JP2000248043A - Polyisocyanate composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyisocyanate composition excellent in reactivity at low temperature, also good in preservation stability and useful as a raw material for various kinds of polyurethanes by including a specific diisocyanate and a specified polydiisocyanate. SOLUTION: The objective composition is obtained by allowing the composition to contain a diisocyanate of formula I [one or both of R1 and R2 are each formula II (k is 0-2; j and m are each 1-5; h is 0-2) with the proviso that when one of them is formula II, the other is a 2-12C alkylene], and a polyisocyanate having a skeleton of formula II regulated so that the content of the compound of the formula I in which n is 0 may be 30-90 wt.%, the content of the one of the formula I in which n is 1 may be 9.5-40 wt.%, and the content of the one of the formula I in which n is 2-4 may be 0.5-30 wt.%. The composition is produced, fop example, by reacting a polycyclic aliphatic diisocyanate of formula III with carbon dioxide gas in the presence of 0.001-10.0 wt.% alkyl group-containing tertiary phosphine based on the amount of the diisocyanate at (-20 deg.C) to 80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyisocyanate composition, a method for producing the same, and uses thereof.

[0002]

2. Description of the Related Art A polyisocyanate compound containing an oxadiazinetrione ring obtained by reacting an organic diisocyanate with carbon dioxide and a method for producing the same are known from many publications [for example, Japanese Patent Publication No. Sho-45]. -3531
No. 4, JP-B-48-43357, JP-A-57
No. 9773]. These polyisocyanate compounds are widely used as raw materials for resins, foams, paints, films, adhesives and the like. Conventionally, as an organic diisocyanate, a polyisocyanate having an oxadiazinetrione ring obtained by reacting an aliphatic polyisocyanate or an araliphatic polyisocyanate with carbon dioxide has been proposed. On the other hand, an oxalate obtained by reacting a polycyclic aliphatic polyisocyanate represented by the general formula (3) or a mixture of the polycyclic aliphatic polyisocyanate and the linear aliphatic diisocyanate represented by the general formula (4) with carbon dioxide gas. Polyisocyanates having a diazinetrione ring are disclosed in
It is known from 199986. It has been known that the reaction solution of the polyisocyanate having an oxadiazinetrione ring has low viscosity and high solubility in a solvent. However, it is desired to further reduce the viscosity of the reaction solution and to improve the solubility in the solvent. I was For example, a conventionally known hexamethylene diisocyanate or a polyisocyanate having an oxadiazinetrione ring obtained from xylylene diisocyanate is heated and reacted with a polyhydroxy compound to generate an allophanate bond. Therefore, there are various restrictions in using it as a raw material for polyurethane. Therefore, a polyisocyanate having an oxadiazinetrione ring that is reactive even at lower temperatures has been desired.

In addition, these known polyisocyanates having an oxadiazinetrione ring have poor drying properties when used as a curing agent for a two-part urethane paint, and are sufficiently crosslinked to form a tough coating film. In order to do so, it was necessary to take a method such as standing for a long time or forced drying. However, this method has a drawback that yellowing is inevitable during forced drying due to poor heat resistance, and gloss is reduced. Therefore, development of a two-pack type urethane coating resin having good weather resistance and excellent drying properties has been strongly desired. Further, it has been desired to further improve the storage stability of a prepolymer obtained by urethane-forming or urea-forming the isocyanate group of these known polyisocyanates having an oxadiazinetrione ring.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyisocyanate composition useful for a polyisocyanate curing agent, a curable composition for urethane paint, a resin for urethane paint, a method for producing the same, and a method for producing the same. Provide its use.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that polycyclic aliphatic polyisocyanate or polycyclic aliphatic polyisocyanate and linear fatty acid An oxadiazinetrione ring-containing polyisocyanate obtained by reacting a mixture of aromatic diisocyanates with carbon dioxide under specific conditions is a polyisocyanate having a large number of oxadiazinetrione rings obtained by a conventional method. The polyisocyanate containing one oxadiazinetrione ring can be obtained in a large amount, and the polyisocyanate containing 0 to 1 oxadiazinetrione ring as a main component makes the reaction solution viscous. Was found to be low, and the solubility in a solvent was good. Such a polyisocyanate composition was found to have excellent reactivity at low temperatures, good storage stability, and particularly preferred properties as various polyurethane raw materials, and completed the present invention.

That is, the present invention provides the following 1) to 13). (1) General formula (1)

[0007]

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[Wherein, one or both of R ₁ and R ₂ is a group represented by the general formula (2), and when one of them is a group represented by the general formula (2), Is an alkylene group having 2 to 12 carbon atoms. And a diisocyanate represented by the general formula (2)

[0009]

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Wherein k is from 0 to 2 and j and m are from 1 to
A polyisocyanate having a skeleton represented by the following formula (1), wherein h is an integer of 0 to 2): -90% by weight and n in the general formula (1) is 1
Is 9.5 to 40% by weight, and the polyisocyanate of the general formula (1) in which n is 2 to 4 is 0.1%.
5 to 30% by weight of the polyisocyanate composition. (2) General formula (3)

[0011]

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(Where k is 0 to 2, j and m are 1 to 2)
5, h is an integer of 0 to 2) in the presence of 0.001 to 10.0% by weight of a tertiary phosphine having an alkyl group with respect to the diisocyanate. The method for producing a polyisocyanate composition according to (1), wherein carbon dioxide gas is reacted at a reaction temperature of -20 to 80 ° C. (3) General formula (3) (where k is 0 to 2, j and m
Represents an integer of 1 to 5 and h represents an integer of 0 to 2), and a polycyclic aliphatic diisocyanate represented by the following general formula (4):

[0013]

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(Wherein, R ₃ represents an alkylene group having 2 to 12 carbon atoms) and a mixture of a linear aliphatic diisocyanate and a tertiary phosphine having an alkyl group with respect to the diisocyanate. The method for producing a polyisocyanate composition according to (1), wherein carbon dioxide gas is reacted at a reaction temperature of -20 to 80 ° C in the presence of 0.001 to 10.0% by weight. (4) The method for producing a polyisocyanate composition according to any one of (1) to (3), wherein the reaction temperature is 0 to 30 ° C. (5) The method for producing a polyisocyanate composition according to any one of (1) to (3), wherein a reaction rate of the isocyanate group is maintained in a range of 10 to 60%. (6) The polycyclic aliphatic diisocyanate represented by the general formula (3) is 2,5- or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane or a mixture thereof. The method for producing a polyisocyanate according to any one of (3) to (5), wherein (7) The method for producing a polyisocyanate according to any one of (4) to (5), wherein the linear aliphatic diisocyanate represented by the general formula (4) is hexamethylene diisocyanate. (8) The method for producing a polyisocyanate according to any of (2) to (5), wherein the alkyl group of the tertiary phosphine having an alkyl group has 2 to 12 carbon atoms. (9) A curing agent for polyurethane, comprising the polyisocyanate composition according to (1). (10) A curable composition for polyurethane, comprising the curing agent for polyurethane according to (9) and a main agent containing a compound having one or more active hydrogens. (11) The compounding ratio of the curing agent for polyurethane according to (9) and the compound having one or more active hydrogens is equivalent ratio (H
The curable composition for polyurethane according to claim 10, wherein (NCO group) is in the range of 0.8 to 1.2. (12) A non-yellowing polyurethane cured product obtained from the curable composition for polyurethane according to any one of (10) and (11). (13) A paint containing the non-yellowing polyurethane cured product according to (12).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [Polyisocyanate composition] The polyisocyanate composition according to the present invention is a polyisocyanate containing a diisocyanate represented by the general formula (1) and a polyisocyanate having a skeleton represented by the general formula (2). An isocyanate composition, wherein 30 to 90% by weight of a polyisocyanate in which n is 0 in the general formula (1) and 9.5 to 40% by weight of a polyisocyanate in which n is 1 in the general formula (1) Is a polyisocyanate composition characterized by the fact that, if the content of each component, which is an essential component of the present invention, is within the above range, other components are added within a range where the total amount of all components is 100%. It may be contained. The polyisocyanate composition of the present invention can be used in the fields of curing agents for polyurethane, paints, and the like. Those having the skeleton of the general formula (1) are sometimes referred to as oxadiazinetriones. When the polyisocyanate composition of the present invention is used as a curing agent for a solvent-based paint, a polyurethane resin, or the like, the polyisocyanate of general formula (1) in which n is 0 is 35 to 89.
10 to 38% by weight of the polyisocyanate where n is 1 in the general formula (1) and 1.0 to 28% by weight of the polyisocyanate where n is 2 to 4 in the general formula (1). It is preferable that the composition is a polyisocyanate composition.

The polyisocyanate composition of the present invention comprises a polyisocyanate of the general formula (1) wherein n is 0 and an oxadiazinetrione ring of the general formula (1) wherein n is 1.
Containing a large amount of polyisocyanate and having very good compatibility with solvents commonly used in the field of coatings such as ethyl acetate, butyl acetate, and xylene;
By containing a large amount of polyisocyanate in which n is 0, the polymer exhibits excellent fluidity at room temperature, high reactivity, and excellent curability. A polyisocyanate composition produced from a polycyclic aliphatic diisocyanate and a linear aliphatic diisocyanate is particularly preferable because it has excellent compatibility with a solvent and exhibits high fluidity in a wide temperature range.

(Polycyclic Aliphatic Diisocyanate) The polycyclic aliphatic diisocyanate suitably used in the method for producing a polyisocyanate of the present invention is represented by the following general formula (3). And the following compounds. k =
As those having 0 and h = 0, 1,3-di (isocyanatomethyl) -cyclohexane 1,4-di (isocyanatomethyl) -cyclohexane 1,3-di (isocyanatoethyl) -cyclohexane, 1,4 -
Di (isocyanatoethyl) -cyclohexane, 1-isocyanatomethyl-3 (4) -isocyanatoethyl-cyclohexane, 1-isocyanatomethyl-3 (4) -isocyanatopropyl-cyclohexane, 1-isocyanatomethyl-3 (4) −
Isocyanatobutyl-cyclohexane, 1-isocyanatomethyl-3 (4) -isocyanatopentyl-cyclohexane, 1-isocyanatoethyl-3 (4) -isocyanatopropyl-cyclohexane, 1-isocyanatoethyl-3 (4) -Isocyanatobutyl-cyclohexane, 1-isocyanatomethyl-3 (4) -isocyanatopentyl-cyclohexane and the like.

Assuming that k = 0 and h = 1, 3 (4), 7
(8) -Di (isocyanatomethyl) bicyclo [4,3,0 ^1,6 ] nonane, 3 (4) -isocyanatomethyl-7 (8) -isocyanatoethylbicyclo [4,3,0 ^1,6 Nonane, 3 (4) -isocyanatoethyl-7 (8) -isocyanatomethylbicyclo [4,3,0 ^1,6 ]
Nonane, 3 (4) -isocyanatomethyl-7 (8) -isocyanatopropylbicyclo [4,3,0 ^1,6 ] nonane, 3 (4) -isocyanatopropyl-7 (8) -isocyanatomethylbicyclo (4,3,
0 ^1,6 ] nonane, 3 (4) -isocyanatomethyl-7 (8) -isocyanatobutylbicyclo [4,3,0 ^1,6 ] nonane, 3 (4) -isocyanatobutyl-7 (8) -Isocyanatomethylbicyclo [4,
3,0 ^1,6 ] nonane, 3 (4) -isocyanatomethyl-7 (8) -isocyanatopentylbicyclo [4,3,0 ^1,6 ] nonane, 3 (4)-
Isocyanatopentyl-7 (8) -isocyanatomethylbicyclo [4,3,0 ^1,6 ] nonane, 3 (4), 7 (8) -di (isocyanatoethyl) bicyclo [4,3,01 ^{, 6} ] nonane, 3 (4) -isocyanatoethyl-7 (8) -isocyanatopropylbicyclo [4,3,0
^1,6 ] nonane, 3 (4) -isocyanatopropyl-7 (8) -isocyanatoethylbicyclo [4,3,0 ^1,6 ] nonane, 3 (4) -isocyanatoethyl-7 (8)- Isocyanatobutyl bicyclo [4,3,0 ^1,6 ] nonane, 3 (4) -isocyanatobutyl-7 (8)-
Isocyanatoethylbicyclo [4,3,0 ^1,6 ] nonane, 3 (4)
-Isocyanatoethyl-7 (8) -isocyanatopentylbicyclo [4,3,0 ^1,6 ] nonane, 3 (4) -isocyanatopentyl
-7 (8) - isocyanatoethyl bicyclo [4,3,0 ^1,6] nonane, and the like.

Assuming that k = 1 and h = 0, 2,5 (6) −
Di (isocyanatomethyl) bicyclo [2,2,1] heptane, 2-isocyanatomethyl-5 (6) -isocyanatoethylbicyclo [2,2,1] heptane, 2-isocyanatomethyl-5 (6) -Isocyanatopropylbicyclo [2,2,1] heptane, 2-isocyanatomethyl-5 (6) -isocyanatobutylbicyclo [2,2,1] heptane, 2-isocyanatomethyl-5 (6) -isocyanate Natopentylbicyclo [2,2,
1] heptane, 2,5 (6) -di (isocyanatoethyl) bicyclo [2,2,1] heptane, 2-isocyanatoethyl-5
(6) -isocyanatopropylbicyclo [2,2,1] heptane, 2-isocyanatobutyl-5 (6) -isocyanatobutylbicyclo [2,2,1] heptane, 2-isocyanatoethyl5 (6) -Pentylbicyclo [2,2,1] heptane and the like.

Also, assuming that k = 2 and h = 0, 2,
5 (6) -di (isocyanatomethyl) bicyclo [2,2,2] octane, 2-isocyanatomethyl-5 (6) -isocyanatoethylbicyclo [2,2,2] octane, 2-isocyanatomethyl -5 (6) -isocyanatopropylbicyclo [2,2,
2] octane, 2-isocyanatomethyl-5 (6) -isocyanatobutylbicyclo [2,2,2] octane, 2-isocyanatomethyl-5 (6) -isocyanatopentylbicyclo [2,2,2] Octane, 2,5 (6) -di (isocyanatoethyl) bicyclo [2,2,2] octane, 2-isocyanatoethyl-5 (6) -isocyanatopropylbicyclo [2,2,2]
Octane, 2-isocyanatoethyl-5 (6) -isocyanatobutylbicyclo [2,2,2] octane, 2-isocyanatoethyl-5 (6) -isocyanatopentylbicyclo [2,2,
2] octane.

In the case of k = 1 and h = 1, 3
(4), 8 (9) -di (isocyanatomethyl) tricyclo [5,
2,1,0 ^2,6 ] decane, 3 (4) -isocyanatomethyl-8 (9)-
Isocyanatoethyltricyclo [5,2,1,0 ^2,6 ] decane,
3 (4) - isocyanatomethyl-8 (9) - isocyanatopropyltrimethoxysilane cyclo [5,2,1,0 ^{2, 6]} decane, 3 (4) - isocyanatomethyl-8 (9) - isocyanatobutyl Tricyclo [5,2,
1,0 ^2,6] decane, 3 (4) - isocyanatomethyl-8 (9) - isocyanatomethyl pen tilt Li cyclo [5,2,1,0 ^{2, 6]} decane,
3 (4), 8 (9) -di (isocyanatoethyl) tricyclo [5,
2,1, 0 ^2,6 ] decane, 3 (4) -isocyanatoethyl-8 (9)
- isocyanatopropyltrimethoxysilane cyclo [5,2,1,0 ^{2, 6]} decane, 3 (4) - isocyanatoethyl -8 (9) - isocyanatobutyl tricyclo [5,2,1,0 ^2,6 ] decane, 14) - isocyanatoethyl -8 (9) - isocyanatomethyl pen tilt Li cyclo [5,2,1,0 ^{2, 6]} decane and the like.

Of these cycloaliphatic diisocyanates, 2,5-diisocyanatomethylbicyclo [2,2,1] heptane and 2,6-diisocyanatomethylbicyclo [2,2 , 1] heptane, or a mixture thereof (hereinafter abbreviated as NBDI) or 3 (4), 8 (9) -di (isocyanatomethyl) tricyclo [5,2,1,0 ^2,6 ] decane (hereinafter, referred to as NBDI)
TCDI). In the polycyclic aliphatic diisocyanate represented by the general formula (3), k is 1-2, j
And m is preferably an integer of 1 to 5, and h is an integer of 0 to 2. In particular, when further improvement in curability, drying property and heat resistance is required, among the polycyclic aliphatic diisocyanates represented by the general formula (3), when R ₁ = R ₂ , the formula is used. In the formula, k is preferably from 1 to 2. If further improvement in curability, drying property and heat resistance is required, k is preferable.
= 1 to 2, and h = 1 to 2 are more preferable. These cycloaliphatic diisocyanate compounds may be used alone or in combination of two or more, and may be used alone or in combination with other isocyanate compounds as long as the effects of the present invention are not impaired. Needless to say, it's good.

(Method for producing cycloaliphatic diisocyanate) The method for producing the cycloaliphatic diisocyanate compound is as follows.
Although not particularly limited, for example, DE P 3,018,198.7, D
General formula in E-OS 1,645,595 and 2,819,980
(3) is described as a method for synthesizing a compound in which h = 1, j = 1, and k = 1. The compound is produced from dimerized cyclopentadiene by a sequential reaction of a hydroformylation, a reducing amino compound and a phosgenation. Or US
P 3,143,570 discloses that in general formula (3), h = 0,
As described as a method for synthesizing a compound in which j = 1 and k = 1, the compound can be produced according to a method based on a phosgenation reaction of a corresponding diamine.

(Linear Aliphatic Diisocyanate) The linear aliphatic diisocyanate preferably used in the present invention is represented by the general formula (4). Ethane, 1,3-diisocyanatopropane, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, 1,7-diisocyanatoheptane, 1,8 -
Diisocyanatooctane, 1,9-diisocyanatononane,
Examples thereof include 1,10-diisocyanatodecane, 1,11-diisocyanatoundecane, and 1,12-diisocyanatododecane. Among them, 1,6-diisocyanatohexane (sometimes called hexamethylene diisocyanate, hereinafter abbreviated as HDI) is preferred as a versatile linear aliphatic diisocyanate.

(Production method of polyisocyanate) The production method is not particularly limited as long as the polyisocyanate composition of the present invention can be obtained, but the polycyclic aliphatic diisocyanate represented by the general formula (3) and an alkyl group Tertiary phosphine having the formula
It is preferable to react carbon dioxide gas at a reaction temperature of -20 to 80 ° C. in the presence of 重量 10.0% by weight to produce. A reaction solvent can be used as needed. Alternatively, a mixture of the polycyclic aliphatic diisocyanate represented by the general formula (3) and the linear aliphatic diisocyanate represented by the general formula (4) is added in an amount of 0.001 to 10 based on the diisocyanate. .
In the presence of tertiary phosphine having 0% by weight of an alkyl group,
It is also preferable that carbon dioxide is reacted at a reaction temperature of −20 to 80 ° C. for production. The progress of the reaction can be determined by a method for measuring the residual amount of unreacted raw materials by gas chromatography or di-n-
The excess di-n-butylamine can be back-titrated with hydrochloric acid by reacting a butylamine with an isocyanate group, and the excess di-n-butylamine can be traced by a method of measuring the isocyanate content. In the present production method, it is derived from the polycyclic aliphatic diisocyanate represented by the general formula (3), or the polycyclic aliphatic diisocyanate and the linear aliphatic diisocyanate represented by the general formula (4). It is preferable to keep the reaction rate of the total amount of isocyanate groups in the range of 10 to 60%. In this case, the final reaction rate can be reduced to 1 by controlling the reaction temperature and the like.
The reaction rate of the isocyanate group may be controlled to 0 to 60%. When the conversion of the isocyanate group reaches the range of 10 to 60%, a catalyst poison is immediately added to deactivate the catalyst to stop the reaction. May be kept in the range of 10 to 60%.
In general, if the conversion reaction proceeds too much, the viscosity of the product increases and the compatibility with the polyol decreases. Therefore, it is preferable to lower the conversion rate of the reaction, leave unreacted raw materials, and stop the reaction. The reaction conversion is usually such that the amount of unreacted raw materials is 30 to 90% by weight, and preferably 40 to 80% by weight. Once the reaction has reached the desired conversion and / or the conversion of the isocyanate groups, for example, phosphoric monoesters, phosphoric diesters, polyphosphoric acids, peroxides, p
-Toluenesulfonic acid ester, bromoacetic acid ester,
Trichloroacetic acid, cyanoacetate, dimethyl sulfate,
The reaction is stopped by adding a catalyst poison such as benzoyl chloride or acetyl chloride. The catalyst poison may be used alone or in combination. The amount of addition may be any as long as the reaction can be stopped at the target reaction rate, but it is 1.0 to 4.0 of the equivalent amount for neutralizing the catalyst.
The range of double amount is preferred. Further, the unreacted raw material contained in the polyisocyanate composition obtained as described above may be partially removed by a method such as thin-film distillation or the like, or the polyisocyanate obtained as described above. The unreacted raw materials contained in the composition are removed by a method such as thin film distillation to remove all or a part of the unreacted raw materials.
The polyisocyanate composition of the present invention can be produced by, for example, a method of adding a polyisocyanate having a value of 0. When the reaction is stopped by temperature control, addition of a catalyst poison, or the like, unreacted diisocyanate is usually mixed, and the liquid is a colorless or pale yellow low-viscosity liquid. In such a case, the unreacted raw materials and the used solvent may be removed as necessary. The removal of the unreacted raw materials and / or the solvent may be performed at any timing, and may be performed simultaneously with or before or after the removal of the catalyst poison. Removal of unreacted diisocyanate compound and solvent can be carried out by thin-film distillation or the like. The polyisocyanate composition obtained by removing all or a part of the unreacted diisocyanate may, if necessary, be a polycyclic aliphatic diisocyanate represented by the general formula (3) or a general formula (4) By adding one or more linear aliphatic diisocyanates represented by
The isocyanate group content and viscosity can be adjusted.

The reaction temperature varies depending on the type and amount of the catalyst, but is preferably -20 ° C. or higher from the viewpoint of the reaction rate, and suppresses by-products such as polyisocyanates containing uretdione groups and / or isocyanurate groups. From the viewpoint of improving the selectivity of the oxadiazinetrione derivative.
C. or lower is preferable, preferably in the range of -10 to 50C, and more preferably in the range of 0 to 30C. In the method of the present invention, when a mixture of the polycyclic aliphatic diisocyanate represented by the general formula (3) and the straight-chain aliphatic diisocyanate represented by the general formula (4) is used, At 1:
It can be used in the range of 9 to 9: 1. A mixture in a molar ratio in this range is used as a raw material diisocyanate. The polyisocyanate obtained by reacting in this range is a pale yellow viscous resinous liquid, and its viscosity changes depending on the mixing composition ratio of the raw materials. For example, NBDI and HDI as starting materials exhibit fluidity within this molar ratio range, and the polyisocyanate obtained from the NBDI / HDI composition ratio in this range has fluidity and heat stability.

(Tertiary phosphine having an alkyl group) As the tertiary phosphine having an alkyl group used in the present invention, those having 1 to 12 carbon atoms in the alkyl group are useful, and any one of a chain type and a cyclic type can be used. May be used. As the tertiary phosphine having an alkyl group, for example, trimethylphosphine, triethylphosphine, tri-n-
Examples include propylphosphine, triiso-propylphosphine, tri-n-butylphosphine, trisec-butylphosphine, tritert-butylphosphine, trioctylphosphine, diethylcyclohexylphosphine, and the like. Further, a mixture of tertiary phosphines having two or more alkyl groups may be used. The tertiary phosphine having an alkyl group may be used after being diluted with a solvent having no reaction activity with respect to the isocyanate group. The amount of the tertiary phosphine having an alkyl group varies depending on its kind, reaction conditions and the like, but is generally 0.001 to 10% by weight, particularly 0.01 to 3% by weight based on the diisocyanate.
It is desirable to use it in the range of weight%.

(Other polyisocyanate production conditions, etc.) The carbon dioxide gas used in the reaction may be used in any form as long as it is partially dissolved in the reaction system. For example, carbon dioxide gas is introduced into the reaction system. The reaction can be performed by blowing, supplying liquid carbon dioxide gas, or allowing solid carbon dioxide to coexist in the reaction system. Carbon dioxide, liquefied carbon dioxide, and carbon dioxide on a solid can be reacted under pressure.

In the reaction, a solvent may or may not be used. When a solvent is used, a solvent having no reaction activity for the isocyanate group is usually used. For example, cyclohexane, toluene, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, cellosolve acetate and the like can be used as appropriate. Particularly, as the viscosity of the reaction solution increases as the reaction proceeds, it may be desirable to add a solvent during the reaction. In addition, the reaction may be performed in an atmosphere of an inert gas such as nitrogen, helium, or argon. In the reaction of the present invention, there is no particular limitation on the apparatus and the like, but a reactor equipped with a thermometer, a carbon dioxide gas inlet, and a cooling pipe so that the inside of the reaction solution is sufficiently stirred is preferable.

(Uses of Polyisocyanate Composition) The polyisocyanate composition of the present invention comprises a curing agent for polyurethane, a curable composition for polyurethane and a raw material for a coating composition, and a non-yellow composition obtained by curing the same. It is used as a modified polyurethane cured product, resin, paint and the like. here,
The term “for polyurethane” includes the fields of so-called foams, elastomers, adhesives and the like, and is not limited to the field of paints. Also, the obtained polyisocyanate mixture, if necessary, after blocking the isocyanate group with a blocking agent, mixed with an active hydrogen-containing compound, two-part heat resistance, non-yellowing urethane excellent in weather resistance It can also be a resin for paint.

[Curedant composition for polyurethane] The curable composition for polyurethane of the present invention is represented by the general formula (1)
Or a polyisocyanate composition containing a polyisocyanate obtained by blocking the NCO group of the polyisocyanate represented by the general formula (1) and a compound having at least one or more active hydrogens. The resulting composition.

(Compound Containing Active Hydrogen Used in Curing Agent for Polyurethane) The compound containing at least one active hydrogen used in the curing agent for polyurethane includes:
Compounds and polymers containing at least one active hydrogen in one molecule are included. Specifically, methanol, ethanol, propanol, isopropanol, butanol, monoalcohols such as hexanol alone or a mixture, ethylene glycol, propylene glycol,
β, β'-dihydroxydiethyl ether (diethylene glycol), dipropylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,6-
Hexamethylene glycol, neopentyl glycol,
Polyethylene glycol, polypropylene glycol,
Glycols such as polypropylene-polyethylene glycol and polybutylene glycol; alkane polyols such as glycerin, trimethylolpropane, hexanetriol, pentaerythritol, xylitol and sorbitol; (Eg, ethylene oxide, propylene oxide, 1,2-butylene oxide, etc.) alone or in the form of a mixture of polyether polyols obtained by adding a polyether obtained by reacting an alkylene oxide with a polyfunctional compound such as ethylenediamine or ethanolamine. Polyether polyols such as polyols;

A dibasic acid (for example, alone or in a mixture selected from the group consisting of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid and terephthalic acid) Polyhydric alcohols (for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, glycerin, trimethylolpropane, etc.) Polyester polyol resins obtained by a condensation reaction with a polymerizable monomer having at least one active hydrogen in one molecule and another monomer copolymerizable therewith. A Kuryl polyol resins, specifically, for example, (a) active hydrogen-containing acrylate (eg, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, etc.), active hydrogen Containing methacrylic acid esters (for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid-
2-hydroxybutyl) or glycerin monoester or methacrylate monoester, trimethylolpropane acrylate monoester or methacrylate monoester alone or as a mixture of (b) acrylic acid Esters (for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, etc., methacrylic esters (for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, methacryl Acid n-butyl, isobutyl methacrylate, n-hexyl methacrylate,
And / or (c) unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc.), unsaturated amides (eg, acrylamide,
N-methylol acrylamide, diacetone acrylamide, etc.) and other polymerizable monomers (for example, glycidyl methacrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile, etc.) and are polymerized with a single or a mixture thereof. Acrylic polyol resins;

Novolak type, β-methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, glycol ether type, epoxidized fatty acid unsaturated compound, epoxidized fatty acid ester type, polycarboxylic acid ester type, amino acid Examples include epoxy resins such as glycidyl type, halogenated type, resorcinol type, etc., and monosaccharides such as fructose, glucose, sucrose, lactose, 2-methylglycoxide or derivatives thereof, trimethylolbenzene, tris (2-hydroxy And aromatic or heterocyclic polyhydric alcohols such as ethyl) isocyanurate. These may be used alone or as a mixture of two or more. Further, these and other compounds containing two or more active hydrogens, for example, a compound containing a primary or secondary amino group (for example, ethylenediamine, triamine, etc.) Ethylenediamine, hexamethylenediamine, m-xylylenediamine, diaminodiphenylmethane, isophoronediamine, diethylenetriamine, polyamines obtained by adding various alkylene polyamines and alkylene oxides, N, N′-dimethylethylenediamine, etc., substituted urea compounds (for example, N, N'-dimethylurea, N-methyl-N'-cyclohexylurea, etc., thiol group-containing compounds (e.g., 1,2-ethanedithiol, 1,6
Hexanedithiol, polyether polythiol, polyester polythiol, etc.), a carboxyl group-containing compound (eg, succinic acid, adipic acid, sebacic acid, terephthalic acid, carboxyl group-terminated polybutadiene, etc.), or different active hydrogen-containing groups in one molecule. One or more compounds selected from compounds contained therein (for example, monoethanolamine, thioethanolamine, lactic acid, β-alanine, etc.) can be mixed and used. As described above, various active hydrogen-containing compounds have been specifically exemplified.
The active hydrogen-containing compound of the present invention is not limited to these, and any active hydrogen-containing compound capable of forming a urethane resin by reacting with the polyisocyanate used in the curable composition for polyurethane of the present invention. Can also be used, and various combinations can be selected.

(Formation ratio of curable composition for polyurethane, etc.) In the formation of the curable composition for polyurethane of the present invention, the compounding ratio of the compound containing at least one active hydrogen to the polyisocyanate is The equivalent ratio of / NCO is used in the range of 0.5 to 2, preferably 0.8 to 1.2. In forming the curable composition for polyurethane of the present invention, a compound containing at least one active hydrogen and a polyisocyanate may be used, if necessary, in a suitable solvent such as a hydrocarbon (eg, benzene, toluene, and the like). Solvents such as xylene, cyclohexane, mineral spirit, naphtha, etc., ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone), and esters (eg, ethyl acetate, n-butyl acetate, cellosolve acetate, isobutyl acetate, etc.) It can be appropriately selected and used depending on the purpose and use. These solvents may be used alone or as a mixture. Further, various additives used in the technical field such as a catalyst, a pigment, a leveling agent, an antioxidant, a flame retardant, a plasticizer, and a surfactant can be mixed and used according to the purpose and application.

(Non-yellowing polyurethane cured product) The method for forming the non-yellowing polyurethane cured product of the present invention or a composition containing the cured product is as follows. For example, immediately before the formation of a cured polyurethane, a composition is prepared by adding a polyisocyanate and an active hydrogen-containing compound, and further a solvent or an additive depending on the purpose and application, usually at room temperature to 150 ° C.
A cured product is formed in the range of ° C. to obtain the cured product or a composition containing the cured product. Or NC of polyisocyanate
An active hydrogen-containing compound in a so-called block isocyanate in which an O group is blocked by a blocking agent, and furthermore, a solvent, a catalyst, a pigment, a leveling agent, an antioxidant, a plasticizer, a surfactant and the like according to the purpose and application. The composition is prepared by blending various additives used in
A cured product can be formed in a temperature range of up to 180 ° C. to obtain the cured product or a composition containing the cured product.

When the non-yellowing polyurethane cured product of the present invention is used as a paint, metal, plastic, rubber,
Since it has excellent adhesion to objects to be coated such as leather and concrete, it can be used for a wide range of applications as a paint for vehicles, equipment, building materials, woodwork and the like.

[0038]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In these examples, all percentages are by weight.

(Example 1) (Production of polyisocyanate by reaction of NBDI with carbon dioxide gas) 200 g (0.97 mol) of NBDI was charged into a four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen introduction pipe, and a stirring blade. Then, at 20 ° C., 0.2 g of tri-n-butylphosphine was added while blowing carbon dioxide gas at a rate of 200 ml / min, and the reaction was carried out for 10.5 hours with stirring. The NCO content of the reaction solution was 40.7
Benzoyl chloride from 0.28% to 35.9%.
g, and the mixture was further stirred for 0.5 hour to deactivate the catalyst, and then the supply of carbon dioxide gas was stopped. A slightly yellow transparent liquid was obtained. An aliquot of the methyl carbamate compound obtained by removing a part of the reaction solution and reacting with methyl alcohol was determined by gel permeation chromatography (hereinafter, referred to as GPC analysis) as follows. n = 0 isomer 79.9% n = 1 isomer 18.1% n = 2 or more 2.0% From this GPC analysis, formation of a high polymer having n = 4 or more is hardly recognized. In addition, the said polyisocyanate composition showed fluidity at room temperature, and the polyisocyanate composition of low viscosity was able to be obtained. Further, for the polyisocyanate composition obtained by the above method, NMR spectrum,
The FD-MS spectrum was measured and analyzed. In the analysis, the spectrum of the NBDI monomer was referred to. From the FD-MS spectrum, n = 0, n = 1,
The mass numbers of n = 2 and n = 3 are 206, 456, and 70, respectively.
6 and 956 were detected as peaks. This is NBD
I corresponds to the molecular weight of the compound reacted alone with carbon dioxide. From the above analysis results, it was found that the polyisocyanate compound represented by the general formula (1) was obtained.

(Example 2) (Production of polyisocyanate having oxadiazinetrione ring obtained by reacting TCDI with carbon dioxide gas) TCDI 180 g in a four-necked flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring blade (0.73 mol), 7.2 g of a 10% tri-n-butylphosphine toluene solution was added at 5 ° C. while blowing carbon dioxide gas at a rate of 100 ml / min, and the mixture was reacted for 6.5 hours with stirring. Since the NCO content of the reaction solution decreased from 34.1% to 30.1%, dimethyl sulfate was added.
0.7 g was added, and the mixture was further stirred for 0.5 hour to deactivate the catalyst, and supply of carbon dioxide gas was stopped. A slightly viscous transparent viscous liquid was obtained. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 80.5% n = 1 isomer 18.3% n = 2 or more 1.2% From this GPC analysis, formation of a high polymer having n = 4 or more is hardly recognized.

(Example 3) (Production of polyisocyanate having oxadiazinetrione ring obtained by reacting NBDI with carbon dioxide) NBDI300 was placed in a four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen introduction pipe, and a stirring blade. g (1.45 mol) of the mixture and 20
At 10 ° C while blowing carbon dioxide gas at a rate of 300 ml / min.
20.0 g of a tri-n-butylphosphine toluene solution was added thereto, and the reaction was carried out for 6.9 hours while stirring. NCO of reaction solution
Since the content decreased from 40.7% to 26.1%, 1.9 g of benzoyl chloride was added, and the mixture was further stirred for 0.5 hour to deactivate the catalyst and stop supplying carbon dioxide. A slightly yellow transparent viscous liquid was obtained. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 42.1% n = 1 isomer 30.7% n = 2 or more 27.2% From this GPC analysis, formation of a high polymer having n = 4 or more is hardly recognized.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that 200 g (1.06 mol) of xylylene diisocyanate (hereinafter abbreviated as XDI) was used. NCO content is 4
It decreased from 4.7% to 24.2%. 0.4 g of dimethyl sulfate was used as a catalyst poison. GPC analysis revealed the following ratio of methyl carbamate compounds obtained by reacting a part of this solution with methyl alcohol. n = 0 isomer 20.2% n = 1 isomer 30.4% n = 2 or more 49.4% From this GPC analysis, n = 2 or more components show that n = 3 or 4 or more high polymer It was found that the production was more than n = 2.

(Comparative Example 2) A reaction was carried out in the same manner as in Example 3 except that 300 g (1.18 mol) of HDI was used. The NCO content decreased from 50.0% to 20.5%. As a catalyst poison, 1.9 g of benzoyl chloride was used. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 13.5% n = 1 isomer 20.6% n = 2 or more 65.9% From this GPC analysis, n = 2 or more components show n = 3 or 4 or more high polymer It was found that the production was more than n = 2.

(Example 4) (Production of polyisocyanate having oxadiazinetrione ring by reacting a mixture of HDI and NBDI with carbon dioxide) Thermometer, cooling pipe, nitrogen introduction pipe, stirring blade 4 140 g (0.832 mol) of HDI and NBDI
60 g (0.291 mol) of a mixture was charged, and 10% tri-n- was added at 20 ° C. while blowing carbon dioxide gas at a rate of 300 ml / min.
10.0 g of a butylphosphine toluene solution is added, and the mixture is reacted for 6.9 hours with stirring. The NCO content of the reaction solution is 44.4%
Then, 1.1 g of benzoyl chloride was added, and the mixture was further stirred for 0.5 hour to deactivate the catalyst, and the supply of carbon dioxide gas was stopped. A slightly viscous transparent viscous liquid was obtained. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 40.6% n = 1 isomer 32.1% n = 2 or more 27.3% From this GPC analysis, formation of a high polymer having n = 4 or more is hardly recognized. A methyl carbamate compound obtained by reacting a part of this solution with methyl alcohol was newly subjected to GPC, and each component was fractionated. Where n =
NMR spectrum, FD-M for one fraction
The S spectrum was measured and analyzed. Mass numbers 444, 482, and 520 were detected from the FD-MS spectrum. This is consistent with the molecular weights of NBDI and HDI reacted alone with carbon dioxide and NBDI and HDI reacted with carbon dioxide at a 1: 1 molar ratio, respectively.

(Example 5) (Production of polyisocyanate having oxadiazinetrione ring obtained by reacting a mixture of HDI and NBDI with carbon dioxide) Thermometer, cooling pipe, nitrogen introduction pipe, stirring blade 4 100 g (0.595 mol) of HDI and NBD
I mixture (100 g, 0.485 mol) was charged, and 10% triethanol solution was added at 20 ° C. while blowing carbon dioxide gas at a rate of 200 ml / min.
10.6 g of -butylphosphine toluene solution was added, and the mixture was reacted for 5 hours while stirring. The NCO content of the reaction solution is 4
Benzoyl chloride 1.3% from 5.4% to 25.7%
g, and further stirred for 0.5 hour to deactivate the catalyst.
The supply of carbon dioxide was stopped. A slightly viscous transparent viscous liquid was obtained. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 43.7% n = 1 isomer 33.2% n = 2 or more 23.1% From this GPC analysis, formation of a high polymer of n = 4 or more is hardly recognized.

Example 6 140 g (0.680 mol) of NBDI
The reaction was carried out in the same manner as in Example 5 except that 60 g (0.357 mol) of HDI was used. NCO content from 43.6% to 25.7%
Decreased to. Benzoyl chloride (1.2 g) was added as a catalyst poison, and the mixture was further stirred for 0.5 hour to deactivate the catalyst. A slightly viscous transparent viscous liquid was obtained. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 41.9% n = 1 isomer 33.1% n = 2 or more 25.0% From this GPC analysis, formation of a high polymer of n = 4 or more is hardly recognized.

Example 7 A reaction was carried out in the same manner as in Example 6 except that a mixture of 100 g (0.406 mol) of TCDI and 100 g (0.594 mol) of HDI was used. The NCO content is
It decreased from 42.1% to 28.7%. Benzoyl chloride (1.4 g) was used as a catalyst poison. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 43.0% n = 1 isomer 32.0% n = 2 or more 25.0% From this GPC analysis, formation of a high polymer of n = 4 or more is hardly recognized.

(Example 8) 60 g (0.244 mol) of TCDI,
The reaction was carried out in the same manner as in Example 7 except that 140 g (0.832 mol) of HDI was used. The NCO content decreased from 45.2% to 26.0%. 1.4 g of benzoyl chloride was used as a catalyst poison. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 42.0% n = 1 isomer 32.0% n = 2 or more 26.0% From this GPC analysis, formation of a high polymer having n = 4 or more is hardly recognized.

Example 9 20 g (0.097 mol) of NBDI
And TCDI 20g (0.080 mol) and HDI 160g (0.832
Mol), and the reaction was carried out in the same manner as in Example 8, except that the reaction time was changed to 4.5 hours. NCO content
It decreased from 47.1% to 26.9%. Benzoyl chloride (1.5 g) was used as a catalyst poison. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 43.9% n = 1 isomer 33.2% n = 2 or more 22.9% From this GPC analysis, formation of a high polymer of n = 4 or more is hardly recognized.

Example 10 NBDI 50 g (0.242 mol)
The reaction was carried out in the same manner as in Example 8 except that 50 g (0.203 mol) of TCDI and 100 g (0.594 mol) of HDI were used. N
The CO content decreased from 43.5% to 28.1%. 1.2 g of benzoyl chloride was used as a catalyst poison. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 42.0% n = 1 isomer 30.7% n = 2 or more 27.3% From this GPC analysis, formation of a high polymer having n = 4 or more is hardly recognized.

(Comparative Example 3) (Production of polyisocyanate by reaction of a mixture of HDI and XDI with carbon dioxide gas) 100 g (0.59 mol) of HDI in a four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen introducing pipe, and a stirring blade. And a mixture of 100 g (0.45 mol) of XDI
While blowing carbon dioxide gas at 200ml / min at 10 ℃, 10
2.1% tri-n-butylphosphine toluene solution was added,
The reaction is carried out for 6 hours with stirring. Since the NCO content of the reaction solution decreased from 43.9% to 27.1%, dimethyl sulfate 1.
0 g, and further stirred for 0.5 hour to deactivate the catalyst.
The supply of carbon dioxide was stopped. A slightly viscous transparent viscous liquid was obtained. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 20.0% n = 1 isomer 26.0% n = 2 or more 54.0% From this GPC analysis, n = 2 or more components have n = 3 or 4 or more high polymer. It was found that the production was more than n = 2.

(Example 11) (Production of polyisocyanate by reaction of NBDI with carbon dioxide gas) 200 g (0.97 mol) of NBDI was charged into a four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen introduction pipe, and a stirring blade. Then, at 75 ° C., 0.19 g of trioctylphosphine was added while carbon dioxide gas was blown at a rate of 400 ml / min, and the reaction was carried out for 11.5 hours with stirring. The NCO content of the reaction solution was 40.7
% To 36.5%, 0.14 g of ethyl p-toluenesulfonate was added, and the mixture was further stirred for 1.0 hour to deactivate the catalyst. Then, the supply of carbon dioxide gas was stopped. A slightly yellow transparent liquid was obtained. According to GPC analysis, the ratio by mass of the methyl carbamate compound obtained by reacting a part of this polyisocyanate composition with methyl alcohol was as follows. n = 0 isomer 82.0% n = 1 isomer 15.2% n = 2 or more 2.8% From this GPC analysis, formation of a high polymer of n = 4 or more is hardly recognized.

(Evaluation Examples 1 to 11) After adjusting the polyisocyanate compositions obtained in Examples 1 to 11 to a concentration of 50% with butyl acetate, this solution and an acrylic polyol resin solution Olester Q182 (Mitsui Chemicals, Inc.) ), Number average molecular weight 95
00, a solid content of 50% by weight, and a hydroxyl value of 45 mgKOH / g). Preparation of base enamel A base enamel of acrylic resin Olester Q182 was blended and prepared as follows. Acrylic resin Orester Q182 50 parts Pigment: Titanium oxide R930 (manufactured by Ishihara Sangyo Co., Ltd.) 50 parts The above mixture was added, and the pigment was kneaded with a three-roll mill to prepare a base enamel.

Coating Film Test After the polyisocyanate compositions obtained in Examples 1 to 11 were adjusted to a concentration of 50% with butyl acetate, this solution was mixed with the base enamel prepared with acrylic polyol resin Olester Q182 and isocyanate. Groups and hydroxyl groups are equivalent and the pigment content (PWC) is 40% by weight, and ethyl acetate / toluene / butyl acetate / xylene / cellosolve acetate is used as a thinner (weight ratio = 30/30/20/15).
/ 5) and add 15 seconds / 25 with Ford Cup 4
C. to obtain a non-yellowing type urethane paint resin of the present invention. This is an air spray gun (IWATAW-77 type,
Nozzle diameter 2mmφ) about dry film thickness on steel plate and glass plate
Paint to 25μ (micron), room temperature (20 ℃ / 60
% RH) and left for 7 days before testing. The performance and coating film properties are shown in Tables 1 and 2. For comparison, the same test was performed on the polyisocyanate solutions obtained in Comparative Examples 1 to 3. Table 2 shows the performance and coating film properties.
Shown in The coating film test was performed at 20 ° C./60% RH, and the evaluation method was in accordance with JIS k-5400. In addition, (1) to (6) shown in the table
The test method in section is as follows. (1) Adhesion, according to JIS D-0202. (2) Erichsen extrusion, in accordance with JIS Z-2247. (3) WOM yellowing degree, based on JIS k-7103. (4) Gloss (60 ° gloss), conforming to JIS k-5400. (5) Dupont impact (1 / 2in / 500g), JIS k-5400 compliant. (6) Secondary physical properties: After immersion in boiling water for 4 hours, physical properties are measured.

[0055]

[Table 1]

[0056]

[Table 2]

As is clear from Tables 1 and 2, the evaluation results shown in Examples 1 to 11 show that the polyisocyanate of the present invention is compared with the conventional polyisocyanate derived from xylylene diisocyanate or the like. As a result, it is found that the polymer has excellent reactivity (dry to the touch and complete curing), and also has good gloss and light resistance.

[0058]

The polyisocyanate composition of the present invention is
For example, the reactivity and gloss are much better than polyisocyanate derived from xylylene diisocyanate,
The resulting polyurethane does not substantially yellow or its yellowing can be significantly suppressed. It has good compatibility with solvents, active hydrogen components, etc., and is effective in applications where emphasis is placed on workability, appearance, and coating film performance. In particular, when used as a curing agent for a urethane paint, the coating film has good weather resistance and flexibility, and has excellent curability and drying properties, and thus is suitable.

Continued on front page F-term (reference) 4C056 AA02 AB02 AC10 AD01 AE04 FA01 FB05 FC04 4J034 BA05 CA02 CA03 CA04 CA05 CA24 CA32 CB03 CB04 CB05 CB07 CB08 CC08 CC09 CC12 CC13 CC22 DA01 DB04 DB05 DF01 GA02 GA03 GA33 HC36 GA06 HC33 QB11 RA07 4J038 DG032 DG272 DG291 KA03

Claims (13)

[Claims] 1. A compound of the general formula (1) [In the formula, one or both of R ₁ and R ₂ is a group represented by the general formula (2), and when one of them is a group represented by the general formula (2), the other has a carbon number of 2-12
Is an alkylene group. And a diisocyanate represented by the following general formula (2): (Where k is 0-2, j and m are 1-5, h is 0-2
A polyisocyanate having a skeleton represented by the following general formula (1), wherein the polyisocyanate in which n in the general formula (1) is 0 is from 30 to 90% by weight, 9.5 to 40% by weight of the polyisocyanate where n is 1 in the formula (1) and 0.5 to 30% by weight of the polyisocyanate where n is 2 to 4 in the general formula (1). Characteristic polyisocyanate composition. 2. A compound of the general formula (3) (Where k is 0 to 2, j and m are 1 to 5, h is 0 to 2)
Tertiary phosphine having an alkyl group in the presence of 0.001 to 10.0% by weight of the diisocyanate.
The method for producing a polyisocyanate composition according to claim 1, wherein carbon dioxide gas is reacted at a reaction temperature of -20 to 80 ° C. 3. A polycyclic aliphatic diisocyanate represented by the general formula (3), wherein k is an integer of 0 to 2, j and m are an integer of 1 to 5, and h is an integer of 0 to 2. And the general formula (4) (Wherein, R ₃ represents an alkylene group having 2 to 12 carbon atoms), and a tertiary phosphine having an alkyl group is added to a mixture with a linear aliphatic diisocyanate represented by the following formula: The method for producing a polyisocyanate composition according to claim 1, wherein carbon dioxide gas is reacted at a reaction temperature of -20 to 80 ° C in the presence of up to 10.0% by weight. 4. The method for producing a polyisocyanate composition according to claim 1, wherein the reaction temperature is 0 to 30 ° C. 5. The method for producing a polyisocyanate composition according to claim 1, wherein the reaction rate of the isocyanate group is maintained in the range of 10 to 60%. 6. The polycyclic aliphatic diisocyanate represented by the general formula (3) is 2,5- or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane or a mixture thereof. The method for producing a polyisocyanate according to any one of claims 3 to 5, wherein 7. The method for producing a polyisocyanate according to claim 4, wherein the linear aliphatic diisocyanate represented by the general formula (4) is hexamethylene diisocyanate. 8. The method for producing a polyisocyanate according to claim 2, wherein the alkyl group of the tertiary phosphine having an alkyl group has 2 to 12 carbon atoms. 9. A curing agent for polyurethane, comprising the polyisocyanate composition according to claim 1. 10. A curable composition for polyurethane, comprising the curing agent for polyurethane according to claim 9 and a main agent containing a compound having one or more active hydrogens. 11. The compounding ratio of the curing agent for polyurethane according to claim 9 and a compound having one or more active hydrogens is within an equivalent ratio (H / NCO group) of 0.8 to 1.2. The curable composition for polyurethane according to claim 10, which is present. 12. A non-yellowing type cured polyurethane obtained from the curable composition for polyurethane according to claim 10. 13. A paint containing the non-yellowing polyurethane cured product according to claim 12.