated as the uretdione dimer content in the polyisocyanate composition from the following formula.
Content of uretdione dimer (% by mass) = (peak area corresponding to molecular weight twice that of diisocyanate / total peak area) × 100

(Measurement of isocyanate group mass concentration)
The measuring method of isocyanate group mass concentration was carried out according to the method described in JIS K 7301-1995 (Testing method for tolylene diisocyanate type prepolymer for thermosetting urethane elastomer).

  Specifically, first, 1 g of a sample was collected in a 200 mL Erlenmeyer flask, and 20 mL of toluene was added and dissolved. Then, 20 mL of 2.0N di-n-butylamine / toluene solution was added and allowed to stand for 15 minutes. Then 70 mL of 2-propanol was added. Then, titration was performed using 1.0N hydrochloric acid, and the isocyanate group mass concentration was measured. Even when no sample was added, the measurement was performed in the same manner as described above.

(Isocyanate group average number of functional groups)
The number of isocyanate group average functional groups was calculated from the following equation using the measurement results of the number average molecular weight of polyisocyanate and the isocyanate group mass concentration.
Isocyanate group average functional group number = [(polyisocyanate number average molecular weight × isocyanate group mass concentration) / (42 × 100)]

(Mole ratio of aliphatic diisocyanate unit / alicyclic diisocyanate unit in polyisocyanate composition)
The molar ratio of the aliphatic diisocyanate unit / alicyclic diisocyanate unit was determined from the measurement of proton nuclear magnetic resonance spectrum (1H-NMR) using FT-NMR DPX-400 (trade name) manufactured by Bruker. Specifically, the molar ratio (a) / (b) between the methylene group (a) of the aliphatic isocyanate and the methylene group and methine group (b) of the alicyclic diisocyanate is calculated as follows: aliphatic diisocyanate component / alicyclic diisocyanate component The molar ratio was obtained.

(Storage stability)
After storing the polyisocyanate composition in a nitrogen atmosphere at 40 ° C. for 1 month, the diisocyanate content in the polyisocyanate composition was measured by gas chromatographic measurement under the following conditions. Moreover, content of the diisocyanate in the polyisocyanate composition before storage was measured. Based on the rate of increase of the diisocyanate content before and after storage, storage stability was evaluated according to evaluation criteria.
(Evaluation criteria)
○: The increase rate of the diisocyanate content was 0.5% by mass or less. ×: The increase rate of the diisocyanate content exceeded 0.5% by mass.
(Gas chromatograph measurement conditions)
・ Column Silicon OV17 1m
・ Inlet temperature 160 ℃, Column temperature 120 ℃
・ Carrier Nitrogen ・ Detector Hydrogen flame ionization detector

(Viscosity of paint)
Acrylic polyol (Nuplex Resin trade name Setalux 1903, resin solid content 75%, hydroxyl value 150 mg KOH / resin g) and polyisocyanate composition were mixed so that the equivalent ratio of hydroxyl group to isocyanate group was 1.0, A mixture was obtained. To the resulting mixture was added thinner (ethyl acetate / toluene / butyl acetate / xylene / propylene glycol monomethyl ether acetate (mass ratio 30/30/20/15/5)). It was diluted so that the viscosity measured in 4 was 20 seconds. Based on the paint solid content after dilution, the paint viscosity was evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: The solid content of the paint was 55% or more.
Δ: Paint solid content was 50% or more and less than 55%.
X: Paint solid content was less than 50%.

(Quick-drying)
Acrylic polyol (Nuplex Resin product name, Setalux 1903, hydroxyl value 150 mgKOH / resin g) and a polyisocyanate composition were blended so that the equivalent ratio of hydroxyl group to isocyanate group was 1: 1.3. To this formulation, thinner (ethyl acetate / toluene / butyl acetate / xylene / propylene glycol monomethyl ether acetate = 30/30/20/15/5 (mass ratio)) was added. 4 to 20 seconds to obtain a coating composition. The obtained coating composition was applied onto a glass plate to a film thickness of 40 μm, baked at 60 ° C. for 30 minutes, and allowed to stand at 20 ° C. for 1 hour to obtain a coating film. Five sheets of Japanese pharmacopoeia gauze were piled up on the obtained coating film, and 100 g of weight was put on it for 60 seconds. Thereafter, the weight and gauze were removed, and the gauze trace remaining on the coating film was observed. Based on the gauze trace, quick drying was evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: No gauze trace was observed.
X: A gauze trace was observed.

(Adhesion)
Acrylic polyol (Nuplex Resin product name, Setalux 1903, hydroxyl value 150 mg KOH / resin g) and a polyisocyanate composition are blended so that the hydroxyl group and isocyanate group equivalent ratio is 1: 1.3. Obtained. Thinner (ethyl acetate / toluene / butyl acetate / xylene / propylene glycol monomethyl ether acetate = 30/30/20/15/5 (mass ratio)) was added to the resulting blend, and the paint viscosity was Ford Cup No. 4 to 20 seconds to obtain a coating composition.

The coating composition obtained on the mild steel plate was applied to a resin film thickness of 30 micrometers. After standing at room temperature for 15 minutes, baking was performed in an oven at 90 ° C. for 30 minutes to obtain a coating film. The adhesion test of this coating film was performed by a cross cut test. Specifically, 100 squares were cut into one coating film, a peeling test with a tape was performed, and the adhesion was evaluated based on the number of peeling coating films according to the following evaluation criteria.
(Evaluation criteria)
○: The release coating film was less than 10.
X: The release coating film was 10 or more.

(Synthesis Example 1) (Production of Aliphatic Polyisocyanate Composition A-1)
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel was placed in a nitrogen atmosphere, and 600 parts of hexamethylene diisocyanate (hereinafter also referred to as “HDI”), isobutanol 0.6 2 hours at a reactor internal temperature of 80 ° C. with stirring. Thereafter, tetramethylammonium capryate as an isocyanurate reaction catalyst was added to conduct an isocyanurate reaction. When the isocyanate group mass concentration of the reaction solution reached 46.5%, phosphoric acid was added to stop the reaction. The content of the uretdione dimer in this reaction solution was 1% by mass or less. The reaction solution was further maintained at 160 ° C. for 1 Hr. This heating produced uretdione group-containing polyisocyanate. The reaction was cooled and filtered. Then, unreacted HDI was removed using the thin film distiller, and aliphatic polyisocyanate composition A-1 was obtained.

  The resulting aliphatic polyisocyanate composition A-1 has a viscosity at 25 ° C. of 410 mPa · s, a content of uretdione dimer of 15% by mass, and an allophanate group / isocyanurate group molar ratio of 2/98, The isocyanurate group content was 72 mol%, the isocyanurate trimer content was 63 mass%, the isocyanate group mass concentration was 23.2 mass%, and the isocyanate group average functional group number was 3.0.

(Synthesis Example 2) (Production of Aliphatic Polyisocyanate Composition A-2)
In the same apparatus as in Synthesis Example 1, 600 parts of HDI and 2.5 parts of isobutanol were charged, and the temperature in the reactor was kept at 80 ° C. for 2 hours with stirring. Thereafter, 0.5 part of a solution obtained by diluting trimethyl-2-methyl-2-hydroxyethylammonium hydroxide, which is an isocyanuration reaction catalyst, to 5% by mass with isobutanol was added to perform an isocyanuration reaction. When the isocyanate group mass concentration of the reaction solution reached 45.1%, phosphoric acid was added to stop the reaction. The content of the uretdione dimer in this reaction solution was 1% by mass or less. The reaction solution was further maintained at 160 ° C. for 1 Hr. This heating produced uretdione group-containing polyisocyanate. The reaction was cooled and filtered. Thereafter, unreacted HDI was removed by a thin film evaporator to obtain an aliphatic polyisocyanate composition A-2.

  The obtained aliphatic polyisocyanate composition A-2 had a viscosity at 25 ° C. of 280 mPa · s, a content of uretdione dimer of 13% by mass, and an allophanate group / isocyanurate group molar ratio of 23/77, The isocyanurate group content was 62 mol%, the isocyanurate trimer content was 66 mass%, the isocyanate group mass concentration was 23.0 mass%, and the isocyanate group average functional group number was 2.8.

(Synthesis Example 3) (Production of Aliphatic Polyisocyanate Composition A-3)
In the same apparatus as in Synthesis Example 1, 600 parts of HDI and 0.6 part of isobutanol were charged and maintained at 80 ° C. with stirring for 2 hours under stirring. Thereafter, tetramethylammonium capryate, which is an isocyanuration reaction catalyst, was added to conduct an isocyanuration reaction. When the isocyanate group mass concentration of the reaction solution reached 44.6%, phosphoric acid was added to stop the reaction. After the reaction solution was filtered, unreacted diisocyanate was removed with a thin-film distiller to obtain an aliphatic polyisocyanate composition A-3.

  The obtained aliphatic polyisocyanate composition A-3 had a viscosity at 25 ° C. of 1400 mPa · s, a uretdione dimer content of 1% by mass or less, and an allophanate group / isocyanurate group molar ratio of 2/98. The isocyanurate group content was 98 mol%, the isocyanurate trimer content was 68 mass%, the isocyanate group mass concentration was 23.0 mass%, and the isocyanate group average functional group number was 3.1.

(Synthesis Example 4) (Production of Aliphatic Polyisocyanate Composition A-4)
In the same apparatus as in Synthesis Example 1, 1200 parts of HDI and 93 parts of 2-ethyl-1-hexanol were charged and kept at 90 ° C. for 1 hour with stirring in the reactor. After raising the temperature to 130 ° C., 0.42 part of a 20% mineral spirit solution of zirconyl 2-ethylhexanoate as an allophanatization reaction catalyst was added. After reacting for 1 hour, pyrophosphoric acid solid content 10% 2-ethyl-1-hexanol solution (made by Taihei Chemical Industry, trade name “phosphoric acid (105%)” diluted with 2-ethyl-1-hexanol ) Was added to stop the reaction. The reaction was cooled and filtered. Then, unreacted HDI was removed with a thin film distiller to obtain an aliphatic polyisocyanate composition A-4.

  The obtained aliphatic polyisocyanate composition A-4 had a viscosity at 25 ° C. of 100 mPa · s, a content of uretdione dimer of 10% by mass, and an allophanate group / isocyanurate group molar ratio of 97/3. The isocyanurate group content was 3 mol%, the isocyanurate trimer content was 3 mass%, the isocyanate group mass concentration was 17.4 mass%, and the average number of functional groups was 2.0.

(Synthesis Example 5) (Production of Aliphatic Polyisocyanate Composition A-5)
In the same apparatus as in Synthesis Example 1, 600 parts of HDI was charged, and maintained for 1 hour at 60 ° C. in the reactor with stirring. Thereto, 9 parts of tri-n-butylphosphine (Cytop (trademark) 340, manufactured by Cytec) as a catalyst for uretdioneization reaction was added, and uretdioneization reaction and isocyanuration reaction were performed. When the isocyanate group mass concentration of the reaction solution reached 38.8%, 12 parts of methyl-p-toluenesulfonate was added to stop the reaction. The reaction was cooled and filtered. Then, unreacted HDI was removed with a thin film distiller to obtain an aliphatic polyisocyanate composition A-5.

  The resulting aliphatic polyisocyanate composition A-5 had a viscosity at 25 ° C. of 150 mPa · s, a uretdione dimer content of 40% by mass, and an allophanate group / isocyanurate group molar ratio of 0.2 / The content of the isocyanurate group was 16 mol%, the content of the isocyanurate trimer was 30% by mass, the isocyanate group mass concentration was 22.1% by mass, and the average number of functional groups was 2.3.

(Example 1) (Production of Copolymerized Polyisocyanate Composition C-1 of Aliphatic Diisocyanate and Alicyclic Diisocyanate)
The same apparatus as in Synthesis Example 1 was charged with 700 parts of HDI, 300 parts of isophorone diisocyanate (hereinafter also referred to as “IPDI”), and 4.2 parts of isobutanol, and the mixture was maintained at 80 ° C. for 2 hours with stirring. . Thereafter, tetramethylammonium capryate, which is an isocyanuration reaction catalyst, was added to conduct an isocyanuration reaction. When the conversion reached 37%, phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted diisocyanate was removed with a thin-film distiller to obtain polyisocyanate composition C-1. The properties of the resulting polyisocyanate composition C-1 are shown in Table 1.

(Example 2)
Aliphatic polyisocyanate composition A-1 obtained in Synthesis Example 1 and IPDI isocyanurate type alicyclic polyisocyanate composition B-1 (trade name “T1890 / 100”, manufactured by Degussa, NCO content rate = 17.2%) at a solid content mass ratio of 90/10 and heated and mixed at 100 ° C. for 5 hours to obtain a polyisocyanate composition C-2. The properties of the resulting polyisocyanate composition C-2 are shown in Table 1.

(Examples 3-7, Comparative Example 1)
The polyisocyanate obtained by mixing the aliphatic polyisocyanate composition A-2 and the alicyclic polyisocyanate composition B-1 obtained in Synthesis Example 2 at a solid content mass ratio shown in Table 1 at 100 ° C. for 5 hours. Compositions C-3 to 8 were obtained. The properties of the resulting polyisocyanate compositions C-3 to 8 are shown in Table 1.

(Comparative Example 2)
Aliphatic polyisocyanate composition A-2 obtained in Synthesis Example 2 and IPDI-based adduct type polyisocyanate composition B-2 (trade name “NY260A”, manufactured by Mitsubishi Chemical Corporation, NCO content = 10.5%, 75 % Ethyl acetate diluted product) at a solid content mass ratio of 75/25 at 90 ° C. for 5 hours. After mixing, ethyl acetate was removed by distillation under reduced pressure to obtain polyisocyanate composition C-9. The characteristics of the resulting polyisocyanate composition C-9 are shown in Table 1.

(Comparative Example 3)
The polyisocyanate obtained by mixing the aliphatic polyisocyanate composition A-3 and the alicyclic polyisocyanate composition B-1 obtained in Synthesis Example 3 with heating at 100 ° C. for 5 hours at a solid content mass ratio shown in Table 1. Composition C-10 was obtained. The characteristics of the resulting polyisocyanate composition C-10 are shown in Table 1.

(Comparative Example 4)
Aliphatic polyisocyanate composition A-4 and alicyclic polyisocyanate composition B-1 obtained in Synthesis Example 4 were heated and mixed at 100 ° C. for 5 hours at a solid content mass ratio shown in Table 1, and then polyisocyanate. Composition C-11 was obtained. The properties of the resulting polyisocyanate composition C-11 are shown in Table 1.

(Comparative Example 5)
Aliphatic polyisocyanate composition A-5 and alicyclic polyisocyanate composition B-1 obtained in Synthesis Example 5 were heated and mixed at a solid content mass ratio shown in Table 1 at 100 ° C. for 5 hours to obtain a polyisocyanate. Composition C-12 was obtained. The properties of the resulting polyisocyanate composition are shown in Table 1.

(Examples 8-14, Comparative Examples 6-12)
Acrylic polyol (trade name, “Setalux 1903”, manufactured by Nuplex Resin, hydroxyl value 150 mg KOH / resin g) and polyisocyanate composition C-1-12 were blended so that the hydroxyl group and isocyanate group equivalent ratio was 1.0. A formulation was obtained. Thinner (ethyl acetate / toluene / butyl acetate / xylene / propylene glycol monomethyl ether acetate = 30/30/20/15/5 (mass ratio)) was added to the resulting blend, and the viscosity of the paint was changed to Ford Cup No. 4 was adjusted to 20 seconds. Quick drying, storage stability, paint viscosity, and adhesion were evaluated. The results are shown in Table 2.

(A) / (B): mixed mass ratio of aliphatic polyisocyanate (A) and alicyclic polyisocyanate (B) Aliphatic / alicyclic: aliphatic diisocyanate unit constituting polyisocyanate in polyisocyanate composition And molar ratio of alicyclic diisocyanate unit N amount: content trimer concentration of isocyanurate group in polyisocyanate composition: content dimer concentration of isocyanurate trimer: content A of uretdione dimer / N ratio: molar ratio of allophanate group / isocyanurate group Average functional group: average number of functional groups of isocyanate group NCO%: isocyanate group mass concentration

  The polyisocyanate composition of the present invention has industrial applicability in paints for high solids.

Claims (7)

A polyisocyanate composition comprising an alicyclic polyisocyanate consisting of aliphatic polyisocyanates and alicyclic diisocyanates units consisting of fat-aliphatic diisocyanate units,
The molar ratio of the aliphatic diisocyanate unit / the alicyclic diisocyanate unit in the polyisocyanate composition is 95/5 to 50/50,
The polyisocyanate composition comprises a polyisocyanate having an isocyanurate group;
The content of the isocyanurate group is 100 mol% in total of the isocyanurate group, allophanate group, burette group, urethane group, uretdione group, iminooxadiazinedione group, and urea group in the polyisocyanate composition. , 60 mol% or more,
The polyisocyanate composition comprises a uretdione dimer and a polyisocyanate having an allophanate group;
The content of the uretdione dimer is 1 to 35% by mass,
And the molar ratio of allophanate group / isocyanurate group is from 1/99 to 50/50,
The polyisocyanate composition whose viscosity in 25 degreeC is 100-10000 mPa * s. The polyisocyanate having an isocyanurate group includes an isocyanurate trimer;
The polyisocyanate composition according to claim 1, wherein the content of the isocyanurate trimer is 55 to 95% by mass. The polyisocyanate composition according to claim 1 or 2 , wherein an average functional group number of isocyanate groups of the polyisocyanate composition is 2.5 to 4.0. The aliphatic polyisocyanate includes an aliphatic polyisocyanate having a uretdione dimer and an allophanate group,
The content of the uretdione dimer is 1 to 50% by mass with respect to the total amount of the aliphatic polyisocyanate,
And the molar ratio of allophanate group / isocyanurate group is from 1/99 to 50/50,
The polyisocyanate composition according to any one of claims 1 to 3 . The polyisocyanate composition according to any one of claims 1 to 4 , wherein the aliphatic polyisocyanate has a viscosity at 25 ° C of 150 to 800 mPa · s. A coating composition comprising an active hydrogen compound and the polyisocyanate composition according to any one of claims 1 to 5 . Hardened | cured material obtained using the coating composition of Claim 6 .