WO2006075636A1

WO2006075636A1 - Method for producing allophanate-modified polyisocyanate composition

Info

Publication number: WO2006075636A1
Application number: PCT/JP2006/300245
Authority: WO
Inventors: Yoshizumi Kataoka; Koichi Suzuki; Mitsushige Ikemoto
Original assignee: Nippon Polyurethane Industry Co., Ltd
Priority date: 2005-01-14
Filing date: 2006-01-12
Publication date: 2006-07-20
Also published as: JP2006193642A

Abstract

Disclosed is a method for relatively easily producing an allophanate-modified polyisocyanate composition without using a promoter, which allophanate-modified polyisocyanate composition is practically colorless and substantially contains no urethane group, urethodione group or isocyanurate group. Specifically disclosed is a method for producing an allophanate-modified polyisocyanate composition from an alcoholic hydroxyl group-containing compound (A) and an organic diisocyanate (B) by using an allophanation catalyst (C). This method is characterized in that the allophanation catalyst (C) is a zirconium tetracarboxylate having 6 or more carbon atoms, and a catalyst poison (D) is used for stopping the allophanation reaction.

Description

Specification

Process for producing alophanate-modified polyisocyanate composition

Technical field

[0001] The present invention relates to a method for producing an allophanate-modified polyisocyanate composition. More specifically, the present invention relates to a method for producing an allophanate-modified polyisocyanate composition which substantially contains no urethane group, uretdione group and isocyanurate group and has a transparent appearance.

Background art

[0002] Various methods for producing alophanate-modified polyisocyanate have been conventionally known! For example, Patent Documents 1 to 3 disclose a method for producing an allophanate-modified polyisocyanate.

However, in spite of the fact that most of the methods for producing alophanate-modified polyisocyanate described therein are aimed at the formation of an allophanate group, a self-addition reaction or a self-polymerization reaction is a side reaction. As the process proceeds and by-products are generated, there is a problem. Examples of the by-product include a dimer containing a thermally unstable uretdione group, which dramatically increases the viscosity of the final product, and is soluble in a non-polar solvent, polymer polyester, etc. And a trimer containing an isocyanurate group which reduces the compatibility with the resin. Furthermore, there is a problem that the final product is colored or turbid.

[0004] For example, Patent Document 1 describes a method for producing an allophanate group-containing polyisocyanate in which an isocyanate group-terminated urethane prepolymer and an organic diisocyanate are reacted in the presence of a specific catalyst. The resulting polyisocyanate contains substantially dimers and trimers. In addition, when a catalyst is not used, the reaction takes a long time at a high temperature, resulting in coloring the final product as well as increasing the production cost.

[0005] Patent Document 2 describes a method for producing an allophanate-modified isocyanate of a diisocyanate having a ring structure such as a benzene ring, and describes that the same catalyst as the urethanization reaction can be used for the allophanate reaction. . [0006] In addition, Patent Document 3 describes a method for producing alophanate-modified polyisocyanate containing no dimer or trimer, but this method has an isocyanate group bonded to an aromatic group. It has substantial reactivity only in the compounds and is not suitable for the production of polyisocyanates containing aliphatic esters having aliphatic and Z or alicyclic bonded isocyanate groups.

[0007] Further, Patent Document 4 discloses a process for producing an allophanate group-containing polyisocyanate which is substantially free of isocyanate dimer and which is substantially colorless and has a relatively low viscosity. . In this method, a polyisocyanate is partially urethaned with a hydroxyl group compound and reacted at a temperature of at least 150 ° C. for 90 minutes or less to form an allophanate group, and the product generated by the reaction It is characterized by cooling to a temperature below 100 ° C within 10 minutes. However, in this method, the reaction temperature rises and falls rapidly, making it unsuitable for large-scale batch production, and because the reaction is controlled in a short time, the conversion rate of urethane groups to allophanate groups is high. Low. Therefore, it contains a considerable amount of unreacted urethane groups, and it does not contain dimers, but it is not satisfactory in providing performance specific to allophanate groups.

[0008] Thus, in the conventional method for producing a polyisocyanate containing an allophanate group, dimerization or trimerization of the isocyanate proceeds as a side reaction or the compound having an allophanate group is collected. The problem was solved by each method such as low rate!

[0009] In order to solve such problems, in Patent Document 5, a compound having a urethane group and an isocyanate are reacted using a catalyst having a carboxylic acid metal salt power and a promoter having a phosphite power. A method for producing an allophanate group-containing polyisocyanate is shown.

[0010] Patent Document 1: Specification of British Patent No. 994,890

Patent Document 2: Japanese Patent Publication No. 46-1711

Patent Document 3: Japanese Patent Laid-Open No. 46-1671

Patent Document 4: JP-A-64-66155

Patent Document 5: JP-A-8-188566

Disclosure of the invention Problems to be solved by the invention

The present invention has been made in view of the above problems, and can be produced relatively easily without using a cocatalyst, is substantially free of dimers and trimers, and is substantially colorless alophanate. It aims at providing the manufacturing method of a modified polyisocyanate composition.

Means for solving the problem

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a specific metal salt as an allophanate catalyst, and have completed the present invention.

That is, the present invention is as shown in the following (1) to (5).

(1) In a method for producing an allophanate-modified polyisocyanate composition from an alcoholic hydroxyl group-containing compound (A) and an aliphatic and Z or alicyclic diisocyanate (B) using an allophanate catalyst (C), The production characterized in that the alfaphanate catalyst (C) is a zirconium tetracarboxylate, the carboxylic acid has 6 or more carbon atoms, and the catalyst poison (D) is used when the alfaphanate reaction is stopped. Method.

[0014] (2) The method according to (1), wherein after the allophanatization reaction is stopped, the free organic diisocyanate (B) is removed until the content becomes 1% by mass or less.

[0015] (3) (A) is a monool compound having 1 to 40 carbon atoms, and the obtained allophanate-modified polyisocyanate composition contains 60% by mass or more of a bifunctional component, (1) or (2) production method.

(4) (A) is a monool compound having 1 to 10 carbon atoms, and the viscosity of the obtained allophanate-modified polyisocyanate composition at 25 ° C. is 130 mPa ′s or less, Manufacturing method of said (1)-(3).

(5) (A) is a monool compound having 3 to 40 carbon atoms, and the obtained alophanate-modified polyisocyanate composition is soluble in a poor solvent. 4) Manufacturing method.

The invention's effect

[0018] The alophanate-modified polyisocyanate composition obtained by the present invention is substantially free of dimer and trimer. Note that “substantially free of dimers and trimers” means that traces of the presence of dimers and trimers are recognized by IR and NMR analysis. Or no

It is to meet with a niece who cannot be found.

[0019] Furthermore, the present invention is a process for producing an allophanate-modified polyisocyanate composition having an excellent performance that can be produced relatively easily, has a low viscosity that is substantially uncolored, and is soluble in a poor solvent in some cases. Provide a method.

BEST MODE FOR CARRYING OUT THE INVENTION

[0020] The raw materials used in the present invention will be described.

The “alcoholic hydroxyl group” in the alcoholic hydroxyl group-containing compound (A) used in the present invention means a hydroxyl group directly bonded to the aliphatic hydrocarbon skeleton. That is, the term “alcoholic hydroxyl group-containing compound” is intended to exclude compounds in which a hydroxyl group is directly bonded to an aromatic hydrocarbon skeleton, such as phenol and talesol. In the present invention, the alcoholic hydroxyl group-containing compound (A) may be used alone or in the form of a mixture of two or more.

[0021] Specific examples of (A) include methanol, ethanol, propanol (including various isomers), butanol (including various isomers), pentanol (including various isomers), hexanol (including various isomers). Including various isomers), heptanol (including various isomers), octanol (including various isomers), nonanol (including various isomers), decanol (including various isomers), lauryl alcohol, myristyl alcohol (tetra Decanol), pentadecanol, cetyl alcohol (hexadecol), heptadecanol, stearyl alcohol (octadecanol), nonadeol, oleyl alcohol and other aliphatic monools, cyclohexanol, methylcyclohex Alicyclic monools such as xanol, and araliphatic monooles such as benzyl alcohol Ethylene glycol, 1,2-propanediol, 1,3 propanediol, 1,2 butanediol, 1,3 butanediol, 1,4 butanediol, 1,5 pentanediol, 2-methyl-1,5 pentanediol 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 2,2 jetyl-1,3 propanediol, 2-n-butyl-2 Ethyl-1,3 propanediol, 2,2,4 Trimethyl-1,3 pentanediol, 2 Ethyl-1,3 hexanediol 2-n-hexadecane 1, 2-ethylene glycol, 2-n-eicosane 1, 2-ethylene glycol, 2-n-octacosane-1, 2-ethylene glycol, and other aliphatic diols , Cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, alicyclic diols such as hydrogenated bisphenol A, and araliphatic diols such as bis (j8-hydroxyethyl) benzen , glycerol, trimethylolpropane, aliphatic polyols such as pentaerythritol Le, diethylene glycol, dipropionate glycol, ether group-containing Darikoru such as Toriechire glycol, _a Okishipuropion acid, Okishiko Haq acid, Jiokishikohaku acid, epsilon Okishipuropan 1, 2, 3 Tricarboxylic acid, hydroxyacetic acid, OC-hydroxybutyric acid, hydroxystearic acid Ricinoleic acid, ricinelaidic acid, ricinoleate stearolic acid, salicylic acid, hydroxyl group-containing esters in which the Okishikarubon acid obtained above in motor Nooruka ゝ et such mandelic acid.

[0022] Further, a hydroxyl group-containing polyether obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide using the above-mentioned hydroxyl group-containing compound as an initiator.

Hydroxyl-containing polyesters obtained from the above-mentioned polyol and polycarboxylic acid power, hydroxyl-containing polycarbonates obtained from the above-mentioned polyols and low-molecular carbonates (ethylene carbonate, propylene carbonate, dimethyl carbonate, jetyl carbonate, diphenyl carbonate, etc.) Etc. can also be used suitably.

In the present invention, ease of handling as a raw material, viscosity of the resulting polyisocyanate, etc.

In view of this, polyether polyols having a number average molecular weight of 1,000 to 5,000 and monool compounds having 1 to 40 carbon atoms are preferred! /.

As the aliphatic and 及び or alicyclic diisocyanate (Β) used in the present invention, hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane 1,5 diisocyanate, 3 —Methyl monopentane-1, 1,5 diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, and other aliphatic diisocyanates; xylylene 1,4-diisocyanate, xylylene 1,3 diisocyanate, tetramethylxylylene diisocyanate, etc. Araliphatic diisocyanate; isophorone diisocyanate, hydrogenated hydrogenated diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diisocyanate And alicyclic diisocyanates such as phenol methane diisocyanate and hydrogenated tetramethylxylene diisocyanate. These organic diisocyanates may be used alone or in a mixture of two or more. In consideration of the weather resistance and the like of the allophanate-modified polyisocyanate obtained in the present invention, non-yellowing diisocyanate is preferred, particularly hexamethylene diisocyanate.

[0025] The allophanate catalyst (C) used in the present invention is a zirconium tetracarboxylate. Examples of the carboxylic acid include octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 2-ethylhexanoic acid, and other saturated aliphatic carboxylic acids having 6 or more carbon atoms, cyclohexane carboxylic acid, and cyclopentane. Saturated monocyclic carboxylic acids such as carboxylic acids, bicyclo (4.4.0) decane 2-saturated polycyclic carboxylic acids such as rubonic acid, mixtures of the above carboxylic acids such as naphthenic acid, oleic acid, linoleic acid, Unsaturated aliphatic carboxylic acids such as linolenic acid, soybean oil fatty acid and tol oil fatty acid, aromatic aliphatic carboxylic acids such as diphenylacetic acid, monocarboxylic acids such as aromatic carboxylic acids such as benzoic acid and toluic acid, Phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, adipic acid, pimelic acid, suberic acid, kurtaconic acid, azelaic acid, sebacic acid, 1 , 4-cyclohexyldicarboxylic acid, α-noidromuconic acid, β-hydromuconic acid, —butyl-ethyl taltaltaric acid, a, j8-jetylsuccinic acid, trimellitic acid, pyromellitic acid, and other polycarboxylic acids . These zirconium carboxylates may be used alone or in the form of a mixture of two or more. (C) preferred in the present invention is a zirconium salt of an aliphatic monocarboxylic acid having 6 to 10 carbon atoms.

[0026] By specifying this allophanate catalyst (C), the present invention makes it possible to relatively easily obtain an allophanate-modified polyisocyanate composition having substantially no color without using a cocatalyst or the like. It is done.

Next, a specific manufacturing procedure will be described.

First, an alcoholic hydroxyl group-containing compound (A) and a diisocyanate (B) are charged in an excess amount of the isocyanate group relative to the hydroxyl group and subjected to urethane reaction at 20 to: LOO ° C. The reaction is carried out at 150 ° C. in the presence of the alophanation catalyst (C) until substantially no urethane groups are present. [0028] Here, "the amount in which the isocyanate group is excessive with respect to the hydroxyl group" means that the isocyanate group is excessive with respect to the hydroxyl group when the raw material is charged, and the molar amount of the isocyanate group and the hydroxyl group. A ratio of isocyanate group Z hydroxyl group = 8 or more is preferred, and 10 to 50 is particularly preferred.

[0029] The reaction temperature of the urethanization reaction is 20 to 120 ° C, preferably 50 to 100 ° C. In the urethanization reaction, a known so-called urethanization catalyst can be used. Specific examples thereof include organic metal compounds such as dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof.

[0030] The reaction time of the urethanization reaction varies depending on the presence and type of the catalyst and the reaction temperature, but is generally within 10 hours, preferably 1 to 5 hours is sufficient.

[0031] Upon completion of the urethane reaction, an allophanate reaction is performed. The alophanate reaction is carried out by adding the above-described alophanate catalyst (C) and a reaction temperature of 70 to 150 ° C, preferably 80 to 130 ° C. When the reaction temperature is too low, not a lot of allophanate groups are formed, and the average number of functional groups of the resulting polyisocyanate composition is lowered. When such a polyisocyanate is used as a coating curing agent, the coating film properties tend to be insufficient. If the reaction temperature is too high, the resulting polyisocyanate composition will unnecessarily give a thermal history, which not only wastes energy during production but also causes the polyisocyanate to become colored. There is. The average number of functional groups of polyisocyanate is the average number of isocyanate groups present in one molecule.

[0032] In the present invention, the urethanization reaction and the allophanate reaction can be carried out simultaneously. In this case, the alcoholic hydroxyl group-containing compound (A) and the organic diisocyanate (B) are charged in an amount in which the isocyanate group is excessive with respect to the hydroxyl group, and the catalyst is added to the alophanate catalyst (C In the presence of), the urethanation reaction and the alphaphanation reaction are carried out simultaneously.

[0033] The amount of the halophanation catalyst (C) used varies depending on the type, but 0.0005 to 1% by mass is preferable with respect to the total amount of the above (A) and (B). 0.1% by mass is more preferable. When the amount of the catalyst used is less than 0.0005% by mass, the reaction is substantially slow and it takes a long time, and coloring due to the thermal history may occur. On the other hand, if the amount of catalyst used exceeds 1% by mass However, the reaction control becomes difficult, and side reactions such as dimerization reaction (uretdione formation reaction) and trimerization reaction (isocyanuration reaction) may occur, and the resulting polyisocyanate is cured into a two-part paint. When used as an agent, problems such as shortening the pot life of the paint may occur.

[0034] The reaction time varies depending on the type of catalyst, the amount added, and the reaction temperature. Usually within 10 hours, preferably 1 to 5 hours is sufficient.

[0035] At this time, an organic solvent can be used as necessary. Examples of the organic solvent include aliphatic hydrocarbon organic solvents such as n-hexane and octane, alicyclic hydrocarbon organic solvents such as cyclohexane and methylcyclohexane, acetone, methyl ethyl ketone, and methyl isobutyl. Ketone organic solvents such as ketone and cyclohexanone, ester organic solvents such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate, ethylene glycol ether ether, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl Glycol ether ester organic solvents such as acetate and ethyl 3-ethoxypropionate, ether organic solvents such as jetyl ether, tetrahydrofuran and dioxane, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, odor Methyl iodide, methyl iodide , Harogeni spoon aliphatic hydrocarbon organic solvent such as Jikuroroetan, N- methylpyrrolidone, dimethylformamide, dimethyl § Seth, dimethyl sulfoxide, polar aprotic solvents such as hexa-methyl phosphonyl amides to. The solvent can be used alone or in combination of two or more.

[0036] After the alophanate reaction, the catalyst poison (D) is added to stop the alophanate reaction. The timing of addition of the catalyst poison (D) is not particularly limited as long as it is after the allophanate reaction, but when the thin film distillation method is used to remove free organic diisocyanate, the allophanate reaction is performed.

It is preferred to add the catalyst poison (D) later and before thin film distillation. This is to prevent side reactions from occurring due to heat during thin film distillation.

[0037] As the catalyst poison (D), known acids such as inorganic acids such as phosphoric acid and hydrochloric acid, organic acids having a sulfonic acid group, a sulfamic acid group and the like, esters thereof, and acyl halides can be used.

[0038] The amount of catalyst poison (D) added varies depending on the type and type of catalyst, but it is 0.5 to 2 A preferred amount is 0.8 to 1.5 equivalents. If the catalyst poison is too small, the storage stability of the resulting polyisocyanate tends to decrease. If the amount is too large, the resulting polyisocyanate may be colored.

[0039] In the present invention, basically, free organic diisocyanate is present in the product after the allophanate reaction. Since this free organic diisocyanate causes odor and turbidity with time, it is preferable to remove the unreacted organic diisocyanate (B) until the free organic diisocyanate content is 1% by mass or less.

[0040] As a method for removing free organic diisocyanate from OCR ■ II, there are known methods such as distillation, reprecipitation, extraction and the like.

Three

There is a method, and distillation, particularly thin-film distillation, 0 o c = is preferable because it can be performed without using a solvent or the like. Further, preferable thin film distillation conditions are pressure: 0.1 lkPa or less and temperature: 100 to 200 ° C, and particularly preferable conditions are pressure: 0.05 kPa or less and temperature: 120 to 180 ° C.

[0041] In the present invention, it is preferable to use a monooleic compound having 1 to 40 carbon atoms in (A) because the content of the bifunctional component (see the following formula) in the final product is 60% by mass or more. . The content of the bifunctional component is the ratio of the peak area of gel permeation chromatography (GPC), and the identification of the peak is determined on the assumption that the compound of the following formula is generated from the raw material.

[0042] [Chemical 1]

H

O C R-N-R 2-N C O

RR ₂ represents an organic diisocyanate residue which may be the same or different. R ₃ represents a monool residue. The alophanate-modified polyisocyanate composition obtained by the present invention preferably has a viscosity (25 ° C., solid content = 100% conversion) of 200 mPa ′s or less, particularly preferably 50 to 18 OmPa ′s. Further, Isoshianeto content (solid content = 100% basis) is preferably from 10 to 20 weight ^_0/0, and particularly preferably 12 to 18 wt%. [0044] When the introduction amount is constant, the viscosity of the allophanate-modified polyisocyanate composition is minimized when the compound used in (A) is a monool having about 6 to 8 carbon atoms. In the present invention, when a monooleic compound having 1 to: LO carbon atoms is used for (A), the viscosity of the obtained phanate-modified polyisocyanate composition at 25 ° C. is 130 mPa's or less. It becomes preferable.

[0045] The compound used in (A) improves the solubility of the obtained alophanate-modified polyisocyanate composition in a poor solvent in the order of methanol, ethanol, and propanol when the introduction amount of the allophanate group is constant. To do. In the present invention, (A) is preferably a monool compound having 3 to 40 carbon atoms. The poor solvent is a solvent in which ordinary polyisocyanate has low solubility, and examples thereof include aliphatic hydrocarbons, mineral spirits, kerosene, and petroleum-based mixed solvents.

[0046] The alophanate-modified polyisocyanate composition obtained by the present invention may be added to an antioxidant such as 2,6-di-tert-butyl-4-methylphenol, an ultraviolet absorber, a pigment, or a dye, if necessary. Additives such as solvents, flame retardants, hydrolysis inhibitors, lubricants, plasticizers, fillers, storage stabilizers and the like can be appropriately blended.

[0047] [Use of composition]

The alophanate-modified polyisocyanate composition obtained by the present invention is used for paints, adhesives, various binders, printing inks, magnetic recording media, coating agents, sealing agents, elastomers, sealants, synthetic leather, various leathers. Applicable to a wide range of foam, civil engineering foam fillers, etc. It is particularly suitable as a curing agent for high solid paints and a curing agent for turpentine paints.

Example

[0048] The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “%” means “% by mass”.

[Manufacture of alophanate-modified polyisocyanate]

Example 1

Capacity with stirrer, thermometer, cooler and nitrogen gas inlet tube: 1L reactor, hex 975 g of samethylene diisocyanate and 25 g of methanol were charged, and urethanization reaction was performed at 90 ° C for 2 hours. When the reaction product was analyzed by FT-IR, the hydroxyl group disappeared. Next, 0.2 g of power zirconium zirconium pyrrate (zirconium tetraoctylate, manufactured by Mitsuwa Chemicals, the same applies below) was charged and reacted at 90 ° C for 3 hours. When the reaction product was analyzed by FT-IR and 13C-NMR, the urethane group had disappeared. Subsequently, 0.1 g of phosphoric acid was charged, and a stop reaction was performed at 50 ° C. for 1 hour. The isocyanate content of the reaction product after the termination reaction was 42.1%. This reaction product was subjected to thin-film distillation at 130 ° C '0.04 kPa, the isocyanate content was 21.1%, the viscosity at 25 ° C was 118 mPa's, and the free hexamethylene diisocyanate content was 0. Polyisocyanate P-1 with 1%, 20APHA color number and 73% difunctional component was obtained. When P-1 was analyzed by FT-IR and 13C-NMR, the presence of a urethane group was not confirmed, and the presence of an allophanate group was confirmed. In addition, traces of uretdione groups and isocyanurate groups were observed. The results are shown in Table 1.

[0050] Examples 2-9

Using the raw materials and reaction conditions shown in Table 1, polyisocyanate P-2 to 9 were obtained by the same procedure as in Example 1. The results are shown in Table 1.

[0051] Example 10

The same reactor as in Example 1 was charged with 975 g of hexamethylene diisocyanate, 25 g of methanol, and 0.1 lg of strong zirconium pyrophosphate, and reacted at 90 ° C. for 5 hours. When the reaction product was analyzed by FT-IR and 13C-NMR, a hydroxyl group and a urethane group were not confirmed. Next, 0.05 g of phosphoric acid was added, and a stop reaction was performed at 50 ° C. for 1 hour. The isocyanate content of the reaction product after the termination reaction was 42.0%. This reaction product was subjected to thin-film distillation at 130 ° C '0.04kPa, the isocyanate content was 21.2%, the viscosity at 25 ° C was 112mPa's, and the content of free hexamethylene diisocyanate was 0. A polyisocyanate P-12 with 1%, 20 APHA color number and 72% difunctional component was obtained. When P-12 was analyzed by FT-IR and 13C-NMR, the presence of urethane groups was not confirmed, and the presence of allophanate groups was confirmed. In addition, traces of uretdione groups and isocyanurate groups were observed. The results are shown in Table 1.

[0052] Comparative Examples 1 to 4 Using the raw materials and reaction conditions shown in Table 2, the production operation was performed in substantially the same procedure as in Example 1. In P-11 and 12, since the allophanate reaction did not proceed, the operation after the distillation for removing the monomer was powerful. Table 2 shows the results for P-13 and P-14.

[0053] Comparative Example 5

The same reactor as in Example 1 was charged with 930 g of hexamethylene diisocyanate and 70 g of normal hexanol, and a urethane reaction was performed at 90 ° C. for 2 hours. When the reaction product was analyzed by FT-IR, the hydroxyl group disappeared. Next, it was heated to 160 ° C and reacted at the same temperature for 5 hours. The isocyanate content after the reaction was 40.7%. This reaction product was subjected to thin-film distillation at 130 ° C -0.04 kPa, the isocyanate content was 17.8%, the viscosity at 25 ° C was 84mPa's, and the content of free hexamethylene diisocyanate was 0.1% of polyisocyanate P-15 having a color number of 20 OAPHA and a bifunctional component of 68% was obtained. When P-15 was analyzed by FT-IR and 13C-NMR, it was also confirmed that a urethane equivalent of a strong phase equivalent to the presence of an allophanate group was present. The presence of uretdione groups was also confirmed, and the presence of isocyanurate groups was recognized to a trace. The results are shown in Table 2.

[0054] Comparative Example 6

A reactor similar to that in Example 1 was charged with 995 g of hexamethylene diisocyanate and 5 g of neopentyl glycol and subjected to urethane reaction at 90 ° C. for 2 hours. When the reaction product was analyzed by FT-IR, the hydroxyl group disappeared. Next, tributylphosphine was charged with 1. Og and reacted at 50 ° C for 14 hours. When the reaction product was analyzed by FT-IR and 13C-NMR, the presence of urethane groups, uretdione groups, and isocyanurate groups was confirmed. Further, 0.6 g of phosphoric acid was added, and the reaction was stopped at 50 ° C for 1 hour. The isocyanate content of the product was 42.1%. This reaction product was subjected to thin-film distillation at 130 ° C '0.04kPa, the isocyanate content was 22.3%, the viscosity at 25 ° C was 78mPa's, and the free hexamethylene diisocyanate content was 0. Polyisocyanate P-16 with 2% and 40 APHA color number was obtained. The results are shown in Table 2.

[0055] [Table 1] Real E example

1 2 3 4 5 6 7 8 9 1 0 Organic diisocyanate (g)

H D I 975 950 930 910 910 900 800 800 965 975 Hydroxyl-containing compound (g)

Methanol 25 25 Isopropanol 50

Normal hexanol 70 90

2-Ethylhexanol 90

Tridecanol 100

e P PG-400 200

Me P EG-400 200

1,3-Butanediol 35-arophaneization catalyst (g)

Power Zirconyl Pyrrate 0.2 0.2

(Mitsuwa Chemicals)

Catalyst poison (g)

Phosphoric acid 0.1 0.05 Isocyanate content before thin film distillation (%) 42.1 40.3 40.7 38.5 39.9 40.8 35.7 35.7 41.3 42.0 Polyisocyanate name P-1 P-2 P-3 P-4 P- 5 P-6 P-7 P-8 P-9 P-10 Manufacturing result

Isocyanate content (»21.1 19.3 17.7 17.2 16.7 14.6 10.5 10.6 20.2 21.2

Viscosity at 25 ° C (mPa-s) 118 105 79 120 110 160 171 183 2, 550 112 Free HD I content (%) 0.1 0.2 0.1 0.2 0.2 0.2 0.2 0.2 0.1 0.1 Color number (APHA) 20 10 20 20 20 20 30 40 10 20

Bifunctional component content 73 71 71 61 68 73 70 70 ― 72 Urethane group X X X X X X X X X X

O O O O O O O O O O

Functional group C: Δ △ Δ Δ Δ Δ Δ Δ △ Δ Isocyanurate group Δ 厶厶 Δ 厶厶厶 Δ Δ 厶

* Functional group: 0 → Ari △ —Trace level X—None 2]

Comparison example

1 2 3 4 5 6 Organic diisocyanate (g)

H D I 950 965 950 965 930 995 Hydroxyl-containing compound (g)

Isopropanol 50 50

1,3-Butanediol 35 35

Normal hexanol 70 Neopentyl glycol 5 alphaphanate catalyst (g)

Zirconyl acetate (Zr0 ₂ = 30%) Made by Daiichi Rare Elemental Chemistry 0.2

2-Ethylhexanoic acid IS 0.2

Isocyanurate catalyst (g)

Tributylphosphine 1.0 Catalyst poison (g)

Phosphoric acid 0.1 0.6 Isocyanate content before thin film distillation (¾) 40.5 41.6 40.5 41.5 40.7 42.1 Polyisocyanate name P- 11 P-12 P-13 P-14 P-15 P-16 Production result

Isocyanate content (%) 19.9 21.5 17.8 22.3

Viscosity at 25 ° C (mPa-s) No reaction progress 240 2840 84 78 Free HD I content (%) 0.2 0.2 0.1 0.2 Color number (APHA) Undistilled 20 10 200 40

Bifunctional component content 55 ― 68

Urethane group OO △ Δ O 〇 government ^ 其 * Alophaneate group Δ Δ OOOXH ^c "Uretodione group Δ Δ △ Δ OO Isocyanurate group △ Δ OO Δ O

* Functional group: o → Ari △ —Trace level X—None

[0057] In Tables 1 and 2

HDI: Hexamethylene diisocyanate

MePPG— 400: Methoxypolypropylene glycol

Number average molecular weight = 400

MePEG 400: Methoxypolyethylene glycol

Number average molecular weight = 400

Free HDI content: measured by gas chromatography (GC)

Bifunctional component content: GPC, power of raw materials calculated

Functional group: FT-IR, 13C- NMR peak intensity of each functional group is judged

[0058] The number of colors of the polyisocyanate composition in the examples was low L. Carbon number Polyisocyanates obtained using monools of 10 or less are all low in viscosity at 25 ° C of 13 OmPa · s or less, and have good workability when handling. It was. However, polyisocyanate produced using zirconyl acetate (Daiichi Rare Element Chemical Co., Ltd.)

Although urethanization proceeds, the effect as an allophanate catalyst is not recognized. In addition, comparing P-2 and P-13, which have the same yarn and different composition except for the catalyst, the one using 2-ethyl hexyl hexanoate has a high isocyanurate group content and a high viscosity. The active ingredient content was low!

[0059] [Storage stability test]

P-2 and P-13 were placed in a sealed container, and the void content was replaced with nitrogen, and the isocyanate content after storage at 50 ° C for 2 weeks was measured. As a result, P-2 decreased slightly from 19.4% to 19.3% by weight, while P-13 decreased significantly from 19.9% to 18.8% by weight. From this, it was found that when a zirconium tetracarboxylate-based catalyst (wherein the carboxylic acid has 6 or more carbon atoms) is used, an allophanate-modified polyisocyanate composition having excellent storage stability can be obtained.

[0060] [Thermal stability test]

Application Examples 1-10, Application Comparison Examples 1-4

The obtained polyisocyanate (excluding P-11 and 12) was heated at 150 ° C for 2 hours, and then the free HDI content was measured by GC. The results are shown in Tables 3 and 4.

[0061] [Table 3]

[0062] [Table 4] Application comparison example

1 2 3 4

Polyisocyanate P-13 P-14 P-15 P-16

Before heating 0. 2 0. 2 0. 1 0. 2

Free H D I content (%)

After heating 0. 3 0. 2 3. 4 15. 6

[0063] From Tables 3 and 4, it can be said that the polyisocyanate compositions in the examples have good thermal stability because the free HDI content before and after heating did not change significantly. On the other hand, P-15 and 16 have increased free HDI content after heating. This is probably due to the thermal decomposition of the uretdione group with low heat resistance.

[0064] [Poor solvent dissolution test]

Application Examples 11-16, Application Comparison Examples 5-8

The resulting polyisocyanate is dissolved in Solvent A (Nippon Mitsubishi Petroleum Mixed Solvent, poor solvent) with Polyisocyanate Z Solvent A = 1/2 (mass ratio) to confirm the appearance of the solution. did. The results are shown in Tables 5 and 6.

[0065] [Table 5]

[0066] [Table 6] Application comparison example

5 6 7 8 Polyisocyanate P-13 P-14 P-15 P-16 Appearance when diluted XXXX [0067] In Tables 5 and 6

Appearance: ○ → Completely dissolved to become a transparent solution.

X → Precipitation or turbidity occurs.

[0068] From Tables 5 and 6, the solubility of the polyisocyanate of Examples in a poor solvent was good. On the other hand, the solubility of the polyisocyanate of the comparative example in a poor solvent was good. From this result, the polyisocyanate of the example can be used as a curing agent for so-called turpentine paints.

[0069] [Evaluation of coating film]

Application Examples 17, 18

In the formulation shown in Table 7, polyisocyanate, acrylic polyol solution (Atalidic A-823, manufactured by Dainippon Ink and Chemicals, solid content = 50%, hydroxyl value = 30 mgKOHZg), and butyl acetate are mixed to form a solid A min = 50% Talia paint was prepared. After that, the prepared coating was applied on a steel plate and allowed to stand at 20 ° C and 65% RH for 1 week to obtain a test piece on which a coating film having a dry film thickness of 30 to 40 µm was formed. . The obtained test piece was subjected to the following tests. The results are shown in Table 7.

[0070] [Table 7]

Application examples

1 7 18 Acrylic polyol solution (g) 100

Curing agent (g)

P— 2 19. 3

P— 9 18. 3 Butyl acetate (g) 19. 3 18. 3 Coating evaluation

Pencil hardness HB H Adhesion 100 100 Flexibility 〇〇 Erichsen value 9 Material break 9 Material break Test items and methods are as follows.

• Pencil hardness test:

The tip of the pencil specified in JIS S-6006 was extruded at an angle of 45 degrees, and the hardness of the pencil with the highest hardness at which the coating did not break was defined as the coating hardness.

• Adhesion test:

Using a cutter knife with a cutter guide on the coating film, make 100 square cuts in 1 mm square, press the cellophane tape on top of it, and then peel it off instantaneously to determine the number of remaining coating film pieces. I counted.

• Eriksen value:

The steel ball was also pressed slowly against the back surface of the painted surface, and the extrusion distance of the steel ball when the coating film was cracked or peeled off was measured.

'Bend resistance:

With the painted surface facing up, apply the coating plate to a 2mm diameter rod, fold it 180 degrees, crack the coating, The peeling was examined.

Evaluation: ○ → No change X → There are cracks and peeling

[0072] From Table 7, the coating film using the polyisocyanate of the example had good physical properties.

[0073] As described above, the polyisocyanate composition obtained by the present invention had a good appearance. In addition, polyisocyanate composition obtained using monool having 10 or less carbon atoms

The product was particularly low in viscosity. Further, the polyisocyanate composition obtained using monool having 3 to 40 carbon atoms had good solubility in a poor solvent.

Claims

The scope of the claims

[1] In a method for producing an allophanate-modified polyisocyanate composition from an alcoholic hydroxyl group-containing compound (A) and an aliphatic and Z or alicyclic diisocyanate (B) using an allophanate catalyst (C) The alfaphanate catalyst (C) is a zirconium tetracarboxylate, the carboxylic acid has 6 or more carbon atoms, and the catalyst poison (D) is used when stopping the alfaphanate reaction. Production method.

[2] The production method according to claim 1, wherein the free organic diisocyanate (B) is removed until the content becomes 1% by mass or less after the allophanatization reaction is stopped.

[3] (A) is a monooleic compound having 1 to 40 carbon atoms, and the obtained allophanate-modified polysocyanate composition contains 60% by mass or more of a bifunctional component. 2. The production method according to 2.

[4] (A) is a mono-ol compound having 1 to C carbon atoms, and the viscosity of the obtained allophanate-modified polysocyanate composition at 25 ° C. is 130 mPa's or less. The manufacturing method in any one of Claims 1-3.

[5] (A) is a monooleic compound having 3 to 40 carbon atoms, and the obtained allophanate-modified polysocyanate composition is soluble in a poor solvent, The manufacturing method of crab.