JP2003277341A - New triisocyanate and polyurethane coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a triisocyanate which is odorless, low toxic, and low viscous, and has excellent workability and storage stability, and to provide a polyurethane coating and a polyurethane resin coating film which have excellent acid resistance, hot water resistance, solvent resistance, flexibility, whether resistance, yellowing resistance, adhesiveness and stain resistance, and high gloss. <P>SOLUTION: The triisocyanate represented by formula (1) äR<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each independently a specific alkylene or cycloalkylene; (p), (r) and (s) are each an integer of 0 to 9; (q) is an integer of 1 to 9; 1≤(p)+(q)+(r)+(s)≤9, and (r)<(s) or [(r)=(s) and (p)≤(q)]}, and the polyurethane coating using the same are provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to odorless, low toxicity, low viscosity, excellent workability, and excellent storage stability.
It relates to novel triisocyanates. Further, using this novel triisocyanate, a polyurethane coating and polyurethane resin excellent in gloss, acid resistance, warm water resistance, solvent resistance, flexibility, weather resistance, yellowing resistance, adhesion and stain resistance are obtained. Regarding coating film.

[0002]

BACKGROUND OF THE INVENTION Conventional polymethylene diisocyanates and isophorone diisocyanate derivatives, which are generally used, are used because they are oligomerized because the raw material diisocyanate has a high vapor pressure. However, it has the drawback that its viscosity becomes extremely high and its use in high solids paints is limited. Therefore, lysine ester triisocyanate has been proposed as an odorless, low-toxicity, low-viscosity triisocyanate (Japanese Patent Publication No. 60-2).
6775).

On the other hand, in order to obtain a highly active polyisocyanate compound having excellent storage stability, a method has been proposed in which an organometallic urethane-forming catalyst and an acyl chloride compound are added to the polyisocyanate compound (JP-A-5-255).
469 publication). However, a triisocyanate that is odorless, low in toxicity, low in viscosity and excellent in storage stability without adding a compound such as a catalyst has not been proposed yet. In addition, it is said that when a lysine ester triisocyanate is used in a polyurethane coating composed of a polyol and a polyisocyanate, a polyurethane coating excellent in coating appearance such as gloss, acid resistance and water resistance can be obtained (special characteristics JP-A-57-20343).

On the other hand, Japanese Unexamined Patent Publication No. 5-32759 discloses that
Containing a polyisocyanate compound obtained from hexamethylene diisocyanate and a polyol, weather resistance,
Polyurethane paints having excellent flexibility have been proposed.
However, a polyurethane coating having high gloss, acid resistance, warm water resistance, solvent resistance, flexibility, weather resistance, yellowing resistance, adhesion, and stain resistance has not been proposed yet.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a triisocyanate that is odorless, has low toxicity, low viscosity, excellent workability, and excellent storage stability. It is also an object of the present invention to provide a polyurethane paint and a polyurethane resin coating film which are excellent in high gloss, acid resistance, warm water resistance, solvent resistance, flexibility, weather resistance, yellowing resistance, adhesion and stain resistance. It is what

[0006]

As a result of intensive studies to solve the above problems, the present inventors have found that triisocyanate having a specific structure can be suitable for the purpose. The present invention has been completed based on. That is, the first aspect of the present invention is a novel triisocyanate represented by the formula (1).

[0007]

[Chemical 2]

[R ¹ , R ² and R ³ are each independently an alkylene group having 2 to 20 carbon atoms, or an unsubstituted or alkyl group having 1 to 18 carbon atoms or 1 to 8 carbon atoms.
Represents a cycloalkylene group having 5 to 20 carbon atoms, which is substituted with an alkoxy group. Further, the alkylene group and the cycloalkylene group may contain a hetero atom, or may contain a substituent other than an alkyl group such as a phenyl group, an aryl group, a nitro group, a halogen group and an amino group. The alkyl part of the above-mentioned alkyl group, alkylene group, and alkoxy group may be linear or branched. p, r, s are integers of 0-9, q is an integer of 1-9,
1 ≦ p + q + r + s ≦ 9 and {r <s or (r = s and p ≦ q)}]

A second aspect of the present invention is the triisocyanate of the first aspect of the present invention, in which p + q + r + s = 3. A third aspect of the present invention is the triisocyanate of the first aspect of the present invention, in which p = 1, q = 2, and r = s = 0. The fourth aspect of the present invention is
R ¹ , R ² , and R ³ are all —CH ₂ CH ₂ —, and the triisocyanate according to any one of the first to third inventions of the present invention. A fifth aspect of the present invention is a polyurethane coating comprising a polyol and a polyisocyanate, wherein the triisocyanate according to any one of the first to fourth aspects of the present invention is used as at least one of the polyisocyanates. A sixth aspect of the present invention is a coating film made of a polyurethane resin obtained by reacting a polyol and a polyisocyanate,
The first aspect of the present invention as at least one of polyisocyanates
It is a polyurethane resin coating film which uses the triisocyanate in any one of -4.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The novel triisocyanate of the present invention has the formula (1)
Indicated by.

[0011]

[Chemical 3]

Since three isocyanate groups are contained in the molecule, three-dimensional cross-linking is possible, and the cross-linking density can be increased as compared with the bifunctional isocyanate. Therefore, when the triisocyanate represented by the formula (1) is used as a crosslinking agent for the polyol, the hot water resistance of the resulting polyurethane resin coating film can be dramatically improved. In the formula (1), p, r, and s are integers of 0 to 9, q is an integer of 1 to 9, and 1 ≦ p + q + r + s ≦ 9 and {r <s or (r =
s and p ≦ q)}. That is, although the triisocyanate represented by the formula (1) can be regarded as a triester derivative of a linear aliphatic tricarboxylic acid, it is said that all three substituents bonded to the aliphatic linear chain are bonded to adjacent carbon atoms. Therefore, the steric hindrance is low and the difference in reactivity between the three isocyanate groups is small, so that the crosslinking reaction easily proceeds and a sufficient crosslinking effect is obtained.

Further, as compared with the aromatic polyisocyanate obtained by oligomerizing aromatic diisocyanate,
Due to the high degree of freedom of the molecule in terms of structure, steric hindrance is low and a sufficient cross-linking effect is obtained, and the aliphatic straight chain and the three isocyanate groups are respectively bonded through an ester bond, so Great flexibility,
There is an advantage that the flexibility of the polyurethane resin coating film obtained by the reaction with the polyol is also extremely high.

When the value of p + q + r + s is 9 or less, the acid resistance of the polyurethane resin coating film obtained by the reaction with the polyol is expressed, and the value is preferably 1 to 5, and more preferably 3. Also, from the viewpoint of the flexibility of the polyurethane resin coating film obtained by the reaction with the polyol,
More preferably, p = 1, q = 2 and r = s = 0. R ¹ , R ² and R ³ each independently have 2 to 20 carbon atoms.
Or an unsubstituted alkylene group or a cycloalkylene group having 5 to 20 carbon atoms, which is unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. The alkyl part of the above-mentioned alkyl group, alkylene group, and alkoxy group may be linear or branched.

As the linear alkylene group, ethylene,
Trimethylene, tetramethylene, pentamethylene, hexamethylene, icosamethylene, etc., branched alkylene groups such as propylene, 1,1-dimethylethylene, ethylethylene, 2,2-dimethyltrimethylene, etc., and cycloalkylene groups such as 1 , 3-cyclopentylene,
1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene and the like can be mentioned.

Further, the alkylene group and cycloalkyl thereof
Those containing hetero atoms in the len group or those containing substituents
May be In the present application, a hetero atom is a carbon atom.
An atom that can form a molecule by combining with
C, nitrogen, phosphorus, arsenic, etc. can be mentioned. Inside
However, oxygen, sulfur and nitrogen are preferable. An example with oxygen and
Include ethers, esters, lactones, sulfur
Examples include thioether and nitrogen-containing examples include
Examples include amide, urethane, urea, imine, etc.
It Further, as the substituent, a phenyl group, an aryl
Groups, nitro groups, halogen groups, amino groups, etc.
it can. Specific examples of these include -CH ₂CH₂OCH
₂CH₂-, -CH₂CH₂SCH₂CH₂-, -CH₂CH
ClCH₂-And the like. Furthermore, two or more of the above groups
The above may be mixed and used. Among these, synthetic
Of poly (ethylene glycol) obtained by reaction with polyol
From the viewpoint of flexibility of urethane resin coating film, straight-chain alkylate
Group is preferred, and ethylene group is more preferred.

The triisocyanate of the present invention includes
1,2,4-Butanetricarboxylic acid tris (2'-isocyanatoethyl) ester, 1,3,5-hexanetricarboxylic acid tris (2'-isocyanatoethyl) ester, 1,3,6-hexanetricarboxylic acid tris (2 '
-Isocyanatoethyl) ester, 1,4,8-octanetricarboxylic acid tris (3'-isocyanatopropyl) ester, 1,6,9-decanetricarboxylic acid tris (2'-isocyanatoethyl) ester, 2,5 , 1
Examples thereof include 0-dodecanetricarboxylic acid tris (2′-isocyanatobutyl) ester, but due to the above reason, 1,2,4-butanetricarboxylic acid tris (2′-
Isocyanatoethyl) ester, 1,3,5-hexanetricarboxylic acid tris (2'-isocyanatoethyl) ester, 1,3,6-hexanetricarboxylic acid tris (2'-isocyanatoethyl) ester, 1,4. 8-
Octanetricarboxylic acid tris (3'-isocyanatopropyl) ester and the like are preferable, and 1,3,6-hexanetricarboxylic acid tris (2'-isocyanatoethyl) ester is particularly preferable.

The triisocyanate of the present invention can be obtained by a known method. The production method is not limited, and, for example, using a linear aliphatic tricarboxylic acid as a raw material, (a)
Triesterification with amino alcohols, followed by (b)
Obtained by phosgenation. Regarding the esterification step (a), for example, JP-B-45-14771, JP-B-46-35246, and JP-A-5-65
No. 253 and the like, and the phosgenation step (b) is described in, for example, JP-A-57-77656, JP-A-3-204851, and JP-A-6-234723. .

The polyurethane paint of the present invention is obtained from at least one polyisocyanate containing the triisocyanate represented by the formula (1) as an essential component and a polyol. As the polyisocyanate, one triisocyanate represented by the formula (1) is necessarily contained, and further, another triisocyanate represented by the formula (1) and other polyisocyanate not represented by the formula (1) may be contained.

As the other polyisocyanate, one or more of aliphatic, alicyclic, aromatic and heterocyclic polyisocyanates and their oligomers, carbodiimide modified products, polyol modified products, allophanate modified products and the like can be used. Is used. Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate and 1,4
-Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate, etc. Examples of the alicyclic polyisocyanate include cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4. -Diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, etc., are aromatic polyisocyanates such as m- Phenylene diisocyanate, p
-Phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m
-Xylylene diisocyanate, p-xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate,
m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, methine tris (4-phenylisocyanate), tris (4-isocyanatophenyl) methane, thiophosphoric acid tris (4-isocyanatophenyl ester), 3-isopropenyl −
Examples include α ′, α′-dimethylbenzyl isocyanate and mixtures of these oligomers, or modified products of these polyisocyanate compounds such as carbodiimide, polyol and allophanate.

The oligomer of polyisocyanate can be obtained, for example, by forming a buret bond, a urea bond, an isocyanurate bond, a urethane bond, an allophanate bond, a uretdione bond or the like into a diisocyanate to be oligomerized. The above-mentioned other polyisocyanates are used in the range of 0 to 99% (mass ratio), preferably 0 to 90% (mass ratio) of the total polyisocyanates in view of the ease of exhibiting the effect expected in the present invention. Used in the range. From the viewpoint of the balance of hardness and flexibility of the polyurethane resin coating film obtained by the reaction with the polyol,
It is preferable to use 5 to 20% of a polyisocyanate such as an oligomer of an aliphatic polyisocyanate.

The polyol used in the present invention includes a compound or polymer containing two or more hydroxyl groups per molecule. For example, diols, triols, tetraols, pentitols, hexitols, and saturated or unsaturated polyesters containing 2 or more hydroxyl groups per molecule (hereinafter referred to as polyester polyols), polyethers (hereinafter referred to as polyether polyols), acrylics. Polymer (hereinafter referred to as polyacrylic polyol), polycaprolactone, saturated or unsaturated oil-modified or fatty acid-modified alkyd resin,
Polymer polyols such as aminoalkyd resins, polycarbonates, epoxy resins, polyurethanes, cellulose acetate butyrate resins, and fluorine-containing resins.

Specifically, as the diol, ethylene glycol, propylene glycol, β, β'-dihydroxydiethyl ether (diethylene glycol), dipropylene glycol, 1,4-butylene glycol,
1,3-butylene glycol, polyethylene glycol, polypropylene glycol, polypropylene-polyethylene glycol, polybutylene glycol, etc., as triols, glycerin, trimethylolpropane,
Examples of tetraol such as 1,2,6-hexanetriol include pentaerythritol and 2-methylglucoside, and hexitol includes sorbitol.

The polyester polyol is adipic acid,
It can be obtained by a condensation reaction of a polybasic acid such as dimer acid, phthalic anhydride or isophthalic acid with a diol or triol such as ethylene glycol, diethylene glycol, propylene glycol, trimethylolpropane or glycerin. Further, the polyether polyol is obtained by adding propylene oxide, ethylene oxide or the like to polyhydric alcohol such as glycerin or propylene glycol, or by reacting ethylene oxide or propylene oxide with a polyfunctional compound such as ethylenediamine or ethanolamine. And those rich in hydroxyl groups are included.

Further, the polyacrylic polyol can be obtained by copolymerizing a polymerizable acrylic monomer having one or more hydroxyl groups in one molecule with another monomer copolymerizable therewith. Examples of the polymerizable acrylic monomer having one or more hydroxyl groups in one molecule include (meth)
2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) 2-Hydroxypentyl acrylate, (meth) acrylic acid monoester of glycerin, (meth) acrylic acid monoester of trimethylolpropane, and 2-hydroxy-3-chloropropyl (meth) acrylic acid, or the above active hydrogen. Examples thereof include ring-opening polymerization adducts of (meth) acrylic acid esters having ## STR6 ## and lactones such as ε-caprolacturone and γ-valerolactone.

Containing the above-mentioned hydroxyl group (meth)
Examples of the other monomer copolymerizable with the acrylic ester include (meth) acrylic acid, or methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (Meta)
Decyl acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid esters such as lauryl (meth) acrylate, styrene, or styrene derivatives such as α-methylstyrene and β-chlorostyrene, vinyl acetate, Examples thereof include vinyl esters such as vinyl propionate and vinyl isopropionate, and nitriles such as (meth) acrylonitrile. Further, a polymerizable adduct obtained by an addition reaction of acrylic acid or methacrylic acid with a monoepoxy compound or an epoxy resin can also be used.

The polymer polyol obtained by copolymerizing the above monomers can be produced by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization. You may use these polyols in mixture of 2 or more types. Generally, it is preferable to use polyester polyol or polyacrylic polyol. The hydroxyl value of the polyol is preferably 1 to 1000 mgKOH / g,
More preferably, it is 10 to 500 mg KOH / g. When the hydroxyl value is 1 mgKOH / g or more, the polyurethane resin coating becomes tough, which is preferable, and the hydroxyl value is 1000 mgKOH / g.
When it is at most g, the surface smoothness and flexibility of the polyurethane resin coating film will be improved, which is preferable.

The number average molecular weight of the polyol is 300 to 2
About 0000 is preferable, and about 500 to 12000 is more preferable. When it is 300 or more, the cured coating film has high mechanical properties and is preferable. Further, when it is 20,000 or less, the viscosity of the polyol is low, and the diluent solvent required for adjusting the viscosity of the coating material suitable for coating is not necessary, or the amount thereof is small, which is preferable. The number average molecular weight of the polyol is 50 in order to achieve a coating composition having a low VOC (volatile organic compound) concentration which will be described later.
About 0 to 5000 is preferably used.

NCO / OH of the polyurethane coating of the present invention
The (isocyanate group / hydroxyl group) ratio (molar ratio) was 0.
1 to 5.0 is preferable, and 0.3 to 3.0 is more preferable. If it is less than 0.1, the polyurethane resin coating film may become brittle, which is not preferable, and if it exceeds 5.0, a large amount of polyisocyanate that does not participate in crosslinking is present, which adversely affects the mechanical properties of the polyurethane resin coating film. Is not preferable. The polyurethane coating material of the present invention can be applied to any method that is usually used in a two-component type or a one-component type. Examples of the types of paint are as follows.

(1) The urethane bond is formed by the addition reaction between the two-pack type polyol-curable isocyanate group and the hydroxyl group of the polyol to form a coating film. It is composed of a kneading liquid (Liquid A) of a polyol and a pigment added if necessary, and a polyisocyanate mixture (Liquid B) diluted with a solvent if necessary. At the time of use, the liquids A and B are mixed, and the viscosity is adjusted with a thinner if necessary. A two-liquid discharge gun can also be used to mix the two liquids.

The solvent and thinner of the liquid B used may be the same or different if necessary, but it is necessary that they are compatible with each other. As the polyol component, a polyester polyol composed of a polybasic acid and a hydroxyl compound, a polyether polyol composed of a diol or triol-type propylene oxide polymer, a polyacrylic polyol composed of a copolymer of an acrylic monomer having a hydroxyl group are excellent. There is. This mold has excellent adhesion to coated objects such as metals, non-ferrous metals, plastics, rubbers, leathers, and concrete, and can be used for building materials, automobiles, machinery, equipment, aircraft, railway vehicles, ships, woodworking products, etc. Widely used.

(2) The isocyanate group of the one-pack type heat-curable isocyanate compound is blocked with a blocking agent, and stable heating at room temperature causes the blocking agent to dissociate to regenerate the isocyanate group. It forms a coating film.

As the blocking agent, phenol, m-nitrophenol, p-chlorophenol, catechol,
Dialkyl malonate, acetylacetone, alkyl acetoacetate, cresol, ε-caprolactam, methyl ethyl ketoxime, cyclohexanone oxime, butyl mercaptan, methanol, ethanol, ethylene chlorohydrin and the like can be used. As the polyol, mainly polyester polyol and acrylic polyol are excellent. This method is suitable for applications requiring long-term storage stability at room temperature, such as automobile line painting.

(3) Addition of catalysts such as amines and metal salts of naphthenic acid to an adduct of polyisocyanate (a free isocyanate group) with a two-component catalyst-curing castor oil or castor oil modified with a polyol, and the action of moisture. To cure. (4) A one-component moisture-curable coating composition comprising various polyols and a prepolymer obtained from polyisocyanate. Moisture in the air reacts with the terminal isocyanate groups to crosslink. (5) It is made by reacting a fatty acid partial ester of a one-pack type oil-modified polyol with a polyisocyanate. Cured by oxygen. (6) A coating film is formed only by volatilization of the urethane lacquer solvent. A thermoplastic urethane obtained by reacting a polyol, a diisocyanate, and a diamine is dissolved in a solvent such as an ester or a ketone.

The polyurethane paint of the present invention has the above (1)
Applicable to any of (6) to (6). A solvent and thinner may be used for the polyurethane paint, if necessary. Solvents that can be used include benzene, toluene, xylene,
Hydrocarbon solvents such as aromatic naphtha, ethyl acetate, butyl acetate, cellosolve, hexyl acetate, amyl acetate, ethyl propionate, ester solvents such as butyl propionate, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl Ketone,
Examples thereof include ketone solvents such as cyclohexanone and glycol ester solvents such as ethylene glycol monoethyl ether acetate and diethylene glycol monoethyl ether acetate. Moreover, you may use these 2 or more types in mixture. In particular, when a hydrocarbon-based solvent is used as a solvent for the polyol component or the isocyanate compound and a heterogeneous or opaque solution is obtained, it is preferable to mix it with another solvent to form a uniform solution.

After the polyurethane paint is applied, a cross-linking reaction (other than urethane lacquer) is allowed to proceed under conditions suitable for each paint, and a solvent or thinner is volatilized to form a polyurethane resin coating film. In the urethane coating material of the present invention, generally used antioxidants, pigments, plasticizers, surface active agents, or a small amount of additives or auxiliary agents added during coating or coating within the range of its customary dose. Can be used. A catalyst can also be used to accelerate the drying and curing. For example, tertiary amines such as dimethylethanolamine and triethylenediamine, and organic tin salts such as stannas octoate and dibutyltin dilaurate can be used.

The resin content concentration, which is the total mass ratio of the polyol and the polyisocyanate in the urethane coating composition of the present invention, can be 60% by mass or more, and in many cases, 65% by mass or more can be achieved. The composition prepared in this way can be used as an adhesive, etc., but in particular, by paint such as roll coating, curtain flow coating, spray coating, electrostatic coating, etc., metal such as steel plate, surface treated steel plate, plastic, and cement. It can be applied to inorganic materials such as calcium silicate and gypsum. Among these, especially as a top coat and an intermediate coat of plastics, pre-coated metals including rust-proof steel plates, and materials that have been subjected to treatment such as cationic electrodeposition or anion electrodeposition, and also for automobile coating, etc., cosmetics, weather resistance, and acid resistance. It is useful for imparting properties, rust prevention, chipping resistance and the like.

The polyurethane paint of the present invention has a low VO.
In addition to being able to achieve a C concentration, the formed polyurethane resin coating film has a urethane bond, has good chemical resistance, and has excellent adhesion to an organic coating film and excellent coating film appearance. It is useful in automotive coatings as a non-aqueous basecoat layer containing a pigment, and preferably as a top clearcoat applied over the aqueous basecoat layer. Further, in the above-mentioned automobile coating, it is possible to apply to a so-called 2 coat / 1 bake system in which the base coat and the top clear coat are simultaneously cured.

The present invention will be described below based on Examples, Comparative Examples and Production Examples. First, examples and comparative examples of triisocyanate will be shown. Evaluation of triisocyanate was performed by the following method. (1) Viscosity: B-type viscometer (manufactured by Tokimec Co., Ltd.,
It was measured at 6 rpm using a model BM). (2) Storage stability: Expressed by the curtaining time (hr) when exposed to the air.

[0040]

Example 1 1,3,6-Hexanetricarboxylic acid tris (2'-isocyanatoethyl) ester Stirrer, thermometer, gas inlet tube, dropping funnel, and Liebig condenser via a tee. 183.3 g (3.0 mol) of ethanolamine was added to a 5-neck round bottom flask. Hydrogen chloride gas is passed through the gas inlet tube to convert all of the ethanolamine to its hydrochloride salt, then
3,6-Hexanetricarboxylic acid 109.1 g (0.5
Mol) was added.

Hydrogen chloride gas was passed at a rate of 300 ml / min (converted to normal temperature and atmospheric pressure), the reaction mixture was heated to 120 ° C., and the pressure was gradually reduced to 20.0 kPa (absolute) using a water pump. The distilled water was condensed in a Liebig condenser. After reacting for 10 hours, the supply of hydrogen chloride was stopped, the pressure was returned to normal pressure using nitrogen, and then the mixture was cooled to 60 ° C. 1080 g of methanol and 720 g of o-dichlorobenzene
After the mixed solution of (1) was added and dissolved, a small amount of seed crystals were added for crystallization. Crystals are separated by filtration, and the same composition of methanol /
The crystals were washed with a mixture of o-dichlorobenzene and separated by filtration.

The wet crystals were 665 using a vacuum dryer.
It dried at Pa and 100 degreeC for 8 hours. Pale yellowish white solid 16
9.1 g was obtained. By analysis using liquid chromatography, the content of the target 1,3,6-hexanetricarboxylic acid tris (2′-aminoethyl) ester trihydrochloride was 98.6%. The yield including crystallization was 73%. (Elemental _{analysis) C 15 H 29 N 3 O} 6 · 3HCl Calculated for: C39.44%, H7.06%, N9.2
0%, measured value: C39.72%, H7.84%, N1
3.03%.

Subsequently, 780 g of xylene and 1,3,6-hexanetricarboxylic acid tris (2'-amino) described above were placed in a reaction flask having an internal volume of 1 L equipped with a stirrer, a thermometer, a phosgene blowing tube, and a reflux condenser. Ethyl) ester / trihydrochloride 139.0 g (0.30 mol conversion) and cetyltrimethylammonium chloride 4.73 g were added,
Heat to 133 ° C with stirring and raise the phosgene to 1
It was blown in at a rate of 9.8 g / hr and the reaction was continued for 15 hours while maintaining 133 to 138 ° C. After completion of the reaction, nitrogen gas was blown to purge unreacted phosgene and hydrochloric acid, insoluble substances were filtered off, and the solvent was distilled off from the filtrate under reduced pressure.
Oily 98% pure 1,3,6-hexanetricarboxylic acid tris (2'-isocyanatoethyl) ester 12
1.0 g (purity conversion yield 92.9%) was obtained. The evaluation results of NCO content 29.5% (calculated value 29.6%) are shown in Table 1.

[0044]

Example 2 1,2,4-Butanetricarboxylic acid tris (2'-isocyanatoethyl) ester 1,3,6-hexane Instead of tricarboxylic acid, 1,
Using 1,5.1 g (0.5 mol) of 2,4-butanetricarboxylic acid in the same manner as in Example 1, 1,2,4-
151.2 g of butanetricarboxylic acid tris (2'-aminoethyl) ester trihydrochloride was obtained. The content was 97.8% by analysis using liquid chromatography. The yield including crystallization was 69%. (Elemental _{analysis) C 13 H 25 N 3 O} 6 · 3HCl Calculated for: C3
6.42%, H 6.58%, N 9.80%, measured value: C
36.72%, H6.44%, N9.93%.

Subsequently, in place of 1,3,6-hexanetricarboxylic acid tris (2'-aminoethyl) ester trihydrochloride, the above 1,2,4-butanetricarboxylic acid tris (2'-aminoethyl) ester is used. -Trihydrochloride 131.
Using 5 g (0.30 mol conversion), in the same manner as in Example 1, 117.9 g of 1,2,4-butanetricarboxylic acid tris (2′-isocyanatoethyl) ester oil having a purity of 97% ( The yield in terms of purity was 92.4%). N
Table 1 shows the evaluation results of CO content 31.5% (calculated value 31.7%).

[0046]

Example 3 1,4,8-Octanetricarboxylic acid tris (3'-isocyanatopropyl) ester 225.3 g (3.0 mol) of 3-amino-1-propanol was replaced with 1,3 instead of ethanolamine. Using 12,3.1 g (0.5 mol) of 1,4,8-octanetricarboxylic acid instead of 6,6-hexanetricarboxylic acid,
In the same manner as in Example 1, 165.0 g of 1,4,8-octanetricarboxylic acid tris (3′-aminopropyl) ester · trihydrochloride was obtained. According to analysis using liquid chromatography, the content was 98.3%. The yield including crystallization was 71%. (Elemental analysis value) C ₂₀ H ₃₉
Calculated value for N ₃ O ₆ .3HCl: C 45.59%, H
8.03%, N 7.98%, actual value: C45.71%,
H7.92%, N8.05%.

Then, in place of 1,3,6-hexanetricarboxylic acid tris (2'-aminoethyl) ester trihydrochloride, the above 1,4,8-octanetricarboxylic acid tris (3'-aminopropyl) ester is used.・ Trihydrochloride 13
Using 9.4 g (0.30 mol conversion), oily, 96% pure 1,4,8-octanetricarboxylic acid tris (3′-isocyanatopropyl) ester 148. 7 g (purity conversion yield 92.5%)
Got Table 1 shows the evaluation results of NCO content 25.1% (calculated value 25.4%).

[0048]

[Comparative Example 1] 2,6,2'-triisocyanatoethylhexanoate (lysine ester triisocyanate) With a stirrer, a thermometer, a gas introduction tube, a dropping funnel, and a Liebig condenser via a C-shaped tube 61.1 g (1.0 mol) of ethanolamine was added to the five-necked round-bottomed flask. Hydrogen chloride gas is passed through the gas inlet tube to convert all of the ethanolamine to its hydrochloride salt, and then lysine 1
The hydrochloride salt 91.3 g (0.5 mol) was added.

Hydrogen chloride gas was passed through a gas inlet tube at a temperature of 80 to 120 ° C. to convert it into lysine trihydrochloride.
Further, hydrogen chloride gas was passed at a rate of 300 ml / min (converted to normal temperature and atmospheric pressure), the reaction mixture was heated to 120 ° C., and the pressure was gradually reduced to 20.0 kPa (absolute) using a water-jet pump. The distilled water was condensed in a Liebig condenser. After reacting for 10 hours, the supply of hydrogen chloride was stopped, the pressure was returned to normal pressure using nitrogen, and then the mixture was cooled to 60 ° C. To this, a mixed solution of 360 g of methanol and 240 g of o-dichlorobenzene was added and dissolved, and then a small amount of seed crystal was added for crystallization. The crystals are filtered off and methanol / o of the same composition as at the time of crystallization
The crystals were washed with a dichlorobenzene mixture and filtered off.

The wet crystals were 665 using a vacuum dryer.
It dried at Pa and 100 degreeC for 8 hours. Pale yellowish white solid 9
8.4 g was obtained. Analysis using liquid chromatography
The target 2,6,2'-triaminoethylhexa
The content of Noate trihydrochloride was 97.1%. Akira
The yield including the analysis was 64%. (Elemental analysis value) C₈
H ₁₉N₃O₂Calculated value for 3HCl: C32.18
%, H7.43%, N14.07%, measured value: C32.
38%, H7.43%, N14.22%.

Then, 780 g of xylene and the above 2,6,2'-triaminoethylhexanoate-trihydrochloric acid were placed in a reaction flask having an internal volume of 1 L equipped with a stirrer, a thermometer, a phosgene blowing tube, and a reflux condenser. 92.3 g of salt (0.3
(Converted to 0 mol), 4.73 g of cetyltrimethylammonium chloride, and heated to 133 ° C. with stirring, and phosgene was blown at a rate of 19.8 g / hr,
The reaction was continued for 15 hours while maintaining 133 to 138 ° C.
After completion of the reaction, nitrogen gas was blown to purge unreacted phosgene and hydrochloric acid, insoluble materials were filtered off, and the solvent was distilled off from the filtrate under reduced pressure to obtain an oily 2,8% pure 2,6,2. '
-Triisocyanatoethylhexanoate 85.9g
(Purity conversion yield 90.9%) was obtained. NCO content 47.
Table 1 shows the evaluation results of 1% (calculated value 47.2%).

[0052]

[Comparative Example 2] 1,2,3-propanetricarboxylic acid tri
Sus (2'-isocyanatoethyl) ester 1,3,6-hexanetricarboxylic acid instead of 1,
2,3-Propanetricarboxylic acid 88.1 g (0.5 m
In the same manner as in Example 1, using 1, 2, 3,
Tris (2'-aminoethyl) propane tricarboxylate
152.3 g of ester trihydrochloride was obtained. Liquid chromatography
The content was 98.0 according to the analysis by means of chromatography.
It was. The yield including crystallization was 72%. (Elemental analysis
Value) C₁₂H _{twenty three}N₃O₆-Calculated value for 3HCl: C3
4.75%, H 6.32%, N 10.13%, found:
C 34.83%, H 6.30%, N 10.22%.

Then, in place of 1,3,6-hexanetricarboxylic acid tris (2'-aminoethyl) ester trihydrochloride, the above 1,2,3-propanetricarboxylic acid tris (2'-aminoethyl) ester is used.・ Trihydrochloride 12
Using 7.0 g (0.30 mol conversion), tris (2'-isocyanatoethyl) 1,2,3-propanetricarboxylate having an oily purity of 96% was prepared in the same manner as in Example 1.
114.2 g of ester (purity conversion yield 91.9%) was obtained. Table 1 shows the evaluation results of NCO content 32.8% (calculated value 32.9%).

[0054]

Comparative Example 3 1,3,12-Tridecanetricarboxylic acid tris (2'-isocyanatoethyl) ester 1,3,6-hexane Tricarboxylic acid was replaced by 1,3,6-hexanetricarboxylic acid.
3,8.2-Tridecanetricarboxylic acid 158.2 g
(0.5 mol) in the same manner as in Example 1,
1,3,12-Tridecanetricarboxylic acid tris (2 '
195.6 g of -aminoethyl) ester trihydrochloride were obtained. The content was 97.9% by analysis using liquid chromatography. The yield including crystallization was 69%. (Elemental analysis value) Calculated value for C ₂₂ H ₄₃ N ₃ O ₆ .3HCl: C 47.61%, H 8.35%, N 7.5
7%, measured value: C 47.80%, H 8.30%, N 7.
82%.

Then, in place of the 1,3,6-hexanetricarboxylic acid tris (2'-aminoethyl) ester trihydrochloride, the above 1,3,12-tridecanetricarboxylic acid tris (2'-aminoethyl) salt is used. Ester / Trihydrochloride 1
Example 1 using 70.1 g (0.30 mol conversion)
In the same manner as described above, 160.9 g of oily 1,3,12-tridecanetricarboxylic acid tris (2'-isocyanatoethyl) ester having a purity of 94% (purity conversion yield 92.8)
%) Was obtained. NCO content 24.1% (calculated value 24.1
%) Evaluation results are shown in Table 1.

[0056]

[Table 1]

The polyisocyanates of Examples 1 to 3 are odorless, have low viscosity, and have excellent storage stability.
Next, examples and comparative examples of polyurethane paint and polyurethane resin coating film will be shown. The polyurethane resin coating film (dry film thickness 40 to 50 μm) was used in Examples 4 to 8 and Comparative Examples 4 to 7.
The polyurethane paint obtained in 1. was applied to a steel plate degreased with trichloroethylene, and left standing in an environment of 20 ° C. and 65% for 1 week. However, the coating films for evaluation of specular glossiness, weather resistance, and yellowing resistance of Examples 4 to 7 and Comparative Examples 4 to 6 were degreased in advance, and white enamel paint was applied to the dried steel plate, It was made to stand for 1 week in an environment of 20 ° C. and 65%. Evaluation of these paints and coating films was performed by the following methods.

(1) Coating solid content: The nonvolatile content (mass%) at 105 ° C. for 3 hours was measured. (2) Pencil hardness: The pencil hardness was measured according to the JISK5400 pencil scratch value tester method. (3) Specular gloss: Using a gloss meter GM-268 (manufactured by Minolta Co., Ltd.), the 60% -60 ° specular reflectance (%) was measured. (4) Acid resistance: It was immersed in 40 vol% sulfuric acid at 55 ° C. for 5 hours, and the appearance change of the coating film was visually observed. ○: No change, △: Some deterioration is observed, ×: Significant deterioration is observed

(5) Warm water resistance: 24 in warm water at 50 ° C.
After immersion for a time, the appearance change of the coating film was visually observed. ◯: No change, Δ: Slightly bad, ×: Poor (6) Solvent resistance: Gauze containing xylol was pressed with a finger, the coated surface was strongly rubbed back and forth 30 times, and the appearance of the film was visually judged as follows. It was evaluated according to the standard. ◯: There is no melting, scratching or swelling on the coated surface. Δ: Melt of coated surface,
Some scratches and swelling are noted. X: remarkable melting of the coated surface,
Scratches and swelling are observed. (7) Erichsen value: The Erichsen value was measured according to the breaking distance method of the Erichsen value of JIS K5400. Unit: mm (8) Flex resistance: Acceptability was determined according to JIS K5400. (9) Weight drop resistance: Using a weight drop device and a 1 kg drop weight, the height (mm) at which cracking was first observed was expressed.

(10) Weather resistance: Using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), black panel temperature = 63 ± 3 ° C., spraying time = 18 minutes / 120 minutes, after 2000 hours according to JIS K5400. The gloss retention (%) and the degree of color change (ΔE) were measured. (11) Yellowing resistance: UV lamp (Toshiba germicidal lamp GL15
(15 W, wavelength 254 nm) before and after irradiation for 200 hours (distance 20 cm, radiant intensity 600 μW / cm ² ) was measured with a color difference meter (Model SZΣ80 manufactured by Nippon Denshoku Industries Co., Ltd.). (12) Adhesiveness: Adhesion was performed according to the cross-cut tape method of JIS5400. (13) Contamination resistance: According to JIS5400, the appearance of the film was visually evaluated according to the following criteria. ○: No change, △: Minor change, ×: Significant change

[0061]

[Production Example 1] Acrylic polyol A A reaction vessel equipped with a stirrer, a thermometer, a cooler and a nitrogen gas introducing tube was charged with xylol 53.9 parts and butyl acetate 53.9 parts after sealing with nitrogen, and the temperature was 90 to 95 ° C. The temperature was raised to.
Styrene 68.0 parts, n-butyl acrylate 76.4
Part, 2-hydroxyethyl methacrylate 46.4 parts, acrylic acid 0.8 part, and azobisisobutyronitrile 2.8 parts were continuously dropped into the reaction vessel over 3 hours to carry out the polymerization reaction. went. After completion of dropping the monomer mixture, the mixture was heated and stirred for 1 hour, and then 1.4 parts of azobisisobutyronitrile was added every 30 minutes for a total of 4 times, and the reaction was terminated by further stirring for 1 hour. The resin solution (acrylic polyol A) thus prepared had a resin hydroxyl value of 100 mgKOH / g, a solid content of 65%, and a number average molecular weight of 12,000.

[0062]

[Example 4] Acrylic polyol B (Hitaroid 3083-70B manufactured by Hitachi Chemical Co., Ltd .: resin hydroxyl value =)
100 mg KOH / g, solid content = 70%, number average molecular weight 3300) 706.2 parts, and the coating viscosity of the final coating composition at 20 ° C. is Ford Cup No. Toluene / ethyl acetate / butyl acetate / cellosolve acetate acetate = 25/25/25/25 (wt
%) Mixed solvent (hereinafter, abbreviated as 4 type mixed solvent)
109.6 parts were added and mixed with stirring. The obtained solution 40
A clear coating composition was prepared by adding 67.7 parts of 1,3,6-hexanetricarboxylic acid tris (2'-isocyanatoethyl) ester prepared in Example 1 to 0.0 parts (NCO / OH molar ratio of 1.1). A composition was obtained. The coating solid content of this coating composition was 66%. The evaluation results are shown in Table 2.

[0063]

[Example 5] Acrylic polyol A produced in Production Example 1
755.9 parts has a coating viscosity of the Ford cup No. To be 25 seconds in 4
55.8 parts of the four-type mixed solvent was added and mixed with stirring. 57.6 parts of 1,2,4-butanetricarboxylic acid tris (2'-isocyanatoethyl) ester of Example 2 was added to 400.0 parts of the obtained solution (NCO / OH molar ratio 1.0). A clear coating composition was obtained. The coating solid content of this coating composition was 66%. The evaluation results are shown in Table 2.

[0064]

Example 6 Acrylic Polyol B Used in Example 4
In 688.2 parts, the coating viscosity of the final coating composition at 20 ° C. ford cup No. To be 25 seconds in 4
126.1 parts of the four-type mixed solvent was added and mixed with stirring. 400.0 parts of the resulting solution was prepared in Example 3
84.7 parts of 4,8-octanetricarboxylic acid tris (3'-isocyanatopropyl) ester was added (NCO /
An OH molar ratio of 1.2) was obtained to obtain a clear coating composition. The coating solid content of this coating composition was 66%. Table 2 shows the evaluation results
Shown in.

[0065]

Example 7 Acrylic Polyol A Produced in Production Example 1
773.0 parts, the coating viscosity of the final coating composition at 20 ° C. is Ford Cup No. To be 25 seconds in 4
54.7 parts of the mixed solvent of four kinds was added and mixed with stirring. To 400.0 parts of the obtained solution, 1,3,6-hexanetricarboxylic acid tris (2'-isocyanatoethyl) ester of Example 1 and duranate 24A-100 (polyisocyanate manufactured by Asahi Kasei Corporation, NCO content 23.5%)
And 69.2 parts of a 90/10 (mass ratio) mixture of
A clear coating composition having a CO / OH molar ratio of 1.1) was obtained. The coating solid content of this coating composition was 67%. The evaluation results are shown in Table 2.

[0066]

Example 8 Acrylic Polyol B Used in Example 4
246.0 parts of titanium white (PWC (mass ratio of pigment of the final coating composition) = 40%) is added to 404.1 parts, and then the coating viscosity of the final coating composition at 20 ° C. is Ford Cup No. 4 kinds of mixed solvent 1 so that 4 seconds will be 25 seconds
64.2 parts were added, and further a predetermined amount of glass beads were added, and the mixture was shaken to disperse the pigment, and the glass beads were removed. To 400.0 parts of the resulting dispersion was added 42.3 parts of 1,3,6-hexanetricarboxylic acid tris (2'-isocyanatoethyl) ester prepared in Example 1 (NCO / OH molar ratio 1 .2) An enamel coating composition was obtained. The coating solid content of this coating composition was 68%. The evaluation results are shown in Table 2.

[0067]

Comparative Example 4 Acrylic polyol B used in Example 4
628.2 parts has a coating viscosity at 20 ° C. of the final coating composition of Ford Cup No. To be 25 seconds in 4
187.2 parts of the four-type mixed solvent was added and mixed with stirring. 2, prepared in Comparative Example 1 for 400.0 parts of the resulting solution
6,2'-triisocyanatoethylhexanoate 3
7.7 parts was added (NCO / OH molar ratio 1.1) to obtain a clear coating composition. The coating solid content of this coating composition is 58%
Met. The evaluation results are shown in Table 3.

[0068]

[Comparative Example 5] Acrylic polyol A produced in Example 1
660.5 parts, the coating viscosity of the final coating composition at 20 ° C. is Ford Cup No. To be 25 seconds in 4
158.6 parts of the mixed solvent of four kinds was added and mixed with stirring. 400.0 parts of the obtained solution was compared with 1,2,3-of Comparative Example 2.
Propane tricarboxylic acid tris (2'-isocyanatoethyl) ester 47.9 parts was added (NCO / OH molar ratio 1.0) to obtain a clear coating composition. The coating solid content of this coating composition was 58%. The evaluation results are shown in Table 3.

[0069]

Comparative Example 6 Acrylic Polyol B Used in Example 4
604.8 parts, the coating viscosity of the final coating composition at 20 ° C. is Ford Cup No. To be 25 seconds in 4
227.5 parts of the four-type mixed solvent was added and mixed with stirring. 400.0 parts of the obtained solution was produced in Comparative Example 3,
75.9 parts of 3,12-tridecanetricarboxylic acid tris (2'-isocyanatoethyl) ester was added (NCO
A / OH molar ratio of 1.2) was obtained to obtain a clear coating composition. The coating solid content of this coating composition was 59%. The evaluation results are shown in Table 3.

[0070]

Comparative Example 7 Acrylic Polyol B Used in Example 4
359.6 parts of titanium white 199.6 parts (PWC = 40% of the final coating composition) was added, and then the final coating composition had a coating viscosity at 20 ° C. of Ford Cup No. 273.4 parts of the four-type mixed solvent was added so that the time was 4 seconds and 25 seconds, and a predetermined amount of glass beads was further added, and the mixture was shaken to disperse the pigment, and the glass beads were removed. 23.1 parts of 2,6,2'-triisocyanatoethylhexanoate prepared in Comparative Example 1 was added to 400.0 parts of the obtained dispersion liquid (NCO / OH molar ratio of 1.2), and an enamel coating material was added. A composition was obtained. The coating solid content of this coating composition is 5
It was 7%. The evaluation results are shown in Table 3.

[0071]

[Table 2]

[0072]

[Table 3]

The polyurethane resin coating films of Examples 4 to 8 were
Gloss, acid resistance, warm water resistance, solvent resistance, flexibility, weather resistance,
Excellent resistance to yellowing, adhesion and stain resistance.

[0074]

INDUSTRIAL APPLICABILITY The triisocyanate of the present invention does not contain diisocyanate having a high vapor pressure, has no irritating odor, and has low toxicity to the human body. Further, since it does not contain a high molecular weight substance, it has a low viscosity and is excellent in workability, and it is possible to make a paint into a high solid. Furthermore, it has excellent storage stability. Further, a polyurethane coating material and a polyurethane resin coating film having excellent gloss, acid resistance, warm water resistance, solvent resistance, flexibility, weather resistance, yellowing resistance, adhesion and stain resistance are provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4D075 CA03 CA06 CA13 CA32 CA34                       CA38 CA44 CB04 DB01 DB12                       DB16 DB21 DB31 DC01 DC08                       DC11 DC15 EA07 EA23 EA25                       EA27 EA43 EB22 EB35 EB38                       EB52 EB56                 4H006 AA01 AA03 AB99                 4J038 DG051 DG101 DG261

Claims (6)

[Claims] 1. A novel triisocyanate represented by formula (1). [Chemical 1] [R ¹ , R ² and R ³ are each independently substituted with an alkylene group having 2 to 20 carbon atoms, or an unsubstituted or substituted alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Represents a cycloalkylene group having 5 to 20 carbon atoms. Further, the alkylene group and the cycloalkylene group may contain a hetero atom, or may contain a substituent other than an alkyl group such as a phenyl group, an aryl group, a nitro group, a halogen group and an amino group. The alkyl part of the above-mentioned alkyl group, alkylene group, and alkoxy group may be linear or branched. p, r, and s are integers of 0 to 9, q is an integer of 1 to 9, and 1 ≦ p + q + r +
s ≦ 9 and {r <s or (r = s and p ≦ q)}] 2. The triisocyanate according to claim 1, wherein p + q + r + s = 3. 3. The triisocyanate according to claim 1, wherein p = 1, q = 2 and r = s = 0. 4. R ¹ , R ² and R ³ are all —CH ₂ CH ₂ —
The triisocyanate according to any one of claims 1 to 3. 5. A polyurethane paint comprising a polyol and a polyisocyanate, wherein the triisocyanate according to any one of claims 1 to 4 is used as at least one of the polyisocyanates. 6. A coating film made of a polyurethane resin obtained by reacting a polyol with a polyisocyanate, wherein the triisocyanate according to any one of claims 1 to 4 is used as at least one of the polyisocyanates. And polyurethane resin coating film.