WO2008065732A1

WO2008065732A1 - Process for production of modified isocyanate mixture containing allophanate bond and isocyanurate bond

Info

Publication number: WO2008065732A1
Application number: PCT/JP2007/000864
Authority: WO
Inventors: Ryusuke Kishimoto; Hiroyuki Orito
Original assignee: Nippon Polyurethane Industry Co., Ltd.
Priority date: 2006-11-27
Filing date: 2007-08-10
Publication date: 2008-06-05
Also published as: JPWO2008065732A1

Abstract

[PROBLEMS] To provide a process for producing a modified isocyanate mixture containing an allophanate bond and an isocyanurate bond, which is ensured in excellent curability, drying property and weather resistance, and particularly excellent tolerance to a non-polar organic solvent or a less odorous solvent and which has a low viscosity. [MEANS FOR SOLVING PROBLEMS] A process for producing a modified isocyanate mixture containing an allophanate bond and an isocyanurate bond, comprising the steps of: reacting a monoalcohol with an excess amount of an organic polyisocyanate in the presence of an allophanating catalyst to cause the allophanation of the polyisocyanate; removing unreacted organic polyisocyanate until the content of the organic polyisocyanate reaches 1.0% by mass or less; and isocyanurating the resulting product in the presence of an isocyanurating catalyst.

Description

Specification

Method for producing a mixture of alophane single bond and modified one containing a single bond

Technical field

[0001] The present invention relates to a method for producing a mixture of an allophanate bond and an isocyanurate bond-containing modified isocyanate having excellent solvent solubility (hereinafter referred to as tolerance) in a nonpolar organic solvent or a low odor solvent.

Background art

[0002] Paint ■ In the field of painting and adhesives, 1,6-hexamethylene diisocyanate (hereinafter referred to as HDI), isophorone diisocyanate, and other aliphatic dissociates, alicyclic dissociates Non-yellowing polyisocyanate derived from cocoon has excellent weather resistance, but polyisocyanate type containing isocyanurate bond has high chemical and thermal stability, especially weather resistance. Because of its excellent heat resistance and durability, it is widely used according to its application, and further application development is expected in the future.

[0003] This type containing an isocyanurate bond has better tolerance than the burette type and the urethane type, and is soluble in nonpolar aromatic hydrocarbon solvents such as toluene and xylene, but usually such as toluene and xylene. The solvent currently has practical limitations in terms of solvent selectivity, such as being unable to reapply until the base is cured in the coating process, because it has a strong solubility that affects plastics. .

As a method for solving these problems of the prior art, for example, the method of Patent Document 1 and Patent Document 2 and the method of Patent Document 3 are obtained by modifying a diisocyanate with alcohol to obtain a polyisocyanate containing an isocyanate bond. —Methods have been proposed for improving tolerance to non-polar organic solvents by using a mixture of 卜 and a polysocyanate containing an allophanate bond.

Furthermore, non-polar organic solvents are preferred because they cause pungent odors from the viewpoint of malodor prevention. In the future, there is a movement to use low-odor solvents such as paraffinic hydrocarbons, but there are currently no hardeners with good solubility.

[0004] When the diisocyanate is modified with a dialcohol having a long carbon number as in the methods proposed in Patent Document 1 and Patent Document 2, the molecular weight of the resulting modified polyisocyanate increases, so that the viscosity is high. This is unfavorable because the tolerance is lowered with respect to non-polar organic solvents, in particular, solvents with a high aniline point that are not soluble and low odor solvents.

Similarly, when the method is modified with monoalcohol having a short carbon number as in the method of Patent Document 3, the tolerance to the solvent is insufficient.

[0005] The techniques disclosed in each of the above patent documents are aimed only at improving the tolerance against non-polar organic solvents, and the tolerance is improved by using various modifiers. However, the hardness and drying characteristics when used as a coating composition and adhesive composition tend to be inferior to those of existing curing agents that are easily dissolved in ordinary polar solvents. There was no technology.

In other words, it has not been possible to obtain a curing agent having high tolerance against nonpolar organic solvents, in particular, solvents having a high aniline point that are not soluble, and low odor solvents, and having excellent hardness and drying properties. Is the current situation.

In the field of paints and adhesives, a decrease in hardness leads to a decrease in physical properties, and a decrease in dryness leads to a decrease in workability, which is generally undesirable as a disadvantage.

[0006] In view of this, Patent Document 4 proposes a method for producing a low-viscosity allophanate bond and a isocyanurate bond-containing modified isocyanate compound with further improved tolerance to various solvents, curability, drying property, and weather resistance. However, the modified isocyanate compounds containing allophanate bonds and isocyanurate bonds obtained by the method disclosed in Patent Document 4 are still sufficiently satisfactory in tolerance to nonpolar solvents such as mineral spirits and low odor solvents. It's hard to say.

Patent Document 1: Japanese Patent Publication No. 6 2-5 1 9 6 8

Patent Document 2: Japanese Patent Application Laid-Open No. Sho 62-2-2 1 5 6 6 2

Patent Document 3: Japanese Patent Laid-Open No. 4-3 0 6 2 18

Patent Document 4: Japanese Patent Laid-Open No. 2 0 0 2 _ 6 0 4 5 9

Disclosure of the invention

Problems to be solved by the invention

[0007] The object of the present invention is to ensure excellent curability, drying property, and weather resistance, and in particular, low viscosity allophanate bond and isocyanurate bond-containing modification excellent in tolerance to nonpolar organic solvents and low odor solvents. It is to provide a process for the preparation of a isocyanate mixture.

Means for solving the problem

[0008] Therefore, the present inventors have conducted intensive studies and worked on the development of a modified isocyanate mixture that is soluble in non-polar organic solvents as well as low odor solvents. As a result of earnest research on the production of these solvents in order to achieve “tolerance” at the same time as that of the conventional technology, while ensuring “dryability”, a part of the polyisocyanate was first obtained by monoalcohol. After urethanization and allophanatization, unreacted organic polyisocyanate was removed, and the reaction was carried out in the order of isocyanuration to find that the above problems could be solved, and the present invention was completed.

That is, in the present invention, monoalcohol and an excess amount of an organic polyisocyanate are reacted in the presence of an allophanetization catalyst to form an allophanet, and then an unreacted organic polyisocyanate is converted into The modified isocyanate mixture containing an allophanate bond and an isocyanurate bond, characterized in that it is removed so that its content is not more than 1.0% by mass, and then isocyanurated in the presence of an isocyanuration catalyst. It is a manufacturing method.

[0010] The present invention relates to a monoalcohol and an excess amount of an organic polyisocyanate in the presence of an allophanatization catalyst in a proportion of 1.8 to 2.0 with respect to the hydroxyl group of the monoalcohol. After reacting at 70 to 150 ° C. within the range that consumes a double molar amount of isocyanate group, it is converted to allophanate, and the content of unreacted organic polyisocyanate is 1.0% by mass. The viscosity at 25 ° C is 2, OOO m P a ■ characterized in that it is then removed in the presence of an isocyanuration catalyst and then isothermally converted at 40 to 90 ° C. s The following is a process for producing a modified isocyanate mixture containing allophanate bonds and isocyanurate bonds.

[001 1] In the present invention, the organic polyisocyanate is an aliphatic diisocyanate.

And a method for producing a modified isocyanate mixture containing each alophanate bond and isocyanurate bond.

[0012] Further, the present invention provides a monoalcohol and an excess amount of an organic polyisocyanate, when reacting in the presence of an aromatication catalyst to make an allophanate. This is a process for producing a mixture of modified allophanate bonds and isocyanurate bond-containing modified isocyanates, wherein a mixture of an organic polyisocyanate and a urethane group-containing isocyanate compound is synthesized by reacting with an isocyanate.

The invention's effect

[0013] The modified isocyanate mixture produced according to the present invention is obtained by urethanizing a part of an organic polyisocyanate with monoalcohol and then allocating (all urethane groups) to an organic polyisocyanate (monomer). ) Is removed to synthesize a modified polyisocyanate containing substantially only an allophanate group, which is further isocyanurated, so it has low viscosity and good compatibility with solvents and polyhydric hydroxy compounds. In particular, it can be used as a curing agent (for polyurethane coating compositions and adhesive compositions) that has both tolerance to non-polar organic solvents and / or low odor solvents and curability, drying properties, and weather resistance. Therefore, it can be applied to a wide range of objects such as metal, plastic, concrete, and wood with good workability. In addition, compared with the case of using a conventional polar solvent, it does not cause lifting of the coating film when it is applied over or repaired on a coating film that is easily affected by the polar solvent, and the coating film has a good appearance. Obtainable. BEST MODE FOR CARRYING OUT THE INVENTION

[0014] The present invention is described in detail below.

Examples of the organic polyisocyanate used for the synthesis of the modified isocyanate mixture in the present invention include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,2′-diphenylmethane. Tandiisocyanate, 2, 4_Toluene diisocyanate, 2,6_Toluene diisocyanate, 4, 4 '— Diphenylterdiisocyanate, 2_Nitrodiphenyl-1,4'—Diisocyanate 2, 2 '-Diphenylpropane 4,4'-Diisocyanate, 3, 3 '-Dimethyldiphenyl methane 4,4'-Diisocyanate, 4, 4 '-Diphenylpropanedisorbate, 1, 2_Fue Diylene diisocyanate, 1,3_Phenylene diisocyanate, 1,4_Phenylene diisocyanate, 1,4-Naphtha diisocyanate, 1,5_Naphtha Diisocyanate, 3, 3'-dimethyoxydiphenyl-1,4'-aromatic diisocyanate such as diisocyanate, HD I, 1,4-tetramethylene diisocyanate, aliphatic diisocyanate such as lysine diisocyanate , O-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, tetramethylxylene diisocyanate, and other araliphatic diisocyanates, isophorone diisocyanate, hydrogenated toluene Examples thereof include alicyclic diisocyanates such as diisocyanates, hydrogenated xylylene diisocyanates, hydrogenated diphenylmethane diisocyanates, and hydrogenated tetramethylxylene diisocyanates.

These organic polyisocyanates can be used alone or in admixture of two or more.

Of these organic polyisocyanates, when considering weather resistance and the like, aliphatic diisocyanates are preferable, and HDI is more preferable.

[0015] In the synthesis of the modified isocyanate mixture in the present invention, the monoalcohol is used to further increase tolerance to nonpolar organic solvents and low odor solvents. A monoalcohol having 1 to 20 carbon atoms is preferred. When the monoalcohol has more than 20 carbon atoms, the isocyanate content of the modified isocyanate mixture (hereinafter referred to as NCO content) decreases, and for example, in the case of stearic alcohol, it tends to solidify at a low temperature.

Specific examples of monoalcohols include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, n-pentanol, iso-pentanol, n_hexanol, n-heptanol, n-octanol, 2_ethylhexanol, ethyldimethyl-1-hexanol, methyl_1-nonanol, dimethyl_1-octanol, tetramethyl_1-hexanol, 3_ethyl-4 , 5, 6_trimethyloctanol, 4, 5, 6, 7-tetramethylnonanol, 4, 5, 8-trimethyldephenol, 4, 7, 8_trimethyltridecanol, tridecano 1, tetradecanol, 2_hexyldodecanol, 2-octyldodecanol, 2_decyltetradecanol, 2_hexadecyloctadecanol and the like. These can be used alone or in admixture of two or more.

[0016] The amount of monoalcohol used is preferably such that the urethanation rate in the reaction with the organic polyisocyanate is 2 to 20 mol% based on the total isocyanate groups. If the amount of monoalcohol used is less than 2 mol%, the yield is poor and inefficient. If the urethanization ratio exceeds 20 mol%, the NCO content of the resulting modified isocyanate decreases, and the hardness, dryness and weather resistance of the coating composition or adhesive composition are improved. Cannot be achieved.

The urethanization reaction can be suitably carried out in the range of 20 to 120 ° C.

[0017] The halophanation reaction is carried out using a known halophanation catalyst.

Preferred examples of the halophanation catalyst include a metal salt of a carboxylic acid or a mixed catalyst of this with a phosphite, and more preferably a metal salt of strong sulfonic acid. Examples of the carboxylic acid that is a raw material of the metal salt of the carboxylic acid include acetic acid, propionic acid, butyric acid, caproic acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and 2-ethylhexanoic acid. Saturated aliphatic sulfonic acid, cyclohexane carboxylic acid, saturated monocyclic carboxylic acid such as cyclopentane carboxylic acid, bicyclo (4.4.0) decane _ 2_ saturated carboxylic acid such as carboxylic acid, naphthenic acid A mixture of the above carboxylic acids such as oleic acid, linoleic acid, linolenic acid, unsaturated fatty acid such as soybean oil fatty acid, tall oil fatty acid, etc. arabic acid carboxylic acid such as diphenylacetic acid, benzoic acid, tolyl Aromatic carboxylic acids such as acids can be mentioned.

Examples of the metal in the metal salt of carboxylic acid include alkaline earth metals such as magnesium, calcium, and barium, transition metals such as manganese, iron, cobalt, nickel, copper, zinc, and zirconium, and boron groups such as aluminum, Examples include carbon group metals such as tin and lead.

These metal salts of rubonic acid can be used alone or in admixture of two or more.

Among these, one or more selected from the group consisting of zirconium salts, tin salts, zinc salts and lead salts of saturated aliphatic carboxylic acids are preferred.

Phosphites used as cocatalysts include phosphite diesters and phosphite triesters.

Specific examples of phosphorous acid triesters include triethyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite. , Tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t_butylphenyl) phosphite, diphenyldecyl phosphite, diphenyl (tridecyl) Examples include monophosphites such as phosphites. Distearyl pentaerythrityl diphosphite, ditridecyl pentaerythritol-didiphosphite, dinonylphenylpentaerythritol I rudiphosphite Di, tri or tetra phosphites derived from polyhydric alcohols such as tetraphenyl tetratridecyl pentaerythrityl tetraphosphite, tetraphenyl dipropylene glycol diphosphite, tripentaerythritol I rutriphosphite Also mentioned. In addition, dialkyl bisphenol A diphosphite having 1 to 20 carbon atoms, 4, 4 '— Butylidene monobis (3_methyl _ 6 _ t _ butylphenyl ditridecyl) phosphite, etc. Polyphosphites such as derivatized diphosphites, hydrogenated bisphenol A phosphite polymers (molecular weight 2400-300), tris (2,3-dichloroprop) and phosphites are also listed. I can get lost.

Specific examples of the phosphite diester include dilauryl hydrogen phosphate, diphenyl hydrogen phosphate, and the like.

These phosphites can be used alone or in admixture of two or more.

When a carboxylic acid metal salt and a phosphite are used in combination, the amount of the carboxylic acid metal salt itself may be less than when used alone. The amount of the metal salt of the carboxylic acid varies depending on the type, but is usually preferably from 0.05 to 1% by mass, based on the reaction product of monoalcohol and organic polyisocyanate. 1 to 0.1% by mass is more preferable. When the amount of the metal salt of the carboxylic acid based on the reaction product is less than 0.05% by mass, the reaction is substantially slow and takes a long time. On the other hand, the use of the metal salt of the carboxylic acid is difficult. When the dose exceeds 1% by mass, it is difficult to control the reaction, and problems such as shortening the pot life of the two-component resin containing the reaction product as a curing agent may occur. The amount of phosphite used is preferably from 0.05 to 1% by mass, more preferably from 0.1 to 0.5% by mass, based on the reaction product of monoalcohol and organic polyisocyanate. preferable. When the amount used is less than 0.05% by mass, the effect as a co-catalyst is insufficient. On the other hand, when the amount used exceeds 1% by mass, the final product using the product obtained by the reaction is used. May adversely affect product properties There is.

[0019] It is preferable to carry out the halophanation rate within a range in which 1.8 to 2.0 times the molar amount of isocyanate group is consumed with respect to the hydroxyl group of the monoalcohol. The product obtained by reacting in the range where the conversion rate of isocyanato groups less than 1.8 times the molar amount of hydroxyl groups with respect to the hydroxyl group is consumed is a large amount of monofunctional component, which deteriorates the physical properties of the coating film. When isocyanate groups exceeding a double molar amount are consumed, it is considered that an isocyanuration reaction has occurred. However, it is not efficient to form an isocyanurate with an allophanate catalyst, and turbidity is likely to occur.

The alphaphanation reaction is preferably carried out in the range of 70 to 1550 ° C. If the reaction temperature is less than 70 ° C, the reaction proceeds very slowly. If the reaction temperature exceeds 150 ° C, the color becomes fuzzy.

[0020] The free unreacted organic polyisocyanate (monomer) present in the allophanatization reaction mixture is extracted with, for example, n-hexane or 10 to 1 OOP a under high vacuum. Remove to a residual content of not more than 1.0% by weight by suitable means such as thin-film distillation at ~ 140 ° C.

[0021] The isocyanuration reaction of the allophanatization reaction product is performed using a known isocyanuration catalyst.

Specific examples of the isocyanuration catalyst include triethylamine, N-ethylbiperidine, N, N′-dimethylpiperazine, N-ethylmorpholine, tertiary amine such as phenolic Mannich base, tetramethylammonium Hydroxide of tetraalkylammonium such as tetraethylammonium, tetraptylammonium, organic weak acid salts, trimethylhydroxypropylammonium, trimethylhydroxypropylammonium, triethylhydroxyammonium Hydroxyl ammonium such as humum Hydroxide of humic acid, acetic acid, propionic acid, butyric acid, strength bromic acid, strength purinic acid, valeric acid, isovaleric acid, octylic acid, myristic acid, naphthenic acid, etc. Alkali metal salt of carboxylic acid Etc., and the like. These are simply Can be used alone or in admixture of two or more.

Of these, carboxylic acid metal salts of carboxylic acids are preferred.

The isocyanuration catalyst is preferably used in an amount of 0.000 "! To 1.0% by weight, in particular 0.001 to 0.1% by weight of ⁰ / o, based on the organic polyisocyanate.

The isocyanuration reaction is preferably carried out in the range of 40 to 90 ° C. When the reaction temperature is below 40 ° C or above 90 ° C, the reaction proceeds very slowly.

If it exceeds 90 ° C, it tends to be colored easily.

[0022] After reaching the target isocyanuration reaction rate, a terminating agent such as acidic phosphate ester, phosphoric acid or methyl paratoluenesulfonate is added to stop the isocyanuration reaction.

[0023] The modified isocyanate mixture obtained by the present invention can be diluted with an inert solvent and used as a curing agent for paints and adhesives.

Examples of such inert solvents include HAWS (manufactured by Seal Chemicals Japan Co., Ltd., Anilin Point 15 ° C), Suzusol 3 10 (manufactured by Maruzen Oil Co., Ltd., Anilin Point 16 ° C), Etsonaphtha N o. 6 (Exon Chemical Co., Ltd., Airlin point 43 ° C), Koutus (Shell Chemicals Japan Co., Ltd., aniline point 43 ° C), A Solvent (Japan Oil Co., Ltd., Anilin point 44 Non-polar organic solvents such as 5 ° C) and / or low odor solvents such as isopentane, isohexane, isooctane, and isododecane. These can be used alone or in admixture of two or more. It is also preferable to use a mixture of these inert solvents with a polar organic solvent.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.

Example 1

To a four-flask equipped with a stirrer, thermometer and reflux condenser, H D I (manufactured by Nippon Polyurethane Industry Co., Ltd .; N CO content = 49.9 mass%, solid content =

1 00 mass ⁰ / o) 950 g, then iso propanol 50 g It was crowded. This was heated to 85 ° C with stirring, and stirred at the same temperature for 3 hours to carry out the urethanization reaction. Thereafter, 0.05 g of zirconium octylate was added to the reaction solution as an alophanate catalyst, and the mixture was stirred at 110 ° C. for 4 hours to carry out an alphaphanate reaction. Next, unreacted HD I was removed by thin-film distillation at 130 ° C. and 0.04 kPa (HDI residual ratio: 0.1% by mass) and cooled to 50 ° C. To this, 2.0 g of a solution prepared by dissolving 1.0 g of potassium octylate as an isocyanuration catalyst in a mixed solvent of 4.5 g of dipropylene glycol and 4.5 g of tetrahydrofuran was added, and the mixture was stirred at 80 ° C for 5 hours. Stir to conduct isocyanurate reaction, add 0.8 g of acidic phosphate ester as the reaction terminator when the specified N CO content (N CO content at the time of reaction stoppage) is reached, and stir for 100 minutes Thus, the reaction was stopped to obtain a modified isocyanate mixture P-1.

Table 1 summarizes the raw materials used, the amounts charged, the reaction conditions, reaction results, and the properties of the modified isocyanate mixture.

The residual free HDI content was determined by gas chromatography analysis. The analysis of the modified isocyanate mixture was performed by GPC analysis, IR analysis, and ¹³ C_NMR analysis. Figure 1 shows this GPC analysis chart.

Comparative Example 1

950 g of HD I (manufactured by Nippon Polyurethane Industry Co., Ltd .; NCO content = 49.9 mass%, solid content = 100 mass ⁰ / o) was charged into a four-flask equipped with a stirrer, thermometer and reflux condenser, Next, 50 g of iso_propanol was charged. This was heated to 85 ° C with stirring, and stirred at the same temperature for 3 hours to carry out the urethanization reaction. Thereafter, 0.05 g of zirconium octylate was added to the reaction solution as an alophanate catalyst, and the mixture was stirred at 110 ° C. for 4 hours to carry out an alphaphanate reaction. Next, the solution was cooled to 50 ° C, and 0.5 g of potassium octylate dissolved in a mixed solvent of 4.5 g of dipropylene glycol and 4.5 g of tetrahydrofuran as an isocyanuration catalyst was added to the solution. Add 5 g and stir at 80 ° C for 3 hours to carry out the isocyanuration reaction. When a constant NCO content (NCO content at the time of stopping the reaction) was reached, 0.6 g of acidic phosphate ester as a reaction terminator was added and stirred for 100 minutes to stop the reaction. Unreacted HDI was removed by thin film distillation at 130 ° C and 0.04 k Pa (residual ratio of HDI 0.1 mass%) to obtain a modified isocyanate mixture P _ 2 Raw materials used, those Table 1 summarizes the charge amount of each, reaction conditions, reaction results, and properties of the modified isocyanate mixture.

The residual free HDI content was determined by gas chromatography analysis. The analysis of the modified isocyanate mixture was performed by GPC analysis, IR analysis, and '3C-NMR analysis. Figure 2 shows this GPC analysis chart.

[table 1]

Example 1 Comparative Example 1 Raw material (g)

H D I 950 950 Les i-s o-propanol 50 50 evening

Reaction §

Temperature s rc) 85 85 hours (hrs) 3 3a catalyst (g)

ジルコニウム Zirconium octylate 0.05 0.05

A

Reaction conditions

Temperature r ^c ) 110 110 卜 Time (hrs) 4 4

Existence of distillation process (isolation after alophanate reaction)

Before cyanuration reaction) (0.1%)

Catalyst ( ^σ )

Sodium octylate 1.0 g dipro 2.0 1.5 Cypyrene glycol 4.5 g

4.5 g solution

Nu

Reaction conditions

I Temperature C) 80 80 卜 Time (hrs) 5 3

Reaction terminator (g)

Acid phosphate ester 0.8 0.6 Presence or absence of distillation process (after isocyanuration reaction) Yes

N C O content (mass%)

After urethanization 44.5 After halophaneization 40.6 After isocyanuration 17.0 38.6 Modified isocyanate mixture P-1 Ρ— 2 Yield (mass%) 45 45 NC 0 content (mass%) 17.0 17.0 Viscosity (m P a * sZ2 5 ° C ) 300 300 Free HDI content (mass> 0.1 0.1

[Tolerance]

Take 5 g of each of the products obtained in Example 1 and Comparative Example 1, add various solvents listed in Table 2 little by little in a burette, shake well at 25 ° C and make the cloudy point the end point, and the solvent at that time The required number of m I was calculated. The tolerances corresponding to various solvents were calculated by the following formula. Tolerance = Solvent required m I / sample volume (5 g).

The larger this value, the better the tolerance.

The results are shown in Table 2.

[0028] [Table 2]

Note 1) A Solven®: Non-polar petroleum solvent manufactured by Nippon Oil Corporation

(Anylin point 44.5 ° C)

2) HAWS: Non-polar petroleum solvent manufactured by Shell Chemicals Japan

(Anylin point 15 ° C)

[0029] [Coating film test]

Example 1, modified isocyanate mixture obtained in Comparative Example 1 and acrylol polyol (Aclidick HU_596, manufactured by Dainippon Ink and Chemicals, hydroxyl value 3 Om g KO H / g, N v = 50%) and solvent HAWS (High Aromatic White Spirit) is applied to steel plate (JISG 31 41 S PCC_S B, PF_ 1 077 treatment, manufactured by Nippon Test Panel Industry Co., Ltd.) degreased with methyl ethyl ketone. Using Wet 1 OO m, coating was performed in an environment of 20 ° C. and 65% RH for 1 week to form a coating film with a dry film thickness of 30 to 4 O m.

These coating films were evaluated using the following method.

In order to evaluate the drying property of the coating film, a drying recorder (RIKEN OPTICAL: current Ricoh Co., Ltd.) was used.

Bend resistance test (cylindrical mandrel method) to evaluate resistance to cracks, cracks, and peeling from metal substrate when bent by cylindrical mandrel (J I S

K 5600-5-1)), and a coating resistance test (JISK 5600) to evaluate the resistance to cracking, cracking, and peeling from the metal substrate when the coating is partially deformed by indentation. — 5— 2) Weight drop resistance test (DuPont method) to evaluate the resistance to cracks, cracks, and peeling from metal substrates that deforms underneath (in accordance with JISK 560 0_5_3), to evaluate the hardness of the coating surface Toughness hardness test (pencil method) (according to JISK 5600-5-4), cross-cut tape test to evaluate the adhesion of paint film (according to JISK 5600-8-5-2), QUV A weather resistance test (conforming to JISK 5600-7-8) after 1056 hours of irradiation was conducted. The weathering test equipment is manufactured by Q_Pane I, and the cycle condition is 1 cycle: 70 ° ○, only re is 8 r, then 50 ° C, only water spray is 4 hr.

The results are shown in Table 3.

[0030] [Table 3]

[0031] In each chart in Figs. 1 and 2, the molecular weight of each peak (Mn, M From w), peak (1) is an HDI monoalophanate, peak (2) is an isocyanurate consisting of 3 HDI molecules, peak (3) is an HD I dialophaneate, and peak (4) is 3 molecules. It is presumed that each is a isocyanurate form of monodiaphanated HDI.

When Charts 1 and 2 are compared, the modified isocyanate mixture P-2 has a peak (2) production of 14.2% of its total (total) peak area, and peak (4) is P_2. The total (total) is almost absent in the peak area, whereas the modified isocyanate mixture P_ 1 has a peak (2) production of 3.0% in its total (total) peak area, peak (4) Produced 9.1% of the total peak area of P-1 (total). From the modified isocyanate mixture P-2, which is a mixture of HDI mono and diaphanate and isocyanurate consisting of 3 molecules of HDI, isocyanurate consisting of HD I mono and diaphanate and trimolecular HDI. P_ 1 is more tolerant to non-polar organic solvents and low odor solvents. Isocyanurate compound consisting of 3 molecules of monoarophanate HDI is mixed in a proportion (9.1%) with a certain ratio (9.1%). Is estimated to be high.

Brief Description of Drawings

[Figure 1] GPC analysis chart of the modified isocyanate mixture P_1.

[Fig. 2] GPC analysis chart of modified isocyanate mixture P_2.

Claims

The scope of the claims

[1] After reacting monoalcohol with an excess amount of organic polyisocyanate in the presence of an allophanated catalyst to make an allophanate, the content of unreacted organic polyisocyanate is 1.0. A method for producing a modified isocyanate mixture containing an allophanate bond and an isocyanurate bond, characterized by comprising removing it so as to be less than or equal to mass%, and then performing isocyanuration in the presence of an isocyanuration catalyst.

[2] A mono-alcohol and an excess amount of organic polyisocyanate are added in the presence of an allophanate catalyst so that a 1.8 to 2.0-fold molar amount of iso-isocyanate group with respect to the hydroxyl group of the mono-alcohol is added. After reacting at 70 to 1550 ° C. within the range of consumption to form an allophane, the unreacted organic polyisocyanate is removed so that its content is 1.0% by mass or less, Isocyanuration at 40 to 90 ° C in the presence of an isocyanuration catalyst, characterized by the following: Allophanate bonds and isocyanurates with a viscosity at 25 ° C of 2, OOO m P a s or less A process for producing a bond-containing modified isocyanate mixture.

[3] The method for producing a mixture of allophanate bond and isocyanurate bond-containing modified isocyanate according to claim 1 or 2, wherein the organic polyisocyanate is an aliphatic diisocyanate.

[4] When reacting monoalcohol with an excess amount of organic polyisocyanate in the presence of an allophanate catalyst to make an allophanate, first, monoalcohol and an excess amount of organic polyisocyanate 4. The method for producing a mixture of an allophanate bond and an isocyanurate bond-containing modified isocyanate according to claim 1, wherein a mixture of an organic polyisocyanate and a urethane group-containing isocyanate compound is synthesized.