JP2024039019A - Polyisocyanate compositions, resin compositions and cured resin products - Google Patents

Abstract

The present invention provides a polyisocyanate composition, a resin composition, and a cured resin product. [Solution] A polyisocyanate composition containing polyisocyanate A and polyisocyanate B, wherein the polyisocyanate composition has a weight average molecular weight of 700 or more and a 25°C viscosity of 10000 mPa·s or less. The polyisocyanate A is a polyisocyanate derived from an aliphatic polyisocyanate or an alicyclic polyisocyanate, has a weight average molecular weight Mw of 1200 or less, and contains an isocyanurate group, and the polyisocyanate B is a polyisocyanate containing an isocyanurate group. A polyisocyanate composition derived from a polyisocyanate or an alicyclic polyisocyanate and a polyol, wherein the polyol has a number average molecular weight Mn of 500 or more and a functional group of 2 or more and 5 or less. [Selection diagram] None

Description

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

Coating films formed from coating compositions containing aliphatic polyisocyanates as curing agents are widely used because they have excellent coating properties such as weather resistance.

For example, it is known that a coating film formed using a coating material using an isocyanurate type polyisocyanate having an isocyanurate group is excellent in coating film physical properties such as weather resistance (see Patent Document 1).

Paints and adhesives used outdoors must have physical properties such as weather resistance, strength and elongation that are difficult to break due to external impact or force, hardness, and an appropriate viscosity that takes into account workability during use, as well as physical properties that are compatible with the natural environment. In recent years, there has been a demand for paints, resin compositions, adhesives, etc. to be solvent-free, as they do not use organic solvents, due to concerns about the environment and the working environment.

For example, Patent Document 2 discloses an aqueous urethane emulsion containing a nonionic water-dispersible block polyisocyanate as a main component.

Japanese Patent Application Publication No. 55-038380 JP 62-151419 Publication

Although the conventional water-based urethane emulsion described in Patent Document 2 can be used as a water-based paint without using an organic solvent, the physical properties of the cured film have not been sufficiently studied.

The present invention has been made in view of the above circumstances, and provides a polyisocyanate composition that can be used without a solvent and has excellent physical properties of a cured product obtained by curing the polyisocyanate composition, and a resin containing this polyisocyanate composition. The purpose is to provide a composition and a cured resin product.

Here, the physical properties of a cured product obtained by curing the polyisocyanate composition mean the maximum stress in a tensile test of the cured product, elongation rate, stress at an elongation rate of 10%, Koenig hardness, and weather resistance.

That is, the present invention includes the following aspects.
[1] A polyisocyanate composition containing polyisocyanate A and polyisocyanate B, wherein the polyisocyanate composition has a weight average molecular weight of 700 or more and a 25°C viscosity of 10,000 mPa·s or less. , the polyisocyanate A is a polyisocyanate derived from an aliphatic polyisocyanate or an alicyclic polyisocyanate, has a weight average molecular weight Mw of 1200 or less, and contains an isocyanurate group, and the polyisocyanate B is a polyisocyanate containing an isocyanurate group. A polyisocyanate composition derived from an isocyanate or an alicyclic polyisocyanate and a polyol, wherein the polyol has a number average molecular weight Mn of 500 or more and a functional group of 2 or more and 5 or less.
[2] The polyisocyanate composition according to [1], wherein the polyisocyanate composition has an NCO functional group content of 10.0% or more and 20.0% or less.
[3] The polyisocyanate composition according to [1] or [2], wherein the polyisocyanate A has an average number of isocyanate functional groups of 2.0 or more and 5.0 or less.
[4] The polyisocyanate composition according to any one of [1] to [3], wherein the polyisocyanate B has a weight average molecular weight of 1400 or more.
[5] The polyisocyanate composition according to any one of [1] to [4], wherein the polyisocyanate B has an average number of isocyanate functional groups of 2.0 or more and 5.5 or less.
[6] The polyisocyanate A is a modified polyisocyanate modified with a primary alcohol having 2 to 18 carbon atoms or a secondary alcohol, according to any one of [1] to [5]. Polyisocyanate composition.
[7] The polyisocyanate composition according to any one of [1] to [6], wherein the polyisocyanate A contains an allophanate group.
[8] The polyisocyanate A contains an allophanate group and an isocyanurate group, and the molar ratio of the allophanate group to the total amount of the allophanate group and the isocyanurate group is 10% or more, [1] to [7] The polyisocyanate composition according to any one of .
[9] The polyisocyanate composition according to any one of [1] to [8], wherein the polyol is at least one of polyester polyols and polyether polyols.
[10] The polyisocyanate according to any one of [1] to [9], wherein the content of the polyisocyanate A in the total amount of the polyisocyanate A and the polyisocyanate B is 60% by mass or less. Isocyanate composition.
[11] A resin composition comprising a crosslinkable functional group-containing polymer and the polyisocyanate composition according to any one of [1] to [10].
[12] The resin composition according to [11], wherein the functional group contained in the crosslinkable functional group-containing polymer is at least one of a hydroxyl group, a carboxy group, an epoxy group, an oxetane group, and an amino group.
[13] The resin composition according to [12], wherein the amino group is a primary amino group or a secondary amino group.
[14] The resin composition according to [13], wherein the secondary amino group is an amino group derived from an aspartic acid ester polyamine.
[15] A cured resin product obtained by curing the resin composition according to any one of [11] to [14].
[16] The cured resin product according to [15], which has an elongation rate of 80% or more at 23°C when subjected to a tensile test at a distance between chucks of 20 mm and a speed of 20 mm/min.
[17] The cured resin product according to [15] or [16], which has a maximum stress of 20 MPa or more at 23° C. when subjected to a tensile test with a distance between chucks of 20 mm and a speed of 20 mm/min.
[18] The cured resin product according to any one of [15] to [17], which has a stress at 10% elongation at 23° C. of 7 MPa or more.
[19] The cured resin product according to any one of [15] to [18], wherein the cured resin product formed on glass has a Koenig hardness of 20 times or more and 125 times or less at 23°C.
[20] The cured resin product according to any one of [15] to [20], which has a gel fraction of 80% by mass or more.
[21] The cured resin product according to any one of [15] to [20], wherein the cured resin product is a cured resin sheet having a thickness of 1 μm or more and 2000 μm or less.

According to the present invention, there is provided a polyisocyanate composition that can be used without a solvent and has excellent physical properties of a cured product obtained by curing the polyisocyanate composition, a resin composition containing this polyisocyanate composition, and a cured resin product. be able to.

Note that in this specification, "polyol" means a compound having two or more hydroxy groups (-OH) in one molecule.
Furthermore, in this specification, "polyisocyanate" means a reaction product in which a plurality of monomer compounds having two or more isocyanate groups (-NCO) are bonded.
Furthermore, in this specification, unless otherwise specified, "(meth)acrylic" includes methacryl and acrylic, and "(meth)acrylate" includes methacrylate and acrylate.

<Polyisocyanate composition>
The polyisocyanate composition of this embodiment includes polyisocyanate A and polyisocyanate B. That is, the polyisocyanate composition is a mixture of polyisocyanate A and polyisocyanate B.

(Weight average molecular weight)
The polyisocyanate composition of this embodiment has a weight average molecular weight of 700 or more, preferably 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more. The upper limit of the weight average molecular weight of the polyisocyanate composition is not particularly limited, and is, for example, 20,000 or less, 15,000 or less, 12,000 or less, 10,000 or less, 9,000 or less, or 8,000 or less.

The weight average molecular weight of the polyisocyanate composition is, for example, 700 or more and 20,000 or less, 1,500 or more and 15,000 or less, 2,000 or more and 12,000 or less, 2,000 or more and 10,000 or less, 2,000 or more and 9,000 or less, and 2,000 or more and 8,000 or less.

When a polyisocyanate composition having a weight average molecular weight of at least the above lower limit is cured, a cured polyisocyanate product having excellent maximum stress and elongation is obtained. On the other hand, when a polyisocyanate composition having a weight average molecular weight of not more than the above upper limit is cured, a cured polyisocyanate product having excellent maximum stress and weather resistance can be obtained.

[Method of measuring weight average molecular weight]
The weight average molecular weight of the polyisocyanate composition of this embodiment can be measured, for example, by gel permeation chromatography (hereinafter sometimes abbreviated as "GPC").
The weight average molecular weight of the polyisocyanate composition of this embodiment can be adjusted by appropriately selecting the weight average molecular weights of the aliphatic polyisocyanate, alicyclic polyisocyanate, and polyol used as raw materials.

(viscosity)
The polyisocyanate composition of this embodiment has a viscosity of 10,000 mPa·s or less at 25°C.
The viscosity of the polyisocyanate composition at 25° C. is preferably 9000 mPa·s or less, more preferably 8000 mPa·s or less, more preferably 7000 mPa·s or less, even more preferably 6500 mPa·s or less.
The lower limit of the viscosity of the polyisocyanate composition at 25° C. is not particularly limited, but is, for example, 200 mPa·s or more, 300 mPa·s or more, 400 mPa·s or more, or 500 mPa·s or more.

The viscosity of the polyisocyanate composition at 25° C. is, for example, 200 mPa·s or more and 10,000 mPa·s or less, 300 mPa·s or more and 9,000 mPa·s or less, 400 mPa·s or more and 8,000 mPa·s or less, 500 mPa·s or more and 7,000 mPa·s or less, and 500 mPa·s or more and 7,000 mPa·s or less, for example. s or more and 6500 mPa·s or less.

Since the viscosity at 25° C. is within the above range, the polyisocyanate composition of this embodiment can be used without using a solvent.

The viscosity of the polyisocyanate composition at 25°C can be measured at 25°C using, for example, an E-type viscometer (manufactured by Tokimec Co., Ltd.) when the polyisocyanate composition does not contain an organic solvent.
When the polyisocyanate composition contains an organic solvent, the organic solvent contained in the polyisocyanate composition is removed using an evaporator and a vacuum dryer, and then the organic solvent contained in the polyisocyanate composition is removed using an E-type viscometer (manufactured by Tokimec Co., Ltd.) at 25°C. can be measured.

[Isocyanate group content (NCO group content)]
The content of NCO functional groups in the polyisocyanate composition is preferably 10.0% or more and 20.0% or less.
The isocyanate group content (NCO group content) of the polyisocyanate composition of the present embodiment is 20.0% by mass or less based on the total mass of the polyisocyanate composition in a state that does not substantially contain a solvent or diisocyanate. It is preferably 1.0% by mass or more and 19.5% by mass or less, even more preferably 5.0% by mass or more and 19.3% by mass or less, and 7.5% by mass or more. It is preferably 19.0% by mass or less, preferably 8.5% by mass or more and 19.0% by mass or less, preferably 9.5% by mass or more and 19.0% by mass or less, 10. It is particularly preferably 0% by mass or more and 19.0% by mass or less.

When the isocyanate group content of the polyisocyanate composition is at most the above upper limit, the elongation rate of the cured product obtained by curing the polyisocyanate composition can be made better. On the other hand, by being at least the above lower limit, the hardness of the cured product obtained by curing the polyisocyanate composition can be made better.
The content of NCO groups in the polyisocyanate composition can be determined, for example, by reacting the isocyanate groups of the polyisocyanate composition with an excess of amine (such as dibutylamine) and back titrating the remaining amine with an acid such as hydrochloric acid. Can be done.

≪Polyisocyanate A≫
Polyisocyanate A is derived from aliphatic or cycloaliphatic polyisocyanates. Polyisocyanate A is a polyisocyanate having a weight average molecular weight Mw of 1200 or less and containing an isocyanurate group.
Polyisocyanate A has an isocyanurate group in its molecular structure. By including polyisocyanate A, a cured product obtained by curing the polyisocyanate composition can exhibit weather resistance and high hardness.

Polyisocyanate A has a weight average molecular weight Mw of 1200 or less, preferably 1150 or less, more preferably 1000 or less, and even more preferably 950 or less.
The lower limit of the weight average molecular weight Mw of polyisocyanate A is not particularly limited, and is, for example, 500 or more, 550 or more, 600 or more, or 620 or more.
The weight average molecular weight Mw of polyisocyanate A is 500 or more and 1200 or less, 550 or more and 1150 or less, 600 or more and 1000 or less, and 620 or more and 950 or less.

Since the weight average molecular weight of polyisocyanate A is below the above upper limit, the weight average molecular weight of the polyisocyanate composition can be within the above range, the polyisocyanate composition can be maintained at a low viscosity, and the polyisocyanate composition can be maintained at a low viscosity. The hardness of the cured product can be made good.

[Method of measuring weight average molecular weight]
The weight average molecular weight of polyisocyanate A is, for example, the weight average molecular weight based on polystyrene measured by GPC.
Examples of polyisocyanate A having a weight average molecular weight within the above range include 1,6-diisocyanatohexane, 1,5-pentamethylene diisocyanate, or 3,5,5-trimethyl 1-isocyanato-3-(isocyanato Isocyanurate trimer of methyl)cyclohexane and its modified product with alcohol can be preferably used.

When measuring the weight average molecular weight of polyisocyanate A from a polyisocyanate composition, polyisocyanate A is separated from the polyisocyanate composition and the weight average molecular weight is measured by the method described above.
Methods for separating polyisocyanate A from the polyisocyanate composition include, for example, high performance liquid chromatography (HPLC), GPC, and fractional distillation using thin film distillation.

The aliphatic polyisocyanate or alicyclic polyisocyanate constituting polyisocyanate A will be described later.

[Average number of isocyanate functional groups]
The average number of isocyanate functional groups of polyisocyanate A is preferably 2.0 or more and 5.0 or less, more preferably 2.10 or more and 4.50 or less, from the viewpoint of increasing the curability and coating strength of the polyisocyanate composition. More preferably .20 or more and 4.30 or less.
When the average number of isocyanate functional groups of polyisocyanate A is equal to or greater than the above lower limit, the hardness, tensile strength, and durability of the cured product obtained by curing the polyisocyanate composition can be improved.
On the other hand, by being below the above upper limit, the elongation rate of the cured product obtained by curing the polyisocyanate composition can be made better.
The average number of isocyanate functional groups in polyisocyanate A can be measured using the method described in the Examples below.

Polyisocyanate A is preferably modified with a primary alcohol having 2 or more and 18 or less carbon atoms, or a secondary alcohol. Thereby, a polyisocyanate composition that does not use an organic solvent can be obtained.

Preferably, polyisocyanate A contains allophanate groups.

Polyisocyanate A contains allophanate groups and isocyanurate groups, and the molar ratio of allophanate groups to the total amount of allophanate groups and isocyanurate groups is preferably 10% or more.
The molar ratio of allophanate groups to the total amount of allophanate groups and isocyanurate groups can be determined by, for example, ¹ H-nuclear magnetic resonance (NMR) spectroscopy, ¹³ C-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry ( MS) method.

≪Polyisocyanate B≫
Polyisocyanate B is a polyisocyanate derived from an aliphatic polyisocyanate or an alicyclic polyisocyanate and a bifunctional to pentafunctional polyol having a number average molecular weight Mn of 500 or more.
In polyisocyanate B, the molar ratio NCO/OH of the isocyanate groups of the aliphatic or alicyclic polyisocyanate to the hydroxyl groups of the polyol is 2 or more and 30 or less.

The aliphatic polyisocyanate, alicyclic polyisocyanate, and polyol that constitute polyisocyanate B will be described later.

In polyisocyanate B, the molar ratio NCO/OH of the isocyanate groups of the aliphatic or alicyclic polyisocyanate to the hydroxyl groups of the polyol is 2 or more and 30 or less, preferably 3 or more and 25 or less.
When NCO/OH is at least the above lower limit, the weather resistance of the cured product obtained by curing the polyisocyanate composition can be improved. On the other hand, by being below the above-mentioned upper limit, the elongation of the cured product obtained by curing the polyisocyanate composition can be made good.

NCO/OH can be calculated, for example, using the molar amount of hydroxyl groups in the polyol used in the production of the polyisocyanate composition and the molar amount of isocyanate groups in the diisocyanate monomer that is the raw material for the polyisocyanate.

The weight average molecular weight of polyisocyanate B is preferably 1,400 or more, more preferably 1,500 or more, and even more preferably 1,800 or more.

Since the weight average molecular weight of polyisocyanate B is below the above upper limit, the weight average molecular weight of the polyisocyanate composition can be within the above range, and the hardness of the cured product obtained by curing the polyisocyanate composition is good. It can be done.

[Method of measuring weight average molecular weight]
The weight average molecular weight of polyisocyanate B is, for example, the weight average molecular weight based on polystyrene measured by GPC.

When measuring the weight average molecular weight of polyisocyanate B from a polyisocyanate composition, polyisocyanate B is separated from the polyisocyanate composition and the weight average molecular weight is measured by the method described above.
Examples of methods for separating polyisocyanate B from the polyisocyanate composition include fractional distillation using high performance liquid chromatography (HPLC), GPC, thin film distillation, and the like.

[Average number of isocyanate functional groups]
The average number of isocyanate functional groups of polyisocyanate B is preferably 2.0 or more and 5.5 or less, more preferably 2.01 or more and 4.00 or less, from the viewpoint of increasing the curability, coating strength, and elongation of the polyisocyanate composition. It is preferably 2.01 or more and 3.90 or less, and even more preferably 2.03 or more and 3.80 or less.
When the average number of isocyanate functional groups of polyisocyanate B is equal to or greater than the above lower limit, the hardness and durability of the cured product obtained by curing the polyisocyanate composition can be made better.
On the other hand, by being below the above upper limit, the viscosity of the polyisocyanate can be suppressed to a lower level, and the elongation rate of the cured product obtained by curing the polyisocyanate composition can be made better.
The average number of isocyanate functional groups of polyisocyanate B can be measured using the method described in the Examples below.

In the polyisocyanate composition of the present embodiment, the content of polyisocyanate A in the total amount of polyisocyanate A and polyisocyanate B is preferably 60% by mass or less, more preferably 50% by mass or less. The content is preferably 45% by mass or less, and more preferably 45% by mass or less.

Further, the content of polyisocyanate A in the total amount of polyisocyanate A and polyisocyanate B is, for example, 5% by mass or more, 10% by mass or more, or 15% by mass or more.

The content ratio of polyisocyanate A in the total amount of polyisocyanate A and polyisocyanate B is, for example, 5% by mass or more and 60% by mass or less, 10% by mass or more and 55% by mass or less, 15% by mass or more and 50% by mass or less. be.

When the content ratio of polyisocyanate A satisfies the above range, the hardness, strength, elongation rate, and durability of the cured product obtained by curing the polyisocyanate composition can be improved.

The content rate of polyisocyanate A in the total amount of polyisocyanate A and polyisocyanate B is calculated by the following formula.
Amount of polyisocyanate A (parts by mass)/(Amount of polyisocyanate A (parts by mass) + Amount of polyisocyanate B (parts by mass)) x 100

When measuring the content ratio of polyisocyanate A in the total amount of polyisocyanate A and polyisocyanate B from a polyisocyanate composition, for example, ¹ H-nuclear magnetic resonance (NMR) spectroscopy, ¹³ C- It can be measured by NMR spectroscopy, infrared absorption (IR) spectroscopy, and mass spectrometry.

(Aliphatic or alicyclic polyisocyanate)
The aliphatic or alicyclic polyisocyanate is derived from at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.

Examples of aliphatic diisocyanates include, but are not limited to, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, ethyl (2,6-diisocyanato)hexanoate, and 1,6-diisocyanato. Natohexane (hereinafter sometimes abbreviated as "HDI"), 1,9-diisocyanatononane, 1,12-diisocyanatododecane, 2,2,4- or 2,4,4-trimethyl-1 , 6-diisocyanatohexane and the like. These aliphatic diisocyanates may be used alone or in combination of two or more.

Examples of alicyclic diisocyanates include, but are not limited to, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (hereinafter sometimes abbreviated as "hydrogenated XDI"), 1 , 3- or 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl 1-isocyanato-3-(isocyanatomethyl)cyclohexane (hereinafter sometimes abbreviated as "IPDI"), 4-4' -diisocyanato-dicyclohexylmethane (hereinafter sometimes abbreviated as "hydrogenated MDI"), 2,5- or 2,6-diisocyanatomethylnorbornane, and the like. These alicyclic diisocyanates may be used alone or in combination of two or more.

Any of these aliphatic diisocyanates and alicyclic diisocyanates may be used alone, or two or more kinds of aliphatic diisocyanates and alicyclic diisocyanates may be used in combination.
Further, from the viewpoint of flexibility, the mass ratio of alicyclic polyisocyanate to aliphatic diisocyanate is preferably 0/100 or more and 30/70 or less.

Among these, the diisocyanate is preferably HDI, IPDI, hydrogenated XDI, or hydrogenated MDI, more preferably HDI or IPDI, and even more preferably HDI.

In addition to the above-mentioned diisocyanate, the following isocyanate monomers may also be used in the production of polyisocyanate.
(1) Aromatic compounds such as diphenylmethane-4,4'-diisocyanate (MDI), 1,5-naphthalene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), m-tetramethylxylylene diisocyanate (TMXDI), etc. Diisocyanate.
(2) 4-Isocyanate methyl-1,8-octamethylene diisocyanate (hereinafter sometimes referred to as "NTI"), 1,3,6-hexamethylene triisocyanate (hereinafter sometimes referred to as "HTI") , bis(2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter sometimes referred to as "GTI"), lysine triisocyanate (hereinafter sometimes referred to as "LTI"), and other triisocyanates.

The polyisocyanate having an isocyanurate group is preferably derived from one or more diisocyanate monomers selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates as exemplified above.

Further, the weight average molecular weight of the polyisocyanate having an isocyanurate group is preferably 900 or less, more preferably 880 or less. When the weight average molecular weight of the polyisocyanate having an isocyanurate group is equal to or less than the above upper limit, the weight average molecular weight of the polyisocyanate composition can be within the above range, the viscosity can be suppressed low, and the polyisocyanate The hardness of the cured product can be made good.
On the other hand, the lower limit of the weight average molecular weight is not particularly limited, but may be, for example, 300 or 400.
The weight average molecular weight of the polyisocyanate having an isocyanurate group is, for example, the weight average molecular weight based on polystyrene measured by GPC.
As the polyisocyanate having an isocyanurate group having a weight average molecular weight within the above range, an isocyanurate trimer of HDI or IPDI can be preferably used.

(polyol)
The number average molecular weight of the polyol is 500 or more, preferably 800 or more. When the number average molecular weight of the polyol is greater than or equal to the above lower limit, the polyisocyanate cured product has a large elongation and good flexibility.
On the other hand, the upper limit of the number average molecular weight of the polyol is not particularly limited, but may be, for example, 14,000, preferably 13,000, more preferably 12,500, and particularly preferably 12,000.
The number average molecular weight Mn of the polyol is, for example, the number average molecular weight based on polystyrene measured by GPC. Moreover, when using a mixture of two or more types of polyols, the number average molecular weight of the mixture is calculated.

The polyol may have at least 2 functionalities and at most 5 functionalities, and preferably at least 2 functionalities and at most 4 functionalities.

The polyol is preferably one or more polyols selected from the group consisting of polyester polyols, polyether polyols, epoxy polyols, polyolefin polyols, and polycarbonate polyols, and one or more polyols selected from the group consisting of polyester polyols and polyether polyols. More preferred are polyols.

Examples of the polyester polyol include the following polyester polyols (1) or (2).
(1) A polyester polyol obtained by a condensation reaction of a dibasic acid alone or a mixture of two or more types and a dihydric or higher alcohol alone or a mixture of two or more types.
(2) Polycaprolactone polyol obtained by ring-opening polymerization of ε-caprolactone with a dihydric or higher alcohol.
Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.
Examples of the dihydric or higher alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, Examples include pentaerythritol, 2-methylolpropanediol, and ethoxylated trimethylolpropane.

Among these, as the polyester polyol, polycaprolactone polyol having two or more functionalities is preferable.

Commercially available bifunctional polycaprolactone polyols include, for example, Daicel's product name "Plaxel 210" (number average molecular weight 1000, hydroxyl value 112.8 mgKOH/g, acid value 0.09 mgKOH/g), 210CP" (number average molecular weight 1000, hydroxyl value 112.8 mgKOH/g, acid value 0.16 mgKOH/g), product name "Plaxel 212" (number average molecular weight 1250, hydroxyl value 90.8 mgKOH/g, acid value 0.09 mgKOH /g), trade name "Plaxel 212CP" (number average molecular weight 1250, hydroxyl value 90.2 mgKOH/g, acid value 0.14 mgKOH/g), "Plaxel 220" (number average molecular weight 2000, hydroxyl value 56.7 mgKOH/g) , acid value 0.06 mgKOH/g), "Plaxel 220CPB" (number average molecular weight 2000, hydroxyl value 57.2 mgKOH/g, acid value 0.16 mgKOH/g), "Plaxel 220CPT" (number average molecular weight 2000, hydroxyl value 56 .6mgKOH/g, acid value 0.02mgKOH/g), "Plaxel 230" (number average molecular weight 3000, hydroxyl value 37.6mgKOH/g, acid value 0.07mgKOH/g), "Plaxel 240 (number average molecular weight 4000, Hydroxyl value: 28.5 mgKOH/g, acid value: 0.07 mgKOH/g), etc.

Commercially available trifunctional polycaprolactone polyols include, for example, Daicel's product name "Plaxel 305" (number average molecular weight 550, hydroxyl value 305.6 mgKOH/g, acid value 0.50 mgKOH/g), 308" (number average molecular weight 850, hydroxyl value 195.3 mgKOH/g, acid value 0.38 mgKOH/g), "Plaxel 309" (number average molecular weight 900, hydroxyl value 187.3 mgKOH/g, acid value 0.20 mgKOH/g ), "Plaxel 312" (number average molecular weight 1250, hydroxyl value 136.1 mgKOH/g, acid value 0.38 mgKOH/g), "Plaxel 320" (number average molecular weight 2000, hydroxyl value 85.4 mgKOH/g, acid value 0 .29mgKOH/g).

The polyether polyol is not particularly limited, but for example, an alkylene oxide alone or a mixture is added to a polyhydric alcohol alone or a mixture using an alkali metal hydroxide or a strong basic catalyst. Examples include the resulting polyether polyol, the polyether polyol obtained by reacting a polyamine compound with an alkylene oxide, and the so-called polymer polyol obtained by polymerizing acrylamide or the like using the above-mentioned polyethers as a medium.

Examples of the alkali metal include lithium, sodium, potassium, and the like.
Examples of the strong basic catalyst include alcoholates, alkyl amines, and the like.
Examples of the polyhydric alcohol include the same alcohols as those exemplified as dihydric or higher alcohols in the polyester polyol.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.
Examples of the polyamine compound include ethylenediamine.

≪Method for producing polyisocyanate composition≫
The polyisocyanate composition of this embodiment can be manufactured by mixing polyisocyanate A and polyisocyanate B.
One type of polyisocyanate A may be used alone, or two or more types may be used in combination.
Polyisocyanate B may be used alone or in combination of two or more.

Catalysts for deriving polyisocyanates having isocyanurate groups from aliphatic or alicyclic diisocyanates include commonly used isocyanurate reaction catalysts.

Although the isocyanurate reaction catalyst is not particularly limited, it is generally preferable to use a basic catalyst. Specific examples of the isocyanurate reaction catalyst include those shown below.
1) Tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium, and tetrabutylammonium, and acetates, propionates, octylates, caprates, myristates, and benzoates of the tetraalkylammoniums. weak organic acid salts such as
2) Hydroxide of aryltrialkylammonium such as benzyltrimethylammonium and trimethylphenylammonium, and acetate, propionate, octylate, caprate, myristate, benzoate, etc. of the aryltrialkylammonium. weak organic acid salts.
3) Hydroxides of hydroxyalkylammonium such as trimethylhydroxyethylammonium, trimethylhydroxypropylammonium, triethylhydroxyethylammonium, and triethylhydroxypropylammonium, and acetate, propionate, octylate, and capric acid of the hydroxyalkylammonium. weak organic acid salts such as salts, myristates, and benzoates.
4) Metal salts of tin, zinc, lead, etc. of alkyl carboxylic acids such as acetic acid, propionic acid, caproic acid, octylic acid, capric acid, myristic acid, etc.
5) Metal alcoholates such as sodium and potassium.
6) Aminosilyl group-containing compounds such as hexamethylene disilazane.
7) Mannich bases.
8) Mixtures of tertiary amines and epoxy compounds.
9) Phosphorous compounds such as tributylphosphine.

Among them, from the viewpoint of not producing unnecessary by-products, the isocyanurate reaction catalyst is preferably a quaternary ammonium hydroxide or a weak organic acid salt of quaternary ammonium, and tetraalkylammonium hydroxide, More preferably, it is an organic weak acid salt of tetraalkylammonium, a hydroxide of aryltrialkylammonium, or a weak organic acid salt of aryltrialkylammonium.

The upper limit of the amount of the isocyanurate reaction catalyst used is preferably 1000 mass ppm, more preferably 500 mass ppm, and more preferably 1000 mass ppm, based on the mass of the charged aliphatic or alicyclic diisocyanate. More preferably, the amount is ppm by mass.
On the other hand, the lower limit of the amount of the isocyanurate reaction catalyst used is not particularly limited, but may be, for example, 10 mass ppm.

The isocyanurate reaction temperature is preferably 50°C or higher and 120°C or lower, and more preferably 55°C or higher and 90°C or lower. By keeping the isocyanurate reaction temperature below the upper limit, coloration of the polyisocyanate tends to be more effectively suppressed.

When the desired conversion rate (ratio of the mass of the polyisocyanate produced in the isocyanurate reaction to the mass of the charged aliphatic or alicyclic diisocyanate) is reached, the isocyanurate reaction is carried out using an acidic compound (e.g. phosphorus). It is stopped by the addition of acid, acidic phosphate ester, etc.).
In addition, in order to obtain polyisocyanate, it is necessary to stop the progress of the reaction at an early stage.
However, since the initial reaction rate of the isocyanurate reaction is very fast, it is difficult to stop the reaction at an early stage, and the reaction conditions, especially the amount and method of addition of the catalyst, must be carefully selected. be. For example, a method of adding the catalyst in portions at regular intervals is recommended as a suitable method.
Therefore, the conversion rate of the isocyanurate reaction for obtaining polyisocyanate is preferably 10% or more and 60% or less, more preferably 15% or more and 55% or less, and 20% or more and 50% or less. It is even more preferable.
When the conversion rate of the isocyanurate-forming reaction is at most the above upper limit, the viscosity of the polyisocyanate can be lowered. Furthermore, when the conversion rate of the isocyanurate reaction is equal to or higher than the above lower limit, the reaction termination operation can be performed more easily.

Further, when deriving a polyisocyanate having an isocyanurate group, an alcohol having a valence of 1 or more and 6 or less can be used in addition to the above aliphatic or alicyclic diisocyanate.
Examples of the monohydric to hexavalent alcohol include polyhydric alcohols such as monoalcohols, diols, triols, and tetraols.

Examples of monoalcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, n-pentanol, n-hexanol, n-octanol, n-nonanol, and 2-ethylbutanol. , 2,2-dimethylhexanol, 2-ethylhexanol, cyclohexanol, methylcyclohexanol, ethylcyclohexanol and the like.

Examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1, 6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propane Examples include diol.
Examples of triols include glycerin, trimethylolpropane, and the like.
Examples of the tetraols include pentaerythritol and the like.

<Resin composition>
The resin composition of this embodiment includes a crosslinkable functional group-containing polymer and the polyisocyanate composition of this embodiment.

≪Crosslinkable functional group-containing polymer≫
The functional group of the crosslinkable functional group-containing polymer is preferably at least one of a hydroxyl group, a carboxy group, an epoxy group, an oxetane group, and an amino group.
The crosslinkable functional group-containing polymer may be any polymer containing a crosslinkable functional group that can react with the isocyanate groups of the polyisocyanates A and B described above. The crosslinkable functional group-containing polymer is preferably a polyol or an amino group.

The amino group, which is a functional group included in the crosslinkable functional group-containing polymer, is preferably a primary amino group or a secondary amino group. The secondary amino group is preferably an amino group derived from an aspartic acid ester polyamine.

Specific examples of the crosslinkable functional group-containing polymer include acrylic polyols, polycarbonate polyols, polyester polyols, polyether polyols, epoxy polyols, polyolefin polyols, polyurethane polyols, and polyamines.

Among these, one or more polyols selected from the group consisting of polycarbonate polyols, polyester polyols, polyether polyols, epoxy polyols, polyolefin polyols, and polyurethane polyols having a weight average molecular weight of 500 or more and 100,000 or less are preferred; More preferred are acrylic polyols, polyester polyols, polyether polyols, polycarbonate polyols, and aspartic acid ester polyamines having a molecular weight of 500 or more and 100,000 or less.

[Acrylic polyol]
The acrylic polyol is not particularly limited, but includes, for example, an ethylenically unsaturated bond-containing monomer having a hydroxy group alone or in a mixture, and another ethylenically unsaturated bond-containing monomer that can be copolymerized with this monomer. or a mixture obtained by copolymerizing.

The ethylenically unsaturated bond-containing monomer having a hydroxy group is not particularly limited, but includes, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and methacryl. Examples include hydroxybutyl acid. These may be used alone or in combination of two or more. Among these, hydroxyethyl acrylate or hydroxyethyl methacrylate is preferred.

Other ethylenically unsaturated bond-containing monomers that can be copolymerized with the above monomers include, for example, those shown in (1) to (5) below. These may be used alone or in combination of two or more.

(1) Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylate ) sec-butyl acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Heptyl (meth)acrylate, Octyl (meth)acrylate, Isooctyl (meth)acrylate, Nonyl (meth)acrylate, Isononyl (meth)acrylate, Decyl (meth)acrylate, Isodecyl (meth)acrylate, ( Undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, ( Heptadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. (meth)acrylic acid esters, etc.

(2) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid.

(3) Acrylamide, methacrylamide, N,N-methylenebisacrylamide, diacetone acrylamide, diacetone methacrylamide, maleic acid amide, maleimide, 1,2-epoxy-4-vinylcyclohexane, allyl glycidyl ether, 4-hydroxybutyl Monomers with epoxy groups such as acrylate glycidyl ether. Unsaturated amides such as N-methylolacrylamide, diacetone acrylamide, dimethylaminopropylacrylamide.

(4) Vinyl monomers such as glycidyl methacrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile, dibutyl fumarate, N-vinylpyrrolidone, N-vinylcaprolactam, and acryloylmorpholine.

(5) Vinyl monomers having a hydrolyzable silyl group such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ-(meth)acryloxypropyltrimethoxysilane.

[Polycarbonate polyol]
The polycarbonate polyol is not particularly limited, but examples thereof include those shown in (1) to (4) below.
(1) Dialkyl carbonates such as dimethyl carbonate.
(2) Alkylene carbonates such as ethylene carbonate.
(3) Diaryl carbonates such as diphenyl carbonate.
(4) Those obtained by condensation polymerization of low-molecular carbonate compounds such as those in (1) to (3) above.

Commercially available polycarbonate polyols include, for example, Duranol T5650E (number average molecular weight 500), T5650J (number average molecular weight 800), T5651 (number average molecular weight 1000), and T5652 (number average molecular weight 2000) manufactured by Asahi Kasei Corporation. Can be mentioned.

[Polyester polyol]
A polyester polyol can be obtained, for example, by subjecting a dibasic acid alone or a mixture of two or more types and a polyhydric alcohol alone or a mixture of two or more types to a condensation reaction.

Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, and Examples include methylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, and ethoxylated trimethylolpropane.

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.

[Polyether polyol]
The polyether polyols are not particularly limited, but include, for example, those shown in (1) to (3) below.

(1) Polyether polyols obtained by random or block addition of an alkylene oxide alone or a mixture to a polyhydric hydroxy compound or a mixture using a catalyst.

Examples of the catalyst include hydroxides (lithium, sodium, potassium, etc.), strong basic catalysts (alcolates, alkylamines, etc.), complex metal cyanide compounds (metallic porphyrins, zinc hexacyanocobaltate complexes, etc.), and the like. It will be done.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.

(2) Polyether polyols obtained by reacting a polyamine compound with an alkylene oxide.
Examples of the polyamine compound include ethylenediamines.
Examples of the alkylene oxide include those exemplified in (1).

(3) So-called polymer polyols obtained by polymerizing acrylamide or the like using the polyether polyols obtained in (1) or (2) as a medium.

Examples of the polyhydric hydroxy compound include those shown in (i) to (vi) below.

(i) Diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc.

(ii) Sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, rhamnitol and the like.

(iii) Monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribodesose and the like.

(iv) Disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, and melibiose.

(v) Trisaccharides such as raffinose, gentianose, and meletitose.

(vi) Tetrasaccharides such as stachyose.

[Epoxy polyol]
Examples of the epoxy polyol include novolac type epoxy polyol, β-methylepichloro type epoxy polyol, cyclic oxirane type epoxy polyol, glycidyl ether type epoxy polyol, glycol ether type epoxy polyol, epoxy type aliphatic unsaturated compound, epoxidized fatty acid ester, Examples include epoxy polyols such as ester-type polyhydric carboxylic acids, aminoglycidyl-type epoxy polyols, halogenated epoxy polyols, and resorcinol-type epoxy polyols, and resins obtained by modifying these epoxy polyols with amino compounds, polyamide compounds, and the like.

[Polyolefin polyol]
Examples of the polyolefin polyol include, but are not particularly limited to, polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and the like.

The statistical number of hydroxyl groups that one molecule of the polyol has (hereinafter sometimes referred to as "average number of hydroxyl groups") is preferably 2 or more. When the average number of hydroxyl groups in the polyol is 2 or more, it tends to be possible to further suppress a decrease in the crosslinking density of the coating film obtained by curing the one-component coating composition of the present embodiment.

[Polyurethane polyol]
The polyurethane polyol is not particularly limited, but can be obtained, for example, by reacting a polyol that does not contain a carboxyl group with an isocyanate component by a conventional method.

Examples of the polyol containing no carboxyl group include low molecular weight polyols such as ethylene glycol and propylene glycol. Further, examples of high molecular weight polyols include acrylic polyols, polyester polyols, polyether polyols, and the like.

[Polyamine]
The polyamine is not particularly limited, but one having two or more primary amino groups and two or more secondary amino groups in one molecule is more preferable. Further, the amino group included in the polyamine is preferably a secondary amine.

Specific examples of polyamines include, but are not limited to, diamines such as ethylene diamine, propylene diamine, butylene diamine, triethylene diamine, hexamethylene diamine, 4,4'-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, and isophorone diamine. Class: Chain polyamines having three or more amino groups such as bishexamethylenetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, tetrapropylenepentamine; 1,4,7,10,13 , 16-hexaazacyclooctadecane, 1,4,7,10-tetraazacyclodecane, 1,4,8,12-tetraazacyclopentadecane, 1,4,8,11-tetraazacyclotetradecane, aspartic acid ester Examples include cyclic polyamines such as amines, aliphatic polyamines, and aspartic acid ester polyamines are preferred.

Further, as the polyamine, the following polyamine N1 and polyamine N2 are preferable. Since polyamine N1 has higher reactivity than polyamine N2, it is more preferred in applications requiring quick drying properties. Further, the pot life may be adjusted by blending polyamine N1 and polyamine N2 depending on the required pot life.

[Content ratio with crosslinkable functional group-containing polymer]
In the resin composition of the present embodiment, the content of the above-mentioned polyisocyanate composition is preferably 0.01 parts by mass or more and 200.0 parts by mass or less with respect to 100 parts by mass of the crosslinkable functional group-containing polymer, It is more preferably 0.03 parts by mass or more and 180.0 parts by mass or less, and even more preferably 0.05 parts by mass or more and 160.0 parts by mass or less.

[Other ingredients]
The resin composition used in this embodiment may further contain other additives.
Other additives include, for example, curing agents other than polyisocyanate compositions that can react with crosslinkable functional group-containing polymers, curing catalysts, solvents, pigments (extender pigments, coloring pigments, metallic pigments, etc.), tackifying resins, Photopolymerization initiators, ultraviolet absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress coloring during the baking process, surface conditioners, fluidity conditioners, pigment dispersants, antifoaming agents, thickeners, Examples include film-forming aids and the like.

Examples of the curing agent include melamine resins, urea resins, epoxy group-containing compounds or resins, carboxyl group-containing compounds or resins, acid anhydrides, alkoxysilane group-containing compounds or resins, and hydrazide compounds.

The curing catalyst may be a basic compound or a Lewis acidic compound.
Examples of the basic compound include metal hydroxide, metal alkoxide, metal carboxylate, metal acetylacetinate, onium salt hydroxide, onium carboxylate, onium salt halide, metal salt of active methylene compound, active Examples include onium salts of methylene compounds, aminosilanes, amines, and phosphines. The onium salt is preferably an ammonium salt, a phosphonium salt, or a sulfonium salt.
Examples of the Lewis acidic compound include organic tin compounds, organic zinc compounds, organic titanium compounds, and organic zirconium compounds.

The resin composition of this embodiment is preferably solvent-free from the viewpoint of consideration to the natural environment and working environment, but a solvent may be used depending on the purpose.
When using a solvent, for example, 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy- 3-methyl-1-butanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether (DPDM), propylene glycol dimethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, Ethanol, methanol, iso-propanol, 1-propanol, iso-butanol, 1-butanol, tert-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1, Examples include 4-butanediol, 1,3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso-pentane, hexane, iso-hexane, cyclohexane, solvent naphtha, mineral spirit, and the like. These solvents may be used alone or in combination of two or more.

In addition, pigments (extender pigments, colored pigments, metallic pigments, etc.), ultraviolet absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress discoloration during the baking process, painted surface conditioners, fluidity conditioners, pigments. As the dispersant, antifoaming agent, thickener, and film forming aid, known ones can be appropriately selected and used. Further, from the viewpoint of improving weather resistance, it is preferable to include a light stabilizer (HALS).

≪Method for producing resin composition≫
The resin composition of the present embodiment can be used as either a solvent-based or aqueous-based resin composition, but in view of the recent demand for environmentally friendly products, it is suitably used as a solvent-free or aqueous-based resin composition.

When producing an aqueous-based resin composition (aqueous resin composition), first, a polyol or its aqueous dispersion or aqueous solution is added with a curing agent that can react with the crosslinkable functional group in the polyol. , curing catalysts, solvents, pigments (extender pigments, coloring pigments, metallic pigments, etc.), ultraviolet absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress coloring during the baking process, coating surface conditioners, fluids Additives such as regulators, pigment dispersants, antifoaming agents, thickeners, and film forming aids are added. Next, the polyisocyanate composition or its aqueous dispersion is added as a curing agent, and if necessary, water or a solvent is further added to adjust the viscosity. Next, a water-based resin composition (water-based resin composition) can be obtained by forcibly stirring with a stirring device.

For example, when producing a solvent-based resin composition, first, a polyol or its solvent diluted product is added with a curing agent, a curing catalyst, a solvent, and a pigment that can react with the crosslinkable functional group in the polyol, as necessary. (extender pigments, colored pigments, metallic pigments, etc.), ultraviolet absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress discoloration during the baking process, painted surface conditioners, fluidity conditioners, pigment dispersants, Add additives such as antifoaming agents, thickeners, and film-forming agents. Next, the polyisocyanate composition is added as a curing agent, and if necessary, a solvent is further added to adjust the viscosity. Next, a solvent-based resin composition can be obtained by stirring by hand or using a stirring device such as a Masella.

≪Cured resin material≫
The cured resin product of this embodiment is a cured product obtained by curing the resin composition described above.
The cured resin material of this embodiment is preferably a cured film. When the resin cured product is a cured film, the thickness is preferably 5 μm or more and 5000 μm or less, more preferably 10 μm or more and 2000 μm or less, even more preferably 10 μm or more and 1000 μm or less, and 20 μm or more and 800 μm or less. It is particularly preferable that there be.

The cured resin material of this embodiment is preferably a cured resin sheet. When the resin cured product is a resin cured sheet, the thickness is preferably 1 μm or more and 2000 μm or less.

The cured resin product of this embodiment is cured by applying the above resin composition to a base material using a known method such as roll coating, curtain flow coating, spray coating, bell coating, electrostatic coating, etc., and then heating it. It can be obtained by letting

From the viewpoint of environmental considerations, the resin composition is preferably cured at room temperature. However, depending on the application, curing can be accelerated by heating at a temperature of 40° C. or higher and 160° C. or lower.
From the viewpoint of energy saving and heat resistance of the base material, the heating time is preferably about 1 minute or more and about 60 minutes or less, and more preferably about 2 minutes or more and about 40 minutes or less.

The cured resin of this embodiment has excellent maximum stress, elongation, hardness, and weather resistance.

The cured resin product of this embodiment can be obtained by, for example, applying the above-mentioned polyisocyanate composition directly onto an adherend using a coater or the like without using a solvent, and then applying the polyisocyanate composition as it is on an adherend in an environment of 23° C. and 50% humidity. It can be manufactured by curing for 168 hours. Further, drying or heating may be performed as necessary.
In addition, depending on the application, the above-mentioned polyisocyanate composition may be used after being diluted or dissolved with a solvent.

In the cured resin product of this embodiment, a test piece obtained by cutting the cured resin product with a thickness of 60 μm into 10 mm width and 100 mm length was set in a tensile tester so that the grip distance was 20 mm, and the test piece was set at a speed of 20 mm/min. The elongation rate in the tensile test measured in is preferably 80% or more, more preferably 90% or more, even more preferably 100% or more, and particularly preferably 110% or more. When the elongation rate is equal to or higher than the above lower limit value, flexibility becomes more excellent. On the other hand, the upper limit of the elongation rate is not particularly limited, and can be, for example, 1000%.

In the tensile test, the cured resin of this embodiment preferably has a maximum stress of 20 MPa or more, more preferably 25 MPa or more, particularly preferably 30 MPa or more, particularly 35 MPa or more. It is preferably 40 MPa or more, and most preferably 40 MPa or more. When the maximum stress is greater than or equal to the above lower limit, the strength will be even better. On the other hand, the upper limit of the maximum stress is not particularly limited, and can be, for example, 100 MPa.

It is preferable that the cured resin material of this embodiment has a stress of 7 MPa or more at a 10% elongation rate in the above tensile test. In the above tensile test, it is preferable to use the crosslinkable functional group-containing polymer described in Examples at NCO/OH=1.

The Koenig hardness of the cured resin product having a thickness of 40 μm is preferably 20 times or more and 125 times or less, more preferably 23 times or more and 125 times or less, still more preferably 25 times or more and 125 times or less, and even more preferably 27 times. It is particularly preferable that the number of times is 125 or less. When the Koenig hardness is less than or equal to the above upper limit, it can have appropriate hardness, flexibility, and excellent impact resistance and flexibility.

The cured resin of this embodiment preferably has a gel fraction of 80% by mass or more, more preferably 80.0% by mass or more and 100.0% by mass or less, and 85.0% by mass or more and 100.0% by mass or more. It is more preferably 0 mass% or less, particularly preferably 90.0 mass% or more and 100.0 mass% or less, and most preferably 92.0 mass% or more and 100.0 mass% or less. When the gel fraction is at least the above lower limit, a cured product that is superior in durability, bending resistance, impact resistance, curability, strength, and elongation rate is likely to be obtained.

(Method of calculating gel fraction)
First, a resin composition was applied onto a release-treated polyethylene terephthalate film with a thickness of 38 μm, dried and cured at 80°C for 30 minutes, and then stored for 7 days in an environment of 23°C and 50% RH. A laminate including a 50 μm resin sheet is obtained.
Next, the peel-treated polyethylene terephthalate film is peeled off from the obtained laminate to obtain a resin sheet.
Next, the obtained resin sheet was stored at 23°C and 50% RH for 7 days, then wrapped in a mesh sheet, immersed in acetone at 23°C for 24 hours, taken out, and dried at 120°C for 2 hours. do. This yields the mass of the resin sheet dried after immersion in acetone.
The percentage of the mass of the resin sheet dried after immersion in acetone with respect to the mass of the resin sheet before immersion in acetone is calculated as the gel fraction.

EXAMPLES Hereinafter, the present invention will be explained with reference to examples, but the present invention is not limited to the following examples.

Hereinafter, this embodiment will be described in more detail based on Examples and Comparative Examples, but this embodiment is not limited to the following Examples.

[Physical properties 1]
(Isocyanate group content)
First, a measurement sample of 2 g or more and 3 g or less was accurately weighed in a flask (Wg). Next, 20 mL of toluene was added to dissolve the measurement sample. Next, 20 mL of a 2N di-n-butylamine solution in toluene was added, and after mixing, the mixture was left at room temperature for 15 minutes. Then, 70 mL of isopropyl alcohol was added and mixed. Next, this solution was titrated with a 1N hydrochloric acid solution (Factor F) as an indicator. The obtained titration value was defined as V2mL. The titration value obtained was then taken as V1 ml without the polyisocyanate sample. Next, the isocyanate group content (NCO%) (mass%) of the polyisocyanate composition was calculated from the following formula.

(Isocyanate group content (mass%))
= (V1-V2)×F×42/(W×1000)×100

[Physical properties 2]
(Weight average molecular weight)
The weight average molecular weight is the weight average molecular weight based on polystyrene as measured by gel permeation chromatography (GPC) using the following apparatus.

(Measurement condition)
Equipment: manufactured by Tosoh Corporation, HLC-802A
Column: Tosoh Corporation, G1000HXL x 1
G2000HXL x 1
G3000HXL x 1 Carrier: Tetrahydrofuran Detection method: Differential refractometer

[Physical properties 3]
(Average number of isocyanate functional groups)
The average number of isocyanate functional groups (average number of NCOs) of the polyisocyanate composition was determined by the following formula. In the formula, "Mn" means number average molecular weight, and the value measured in "Physical Properties 2" above was used. For "NCO%", the value calculated in "Physical Properties 1" above was used.

(Average number of isocyanate functional groups) = (Mn x NCO% x 0.01)/42

[Physical properties 4]
(viscosity)
The viscosity was measured at 25°C using an E-type viscometer (manufactured by Tokimec Co., Ltd.). The rotation speed is as follows.

(number of rotations)
100r. p. m. (If less than 128mPa・s)
50r. p. m. (In the case of 128 mPa・s or more and less than 256 mPa・s)
20r. p. m. (In case of 256 mPa・s or more and less than 640 mPa・s)
10r. p. m. (In case of 640mPa・s or more and less than 1280mPa・s)
5r. p. m. (In case of 1280mPa・s or more and less than 2560mPa・s)
2.5r. p. m. (In case of 2560mPa・s or more and less than 5120mPa・s)

[Physical properties 5]
(NCO/OH)
The molar ratio NCO/OH of the isocyanate groups of the polyisocyanate to the hydroxyl groups of the polyol was calculated using the molar amount of the hydroxyl groups of the polyol used for production and the molar amount of the isocyanate groups of the diisocyanate that is the raw material for the polyisocyanate.

<Production method of polyisocyanate>
[Synthesis example 1]
Polyisocyanate A1 was synthesized by the following method.
The inside of a four-necked flask equipped with a stirrer, thermometer, and cooling tube was replaced with nitrogen, and 100 parts by mass of HDI and 3.3 parts by mass of 2-ethylhexanol were charged, and after stirring at 76°C for 1.5 hours, After slowly adding 80 ppm of tetramethylammonium capreate as a catalyst, the reaction was continued for 1 hour. After adding phosphoric acid and further stirring at 90° C. for 2 hours, the reaction was stopped. Thereafter, the reaction solution was filtered, and unreacted HDI monomers were removed using a thin film distillation apparatus to obtain polyisocyanate A1. The yield was 28.5%, the isocyanate group content of the obtained polyisocyanate A1 was 20.5% by mass, and the average number of isocyanate functional groups was 2.98. The weight average molecular weight Mw of polyisocyanate A1 was 730. When analyzed by NMR, allophanate groups and isocyanurate groups were detected, and their molar ratio was 39:61.

[Synthesis example 2]
Polyisocyanate B1 was synthesized by the following method.
The inside of a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube was replaced with nitrogen, and 100 parts by mass of HDI and 7.5 parts by mass of 2-ethylhexanol were charged, and after stirring at 86 ° C. for 1.5 hours, The temperature was raised to 133°C, 2-ethylhexanoic acid ZrO was added, and the mixture was stirred for 3 hours. Thereafter, phosphoric acid was added and the mixture was stirred for an additional 40 minutes to stop the reaction. After filtering the reaction solution, unreacted HDI monomer was removed using a thin film distillation apparatus to obtain a polyisocyanate intermediate. To 100 parts by mass of the polyisocyanate intermediate, 40 parts by mass of trifunctional polyether polyol (polypropylene glycol, triol type) having a number average molecular weight Mn of 10,000 was added, and the mixture was stirred at 105°C for 7 hours to obtain polyisocyanate B1. The isocyanate group content of the obtained polyisocyanate B1 was 12.1% by mass, the Mw was 5920, and the average number of isocyanate functional groups was 2.08. When analyzed by NMR, allophanate groups and urethane groups were detected. Although a small amount of isocyanurate was detected, it was in a very small amount relative to allophanate groups and urethane groups, specifically, less than 2% in molar ratio.

[Synthesis example 3]
Polyisocyanate B2 was synthesized by the following method.
In a four-necked flask equipped with a thermometer, stirring blade, and reflux condenser, 100 parts by mass of HDI was charged under a nitrogen stream, and 7 parts by mass and 13 parts by mass of trifunctional polycaprolactone polyol (Plaxel 305: Mn550) were added. While stirring PTMG (polytetramethylene ether glycol: number average molecular weight Mn 1000), the temperature inside the reactor was maintained at 93° C. for 120 minutes. The reaction was stopped when the yield reached 30% by mass. After filtering the reaction solution, unreacted HDI was removed using a thin film distillation device, and the isocyanate group content was 9.1% by mass and Mw was 3100. Polyisocyanate B2 having an isocyanate average functional group number of 2.78 was obtained.

[Synthesis example 4]
Polyisocyanate B3 was synthesized by the following method.
The inside of a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube was replaced with nitrogen, and 100 parts by mass of HDI and 9.5 parts by mass of 2-ethylhexanol were charged, and after stirring at 86 ° C. for 1.5 hours, After slowly adding 80 ppm of tetramethylammonium caprate as a catalyst, the reaction was allowed to proceed for 1 hour. Thereafter, phosphoric acid was added, and after further stirring at 90° C. for 2 hours, the reaction was stopped. After filtering the reaction solution, unreacted HDI monomer was removed using a thin film distillation apparatus to obtain a polyisocyanate intermediate. To 100 parts by mass of the polyisocyanate intermediate, 40 parts by mass of EXCENOL 840 (trade name, manufactured by Asahi Glass Co., Ltd., polypropylene triol (terminal ethylene oxide added), number average molecular weight 6500) was added, and the mixture was stirred at 105°C for 7 hours. Polyisocyanate B3 was obtained. The isocyanate group content of the obtained polyisocyanate B3 was 12.2% by mass, the Mw was 6740, and the average number of isocyanate functional groups was 2.65. When analyzed by NMR, allophanate groups, urethane groups, and isocyanurate were detected.

[Synthesis example 5]
Polyisocyanate A2 was synthesized by the following method.
The inside of a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube was purged with nitrogen, 1000 g of HDI was charged, and 0.1 g of tetramethylammonium capriate was added as a catalyst while stirring at 67°C. After 4 hours, the set reaction end point was confirmed by measuring the refractive index of the reaction solution, and 0.2 g of phosphoric acid was added to stop the reaction. Thereafter, the reaction solution was filtered, and unreacted HDI monomers were removed using a thin film distillation apparatus to obtain polyisocyanate A2. The isocyanate group content of the obtained polyisocyanate A2 was 23.1% by mass, and the average number of isocyanate functional groups was 3.23.

<Manufacture of polyisocyanate composition>
Polyisocyanates A1, A2, and polyisocyanates B1 to B3 produced by the above method were blended in the amounts shown in Table 1 to produce polyisocyanate compositions of Examples 1 to 6 and Comparative Examples 1 to 2, respectively. .

<Production of crosslinkable functional group-containing compound>
[Synthesis example 6]
(Production of crosslinkable functional group-containing polymer: acrylic polyol)
A four-neck flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet was charged with 29 parts by mass of propylene glycol monomethyl ether, and the temperature was raised to 112° C. under nitrogen gas ventilation. After reaching 112°C, the nitrogen gas supply was stopped, and 22.3 parts by mass of 2-hydroxyethyl methacrylate, 8.0 parts by mass of methyl methacrylate, 26.1 parts by mass of butyl acrylate, and 42.3 parts by mass of A mixture consisting of styrene, 1.3 parts by mass of acrylic acid, and 2 parts by mass of 2,2'-azobis(isobutyronitrile) was added dropwise over 5 hours. Next, the mixture was stirred at 115° C. for 3 hours while flowing nitrogen gas, cooled to 60° C., and a butyl acetate solution was added to obtain a solution of acrylic polyol for producing a coating composition with a solid content of 60% by mass. The acrylic polyol for preparing the coating composition had a glass transition temperature Tg of 29.1°C, a hydroxyl value relative to the resin solid content of 139 mgKOH/g, and a weight average molecular weight Mw of 2.56×10 ⁴ .

<Production method of polyisocyanate cured film>
The polyisocyanates of Examples 1 to 6 and Comparative Examples 1 to 2 and the acrylic polyol of Synthesis Example 6 were mixed at NCO/OH=1, and stirred until homogeneous to obtain a resin composition. Thereafter, each resin composition was applied in the form of a release film with a thickness of 40 μm using an applicator, dried at 90°C for 30 minutes, and then stored at 23°C and 50% RH for 168 hours to cure the resin. Membranes 1 to 8 were obtained.

<Production method of polyisocyanate cured film C (polyurea)>
The polyisocyanates of Examples 1 to 6 and Comparative Examples 1 to 2 and the following polyamine (N1) as a crosslinkable functional group-containing compound were mixed at a ratio of NH/OH = 1.1, and a hindered amine light stabilizer ( HALS) was added at 1000 ppm, stirred until uniform, and then coated on a release film to a thickness of 40 μm using an applicator, stored at 23°C and 50% RH for 168 hours, and peeled off from the release film. Thus, cured resin films C1 to C8 were obtained.

Polyamine (N1): (2S,2'S)-tetraethyl=2,2'-{[methylenebis(cyclohexane-4,1-diyl)]bis(azanediyl)}disuccinate. The chemical formula of polyamine (N1) is shown below.

<Measurement method of maximum stress and elongation rate>
Test pieces of cured resin films 1 to 8 and cured resin films C1 to C8 were cut into pieces of 10 mm in width and 100 mm in length, set in a tensile tester so that the grip distance was 20 mm, and tested at a speed of 20 mm/cm in an environment of 23°C. The measurement was performed for 1 minute, and the values of the maximum stress, elongation rate, and stress at 10% elongation of the cured resin films 1 to 8 were obtained.

A case in which the maximum stress measured by the above method was 20 MPa or more was evaluated as having an excellent maximum stress.
A case where the elongation rate measured by the above method was 80% or more was evaluated as having an excellent elongation rate.
When the stress at 10% elongation measured by the above method was 10 MPa or more, the stress at 10% elongation was evaluated as excellent.

<Method of measuring Koenig hardness>
Cured resin films 1 to 8 and cured resin films C1 to C8 were formed on glass instead of release films, and the Koenig hardness (times) was measured.

A case where the measured Koenig hardness was 20 times or more and 125 times or less was evaluated as having excellent Koenig hardness.

[Measurement of gel fraction]
Approximately 0.1 to 0.2 g of cured resin films 1 to 8 and cured resin films C1 to C8 were collected, wrapped in a mesh sheet, immersed in acetone for 24 hours, dried at 105°C for 1 hour, and gel fraction = It was calculated by 100×(sample weight after drying)/(sample weight before adding acetone).

<Weather resistance test>
Cured resin films 1 to 8 and cured resin films C1 to C8 were formed on a panel instead of a release film, and placed in a super xenon weather meter (SX75, irradiance: 180 W/m ² ).

The conditions for the weather resistance test were that the black panel temperature during light irradiation was set at 65° C. and the humidity was 50%, and after 102 minutes, the cycle was repeated for 18 minutes at 95% humidity while spraying water. Before the start of the weather resistance test and after 2000 hours, the gloss (45° reflectance of light) was measured using a gloss meter. The gloss maintenance rate was calculated as the percentage obtained by dividing the gloss after 2000 hours by the gloss before starting the weather resistance test. Based on the calculated gloss retention rate, weather resistance was evaluated according to the following evaluation criteria.

(Evaluation criteria)
○: Gloss retention rate is 90% or more △: Gloss retention rate is 80% or more and less than 90% ×: Gloss retention rate is less than 80%

The cured products obtained by curing the polyisocyanate compositions of Examples 1 to 6 of the present embodiment were excellent in maximum stress, elongation, hardness, and weather resistance.
On the other hand, in Comparative Example 1 in which polyisocyanate A was used alone, and in Comparative Example 2 in which polyisocyanate B was used alone, no product was obtained that was excellent in maximum stress, elongation, hardness, and weather resistance.

According to the present invention, there is provided a polyisocyanate composition that can be used without a solvent and has excellent physical properties of a cured product obtained by curing the polyisocyanate composition, a resin composition containing this polyisocyanate composition, and a cured resin product. be able to.

Claims (21)

A polyisocyanate composition comprising polyisocyanate A and polyisocyanate B,
The polyisocyanate composition has a weight average molecular weight of 700 or more and a 25°C viscosity of 10,000 mPa·s or less,
The polyisocyanate A is derived from an aliphatic polyisocyanate or an alicyclic polyisocyanate, has a weight average molecular weight Mw of 1200 or less, and is a polyisocyanate containing an isocyanurate group,
The polyisocyanate B is derived from an aliphatic polyisocyanate or an alicyclic polyisocyanate and a polyol,
The polyol has a number average molecular weight Mn of 500 or more, and is a polyisocyanate composition having 2 or more functionalities and 5 or less functionalities. The polyisocyanate composition according to claim 1, wherein the polyisocyanate composition has an NCO functional group content of 10.0% or more and 20.0% or less. The polyisocyanate composition according to claim 1, wherein the polyisocyanate A has an average number of isocyanate functional groups of 2.0 or more and 5.0 or less. The polyisocyanate composition according to claim 1, wherein the polyisocyanate B has a weight average molecular weight of 1400 or more. The polyisocyanate composition according to claim 1, wherein the polyisocyanate B has an average number of isocyanate functional groups of 2.0 or more and 5.5 or less. The polyisocyanate composition according to claim 1, wherein the polyisocyanate A is a modified polyisocyanate modified with a primary alcohol having 2 or more and 18 or less carbon atoms, or a secondary alcohol. The polyisocyanate composition of claim 1, wherein the polyisocyanate A contains an allophanate group. The polyisocyanate A contains an allophanate group and an isocyanurate group,
The polyisocyanate composition according to claim 1, wherein the molar ratio of the allophanate groups to the total amount of the allophanate groups and the isocyanurate groups is 10% or more. The polyisocyanate composition according to claim 1, wherein the polyol is at least one of a polyester polyol and a polyether polyol. The polyisocyanate composition according to claim 1, wherein the content of the polyisocyanate A in the total amount of the polyisocyanate A and the polyisocyanate B is 60% by mass or less. A resin composition comprising a crosslinkable functional group-containing polymer and the polyisocyanate composition according to claim 1 or 2. The resin composition according to claim 11, wherein the functional group contained in the crosslinkable functional group-containing polymer is at least one of a hydroxyl group, a carboxy group, an epoxy group, an oxetane group, and an amino group. The resin composition according to claim 12, wherein the amino group is a primary amino group or a secondary amino group. The resin composition according to claim 13, wherein the secondary amino group is an amino group derived from an aspartic acid ester polyamine. A cured resin product obtained by curing the resin composition according to claim 11. The cured resin product according to claim 15, which has an elongation rate of 80% or more at 23°C when subjected to a tensile test with a distance between chucks of 20 mm and a speed of 20 mm/min. The cured resin product according to claim 15, wherein the cured resin product has a maximum stress of 20 MPa or more at 23° C. when subjected to a tensile test at a speed of 20 mm/min with a distance between chucks of 20 mm. The cured resin product according to claim 15, having a stress of 7 MPa or more at 10% elongation at 23°C. The cured resin product according to claim 15, wherein the cured resin product formed on glass has a Koenig hardness of 20 times or more and 125 times or less at 23°C. The cured resin product according to claim 15, having a gel fraction of 80% by mass or more. The cured resin product according to claim 15, wherein the cured resin product is a cured resin sheet having a thickness of 1 μm or more and 2000 μm or less.