JPH06192364A - Blocked polyisocyanate composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, comprising a specific quaternary ammonium compound and a curing catalyst, having low toxicity and a low curing temperature, excellent in alkali, frictional and fouling resistance and useful as coatings, adhesives, etc. CONSTITUTION:The objective composition comprises (A) a quaternary ammonium compound of formula I (R1 to R3 are >=4C hydrocarbon, etc.; R4 is H, 1-20C hydrocarbon, etc.; X is hydroxyl group or carboxylate or phenolate having 1-20C hydrocarbon group) such as 2-hydroxyethyl-tri-n-butylammonium-2,2- dimethylpropionate and further preferably (B) an organotin compound of formula II [R1 to R4 are >=4C hydrocarbon, carboxylate having 1-20C hydrocarbon, etc.) such as dibutyltin diacetate as a curing catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blocked isocyanate useful as a one-part bake-curable urethane resin in the industrial field of paints, fibers, adhesives and the like.

[0002]

2. Description of the Related Art Conventionally, polyurethane resin paints have very excellent abrasion resistance, chemical resistance and stain resistance, especially polyurethane using polyisocyanates derived from aliphatic and alicyclic isocyanates. The paint has excellent weather resistance. However, since polyisocyanate has a very active isocyanate group, it is unstable with respect to moisture and has a disadvantage such as a short pot life. In order to improve such a defect, a blocked polyisocyanate in which all active isocyanate groups are blocked with an active hydrogen compound (hereinafter referred to as a blocking agent) has been studied.

Generally, oximes, phenols, alcohols, lactams, amide compounds and the like are known as such blocking agents. The blocked polyisocyanate dissociates the blocking agent at a relatively high temperature, the active isocyanate group is regenerated, and the crosslinking reaction with the polyol occurs, so that the above-mentioned drawbacks are temporarily improved. But,
The curing requires heating at a considerably high temperature, which consumes a large amount of energy for heating and may cause thermal deterioration of product quality such as color burn.

Therefore, it has been desired to develop a blocked polyisocyanate in which the blocking agent is dissociated by heating at a lower temperature to regenerate the isocyanate. The aromatic isocyanate-based block polyisocyanate is superior to the aliphatic and alicyclic isocyanate-based block polyisocyanates in low-temperature curability, but has a drawback that the weather resistance of the coating film is poor.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to develop a block polyisocyanate which is more curable at a lower temperature than conventional ones and which can reduce the problem of color burning during printing and which is energy-saving. It is a task to do.

[0006]

Accordingly, the inventors of the present invention have focused on the above-mentioned problems, and combine an aliphatic and alicyclic isocyanate type block polyisocyanate with a curing catalyst having a low curing temperature and a low toxicity. Thus, the present invention was completed by obtaining a blocked polyisocyanate having a low curing temperature and low toxicity.

[0007]

Specifically, the present invention is an aliphatic and / or alicyclic isocyanate-based blocked polyisocyanate composition containing a quaternary ammonium compound represented by the following general formula [1] as a curing catalyst.

General formula [1]

[Chemical 5]

(Any one of R 1, R 2 and R 3 is a hydrocarbon group having 4 or more carbon atoms or a hydrocarbon group having 4 or more carbon atoms containing a hetero atom such as nitrogen, oxygen or sulfur, and the others are 1 carbon atoms. ~ 20 hydrocarbon groups, R1, R2 and R
3 may be connected to each other. R4 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydroxyl group having 1 carbon atom
To 20 hydrocarbon groups, X is a hydroxyl group, and has 1 to 2 carbon atoms.
It is a carboxylate having 0 hydrocarbon groups or a phenolate. )

Preferably, R1, R2 and R of the general formula [1]
A quaternary ammonium compound represented by the general formula [2], wherein 3 is a hydrocarbon group having 4 carbon atoms, R 4 is a hydrogen atom or a methyl group, and X is a carboxylate having a hydrocarbon group having 1 to 20 carbon atoms. A block polyisocyanate composition comprising as a curing catalyst,

General formula [2]

[Chemical 6]

Further, X in the general formula [2] has 1 to 20 carbon atoms.
It is preferable that the blocked polyisocyanate composition contains as a curing catalyst the quaternary ammonium compound which is a tertiary carboxylate having a hydrocarbon group.
An aliphatic and / or alicyclic isocyanate-based blocked polyisocyanate composition containing a quaternary ammonium compound represented by the general formula [1] and an organotin compound represented by the general formula [3] as a curing catalyst is also provided. Included in the present invention.

General formula [3]

[Chemical 7] (Any one of R1 to R4 is a hydrocarbon group having 4 or more carbon atoms and the other has a hydrocarbon group having 1 to 20 carbon atoms, a carboxylate, an alkylmaleate, an alkylthioglycolate or an alkylthiopropionate. Is an organic acid residue such as.)

Preferably, R1 of the general formula [1],
R2 and R3 are hydrocarbon groups having 4 carbon atoms, R4 is a hydrogen atom or a methyl group, and X is a carboxylate having a hydrocarbon group having 1 to 20 carbon atoms; ] A blocked polyisocyanate composition containing an organotin compound represented by the following as a curing catalyst, and X in the general formula [1] is a tertiary carboxylate having a hydrocarbon group having 1 to 20 carbon atoms. A blocked polyisocyanate composition containing a quaternary ammonium compound and an organotin compound represented by the general formula [3] is also preferably used.

Further, any one to one of R1 to R4 represented by the general formula [3] is a hydrocarbon group having 8 carbon atoms, and the other is a carboxylate or alkyl having a hydrocarbon group having 1 to 20 carbon atoms. Blocked polyisocyanate composition characterized by being an organic acid residue such as malate, alkylthioglycolate or alkylthiopropionate, and any one of R1 to R4 represented by the general formula [3].
The present invention also includes a blocked polyisocyanate composition in which one is a hydrocarbon group having 8 carbon atoms and the other is an acetyl group.

Further, these curing catalysts mentioned above are added in a weight ratio of 0.3 to 1 with respect to the solid content of the blocked polyisocyanate.
It is a blocked polyisocyanate composition characterized by containing in an amount of 0.0%.

The present invention will be described in more detail below. So far, 3 such as triethylamine and triethylenediamine
When a mixture of a primary amine and an organic tin compound such as dibutyltin dilaurate or dibutyltin diacetate is used as a curing catalyst for a blocked polyisocyanate, the catalytic effect is more effective than when each is used alone. Urethane Sci
ence and Technology, Vol.
1,1. Stanford, Conn. , (1971)
It is described in.

However, since these tertiary amines have a strong odor, they are troublesome to handle, and when they remain in the cured coating film due to their strong hygroscopicity, they may cause deterioration in coating performance such as water resistance, acid resistance and alkali resistance. Cause a decline. On the other hand, since the quaternary ammonium compound represented by the general formula [1] and / or [2] has a low solubility in water, the coating film performance as described above is not deteriorated. In addition, choline compounds such as quaternary ammonium compounds have no problem in terms of safety to living bodies. Further, the catalytic effect when the quaternary ammonium compound represented by the general formula [1] and / or [2] is used in combination with the organic tin compound is larger than that in the case of other tertiary amines.

In particular, since the quaternary ammonium compound of the general formula [1] and / or [2] has a hydroxyl group in the molecule, it reacts with the isocyanate group regenerated at the time of baking, so that it is free in the coating film. The quaternary ammonium compound has the feature that it does not remain and does not adversely affect the physical properties of the coating film. . Further, any one of R1, R2 and R3 in the general formula [1] is a hydrocarbon group having 4 or more carbon atoms, or a hydrocarbon group having 4 or more carbon atoms containing a hetero atom such as nitrogen, oxygen or sulfur. In this case, even if the film is thermally decomposed to form a tertiary amine during baking, it has a high boiling point and thus has an advantage that no odor is generated.

R4 in the general formula [1] is a hydrogen atom,
It is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms including a hydroxyl group. Furthermore, 4 represented by the general formula [1] and / or [2]
When a primary ammonium compound is mixed in the block polyisocyanate and heated, the blocking agent dissociates to form an isocyanate group, which initiates an isocyanurate-forming reaction, and is effective as a curing catalyst for the block polyisocyanate because curing proceeds. . The following are typical examples of the quaternary ammonium compound.

2-hydroxyethyl tri-n-butylammonium 2,2-dimethylpropionate, 2-
Hydroxyethyl tri-n-butylammonium ・ 2,
2-dimethylbutanoate, 2-hydroxypropyl
Tri-n-butylammonium-2,2-dimethylpropionate, 2-hydroxypropyl-tri-n-butylammonium-2,2-dimethylbutanoate, 2-hydroxypropyl-tri-n-butylammonium-2,2
-Dimethylpentanoate, 2-hydroxypropyl
Tri-n-butylammonium 2-ethyl 2-methylpropionate,

2-hydroxypropyl tri-n-butylammonium 2-ethyl 2-methylbutanoate, 2
-Hydroxypropyl tri-n-butylammonium
2-ethyl 2-methylpentanoate, 2-hydroxypropyl tri-n-octyl ammonium-2,2-dimethylpropionate, 2-hydroxypropyl tri-n-octyl ammonium-2,2-dimethylbutanoate, 2-hydroxypropyl-triamylammonium-2,2-dimethylbutanoate, 2-hydroxypropyl-triamylammonium-2,2-dimethylpentanoate,

2-Hydroxybutyl triisoamyl ammonium-2,2-dimethylbutanoate, 2-hydroxybutyl triisoamyl ammonium-2,2-
Dimethyl pentanoate, 2-hydroxypentyl triisoamyl ammonium-2,2-dimethylbutanoate, 2-hydroxypentyl triisoamyl ammonium-2,2-dimethylpentanoate, 2-hydroxypropyl tripentyl ammonium- 2,2-dimethylbutanoate, 2-hydroxypentyl-tripentylammonium-2,2-dimethylpentanoate, 2-hydroxyoctyl-tri-n-butylammonium-2,2-dimethylpropionate,

2-Hydroxyoctyl-tri-n-butylammonium-2,2-dimethylbutanoate, 2-hydroxypropyl-tri-n-butylammonium-para-t-butylbenzoate, 2-hydroxypropyl-tri-n-butylammonium -Para-t-butylbenzoate, 2-hydroxybutyl-tri-n-butylammonium-para-t-pentylbenzoate, 2-hydroxypropyl-tri-n-butylammonium-para-t-pentylbenzoate, 2-hydroxybutyl-tri-n-butyl Ammonium para t-hexyl benzoate, 2-
Hydroxypropyl tri-n-butylammonium para-t-hexylbenzoate and the like.

The following are typical examples of the organic tin compound. : Monobutyltin triacetate, dibutyltin diacetate, tributyltin monoacetate, dibutyltin di (n-methylmalate), monobutyltin tri (methyl glycolate), monobutyltin tri (methyl propionate), monobutyltin trilaurate, Dibutyltin dilaurate, tributyltin monolaurate, dibutyltin di (n-butyl maleate), monobutyltin tri (butyl glycolate), monobutyltin tri (butyl propionate),

Monohexyltin trioctoate, dihexyltin dioctoate, trihexyltin monooctoate, dihexyltin di (n-octyl maleate), monohexyltin tri (octyl glycolate), monohexyltin tri (octyl propio) Nate), monooctyltin triacetate, dioctyltin diacetate, trioctyltin monoacetate, dioctyltin di (n-methylmalate), monooctyltin tri (methyl glycolate), monooctyltin tri (methyl propionate), monooctyltin Tripropionate, dioctyltin dipropionate, trioctyltin monopropionate,

Dioctyltin di (n-propyl maleate), monooctyltin tri (propyl glycolate), monooctyltin tri (propyl propionate), monooctyltin trioctoate, dioctyltin dioctoate, trioctyltin mono Octoate, dioctyltin di (n-octyl malate), monooctyltin tri (octyl glycolate), monooctyltin tri (octylpropionate), monooctyltin trilaurate, dioctyltin dilaurate,

Examples include trioctyltin monolaurate, dioctyltin di (n-lauryl malate), monooctyltin tri (lauryl glycolate), monooctyltin tri (lauryl propionate) and the like. Among the above-mentioned organic tin compounds, dibutyltin diacetate, dibutyltin dilaurate and the like, which are commonly used as a urethanization catalyst, have a drawback that they have a strong odor and that they are heavy metal compounds and therefore highly toxic. On the other hand, octyltin compounds are generally known to have low toxicity among organic tin compounds, and have been used as stabilizers for vinyl chloride sheets for food packaging.

The compounds preferably used in the present invention are octyltin compounds such as low toxicity monooctyltin triacetate, dioctyltin diacetate and trioctyltin monoacetate. Especially, dioctyltin diacetate is not only low toxicity but also blocked isocyanate. It is effective as a curing catalyst.

The curing catalyst used in the present invention is a quaternary ammonium compound of the general formula [1] and / or [2] alone or a mixed catalyst of these and an organic tin compound. When the quaternary ammonium compound and the organotin compound are used as a mixed catalyst, the mixing molar ratio is 1/9 to 9 /.
1, preferably 2/8 to 8/2, more preferably 3/7
It is desirable to be within the range of 7/3.

The content of the curing catalyst with respect to the block polyisocyanate is 0.3 to 10 in terms of weight fraction with respect to the solid content of the block polyisocyanate as a quaternary ammonium compound alone or as a mixed catalyst of these and an organic tin compound. It is desirable to set it in the range of 0.0%, and 0.5
It is more preferable to set the content to ˜7.0%. When the amount of the catalyst is small, the performance as a curing catalyst is not sufficiently exhibited, and when it is excessively large, the storage stability of the blocked polyisocyanate is deteriorated, which is not desirable.

The aliphatic and alicyclic isocyanate-based blocked polyisocyanate referred to in the present invention is a compound obtained by blocking the active isocyanate group in the aliphatic and alicyclic isocyanate-based polyisocyanate with a blocking agent. Any commonly used aliphatic or alicyclic isocyanate-based polyisocyanate can be widely used in the present invention. Representative examples of these include aliphatic and alicyclic isocyanate-based adduct-type polyisocyanates, aliphatic and alicyclic isocyanate-based isocyanurate-type polyisocyanates, and the like.

Typical aliphatic and alicyclic isocyanate monomers constituting the polyisocyanate include the followings. That is, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3- or 1,4-diisocyanate cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, m- or p -Tetramethyl xylene diisocyanate, 1,4-tetramethylene diisocyanate,

Isocyanate monomers such as 1,12-dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylcyclohexane diisocyanate. Examples of preferable blocking agents include oximes (methyl ethyl ketone oxime, butanone oxime), monophenols (phenol, cresol), tertiary alcohols (t-butanol, dimethylphenylcarbonal), aromatic secondary amines (N-methylaniline). , N-methylxylylene), imide (succinimide),

Examples thereof include lactam (ε-caprolactam, σ-valerolactam), mercaptan (methyl mercaptan, ethyl mercaptan), triazole and the like. When using a blocked polyisocyanate obtained by blocking an aliphatic and alicyclic isocyanate-based isocyanurate type polyisocyanate with a blocking agent, for example, as a coating resin, the polyol used as the main component is, for example, an alkyd resin or a polyester polyol such as polycaprolactone polyol. , A polyether polyol obtained from polyethylene polyol, polypropylene polyol, etc.,

An acrylic polyol obtained by copolymerizing a vinyl monomer having a hydroxyl group with another vinyl monomer can be used. Further, other curable resin such as melamine resin may be added to the composition of the present invention for the purpose of enhancing curability. Furthermore, the blocking reaction of the polyisocyanate of the present invention can be carried out at a reaction temperature of 20 to 150 ° C., which is a usual blocking reaction temperature, preferably at a temperature of 40 ° C. or higher.

The reaction can be carried out without a solvent, but when the reaction is carried out using a solvent, esters such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, toluene, Aromatics such as xylene,
Ketones such as methyl ethyl ketone are preferably used. If necessary, a suitable catalyst, for example, an amine catalyst such as triethylamine or triethylenediamine or a tin catalyst such as dibutyltin diacetate or dibutyltin dilaurate may be added to carry out the reaction. The amount of catalyst added is preferably in the range of 0.1 to 1.0% by weight with respect to the solid content.

The blocked polyisocyanate of the present invention is based on paints (for automobiles, automobile repairs, woodworking, can manufacturing, precoat metal and building exterior, etc.), adhesives (laminate type adhesives, natural or synthetic rubbers). It is useful as an additive for adhesives, for wood and structures, and as a fiber processing agent.

[0039]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples.
This will be described more specifically. In the following, all parts and% are based on weight unless otherwise specified.

Example 1 (1) Synthesis of Block Polyisocyanate Bernock DN-901S (manufactured by Dainippon Ink and Chemicals, Inc .: Aliphatic isocyanurate type polyisocyanate, viscosity: W (Gardner), NCO value: 23.0
%) After dissolving 100 parts in 63.3 parts butyl acetate,
By charging 47.7 parts of methyl ethyl ketone oxime (MEKO), the remaining active isocyanate groups are blocked, and the desired blocked polyisocyanate (nonvolatile component 7
0.1%) was obtained.

100 parts of the blocked polyisocyanate obtained in (1), Acridic A-801 (manufactured by Dainippon Ink and Chemicals, Inc .: acrylic polyol, viscosity: R
(Gardner), OH value: 50 (varnish)) 291.
3 parts, 0.78 parts of dioctyl tin diacetate, 2-
Hydroxypropyl tri-n-butylammonium
0.62 parts of 2,2-dimethylpentanoate and 41.4 parts of butyl acetate are blended. The compounded liquid (nonvolatile content: 50.0%) showed a uniform and slightly yellow characteristic color, and showed Gardner viscosity DE. The compounded liquid was allowed to stand at 40 ° C. for 1 month, but no change was observed in its viscosity.

(2) Baking and Curing Experiment of Blocked Polyisocyanate After immersing a wire net in the compounding solution and drying it, the composition was baked and cured at 120 ° C. and 140 ° C., and then the uncured resin was extracted overnight in acetone. The gel fraction measured by the above is shown in Table 1. Further, a coating film was formed on a tin plate with a bar coder (film thickness 31 μm), and the coating film baked and cured at 140 ° C. for 30 minutes was subjected to an alkali resistance test for 48 hours with a 5% NaOH aqueous solution. Show.

(Example 2) 100 parts of the blocked polyisocyanate obtained in (1) of Example 1, 291.3 parts of Acridic A-801, 0.79 parts of dioctyltin diacetate, and 2-hydroxy. Propyl tri n
-Butyl ammonium-2,2-dimethylbutanoate (0.61 parts) and butyl acetate (41.4 parts) are blended. The formulation had a uniform, slightly yellow characteristic color and a Gardner viscosity DE. (Nonvolatile content 50.0%). The compounded liquid was allowed to stand at 40 ° C. for 1 month, but no change was observed in its viscosity.

In the same manner as in Example 1, the wire net was dipped in the compounded solution, dried, baked and cured at 120 ° C. and 140 ° C., and then the uncured resin was extracted overnight in acetone for measurement. The gel fraction is shown in Table 1. Also, make a coating film on the tin plate with a bar coder (film thickness 32 μm), 140 ° C
Table 3 shows the results of the alkali resistance test of the coating film baked and cured for 30 minutes in a 5% NaOH aqueous solution for 48 hours.

Example 3 (1) Synthesis of Block Polyisocyanate IPDI T-1890 100 (manufactured by Daicel Huls Co., Ltd .: alicyclic isocyanurate type polyisocyanate, pellet, NCO value: 17.0% ) 100 parts was dissolved in 58.0 parts butyl acetate, and then 35.3 parts of methyl ethyl ketone oxime (MEKO) was charged to block the remaining active isocyanate groups, thereby obtaining the desired blocked polyisocyanate (non-volatile content of 70.1%). ) Got.

100 parts of the blocked polyisocyanate obtained in (1) and 235% of Acrydeic A-801.
2 parts, dioctyl tin diacetate 0.77 parts, 2-
Hydroxypropyl tri-n-butylammonium
0.63 parts of 2,2-dimethylpentanoate and 41.4 parts of butyl acetate are blended. (Nonvolatile content 50.1%) The mixed solution was uniform and showed a slight yellow characteristic color, and showed Gardner viscosity EF. The compounded liquid was allowed to stand at 40 ° C. for 1 month, but no change was observed in its viscosity.

(2) Baking and Curing Experiment of Block Polyisocyanate As in Example 1, the wire net was dipped in the compounding solution and dried, and then baked and cured at 120 ° C. and 140 ° C., and then overnight in acetone. The gel fraction measured by extracting the uncured resin in Table 1 is shown in Table 1. Further, a coating film was formed on a tin plate with a bar coder (film thickness 30 μm), and the coating film baked and cured at 140 ° C. for 30 minutes was subjected to an alkali resistance test for 48 hours with a 5% NaOH aqueous solution. Show.

(Example 4) 100 parts of the blocked polyisocyanate obtained in (1) of Example 1, 291.3 parts of Acridic A-801, 2-hydroxypropyl tri-n-butylammonium-2, 2.10 parts of 2-dimethylpentanoate and 41.4 parts of butyl acetate are blended. The formulation has a uniform, slightly yellow characteristic color,
The Gardner viscosity was A2-A3. (Nonvolatile content 49.
9%). The compounded liquid was allowed to stand at 40 ° C. for one month, but no change was observed in its viscosity.

In the same manner as in Example 1, the wire net was dipped in the compounded solution, dried, baked and cured at 120 ° C. and 140 ° C., and then the uncured resin was extracted overnight in acetone for measurement. The gel fraction is shown in Table 1. Also, make a coating film on the tin plate with a bar coder (film thickness 30 μm) and 140 ° C.
Table 3 shows the results of the alkali resistance test of the coating film baked and cured for 30 minutes in a 5% NaOH aqueous solution for 48 hours.

Comparative Example 1 100 parts of the blocked polyisocyanate obtained in (1) of Example 1, 291.3 parts of Acridic A-801, 1.06 parts of dioctyltin diacetate, 1,4 -Diazabicyclo [2,2
2,2] octane 0.34 parts, butyl acetate 41.4
Compound. The compounded solution was uniform and showed a slight yellow characteristic color, and showed Gardner viscosity DE (nonvolatile matter: 50.0).
%).

After immersing the wire mesh in the compounded solution and drying it, after baking and hardening at 120 ° C. and 140 ° C.,
The gel fraction measured by extracting the uncured resin in acetone overnight is shown in Table 2. Further, a coating film was prepared on a tin plate with a bar coder (film thickness 29 μm), and the coating film baked and cured at 140 ° C. for 30 minutes was subjected to an alkali resistance test for 48 hours with a 5% NaOH aqueous solution. Show.

Comparative Example 2 100 parts of the blocked polyisocyanate obtained in (1) of Example 1, 291.3 parts of Acridic A-801, 1,4-diazabicyclo [2,2,2] octane 2.10 parts and 41.4 parts of butyl acetate are blended. The formulation had a uniform, slightly yellow characteristic color and a Gardner viscosity DE. (Nonvolatile content: 50.0%) After immersing a wire net in the liquid mixture and drying it, after baking and hardening at 120 ° C and 140 ° C,
The gel fraction measured by extracting the uncured resin in acetone overnight is shown in Table 2.

Further, a coating film was formed on a tin plate with a bar coder (film thickness 30 μm), and baked on and cured at 140 ° C. for 30 minutes to absorb the absorbent cotton (diameter about 3 cm) impregnated with 5% NaOH aqueous solution. Table 3 shows the results of carrying out the alkali resistance test (spot test) for 48 hours by sealing the test piece in a glass container to prevent evaporation of water.

[0054]

[0055]

[0056] Baking conditions: 140 ° C x 30 minutes Spot test: 48 hours Evaluation was done by visual inspection, ⊚ when no change was observed in the coating, ◯ when slight change was observed on the surface of the coating, and clear whitening of the coating. The ones that were tested or those in which the liquid penetrated into the tin plate and corrosion was observed were marked with x.

[0057]

EFFECTS OF THE INVENTION The present invention has a low curing temperature, is an energy-saving type, has excellent properties of the coating film such as alkali resistance of the cured coating film, and has low toxicity, and is used as a coating material (for automobiles and automobile repairs). , Woodworking, can manufacturing, pre-coated metal and building exteriors, etc.), adhesives (laminate type adhesives, natural or synthetic rubber-based adhesive additives, for wood and construction, etc.), textile finishing agents It is possible to provide a blocked polyisocyanate useful for, for example,

Claims (9)

[Claims] 1. An aliphatic and / or alicyclic isocyanate block polyisocyanate composition comprising a quaternary ammonium compound represented by the following general formula [1] as a curing catalyst. General formula [1] (Any one of R1, R2 and R3 is a hydrocarbon group having 4 or more carbon atoms or a hydrocarbon group having 4 or more carbon atoms containing a hetero atom such as nitrogen, oxygen or sulfur, and the others are 1 to 2 carbon atoms.
It is a hydrocarbon group of 0, and R1, R2 and R3 may be linked to each other. R4 is a hydrogen atom, having 1 to 20 carbon atoms
Is a hydrocarbon group having 1 to 20 carbon atoms, or a hydroxyl group, and X is a carboxylate having a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, or a phenolate. ) 2. R1, R2 and R3 in the general formula [1] have 4 carbon atoms.
Of the general formula [2], wherein R4 is a hydrogen atom or a methyl group, and X is a carboxylate having a hydrocarbon group of 1 to 20 carbon atoms, as a curing catalyst. The blocked polyisocyanate composition according to claim 1, which comprises: General formula [2] 3. The blocked polyisocyanate according to claim 1, which comprises as a curing catalyst a quaternary ammonium compound in which X in the general formula [2] is a tertiary carboxylate having a hydrocarbon group having 1 to 20 carbon atoms. Composition. 4. An aliphatic and / or alicyclic isocyanate block poly containing a quaternary ammonium compound represented by the general formula [1] and an organotin compound represented by the general formula [3] as a curing catalyst. Isocyanate composition. General formula [1] (Any one of R1, R2 and R3 is a hydrocarbon group having 4 or more carbon atoms or a hydrocarbon group having 4 or more carbon atoms containing a hetero atom such as nitrogen, oxygen or sulfur, and the others are 1 to 2 carbon atoms.
It is a hydrocarbon group of 0, and R1, R2 and R3 may be linked to each other. R4 is a hydrogen atom, having 1 to 20 carbon atoms
Is a hydrocarbon group having 1 to 20 carbon atoms, or a hydroxyl group, and X is a carboxylate having a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, or a phenolate. ) General formula [3] (Any one of R1 to R4 is a hydrocarbon group having 4 or more carbon atoms and the other has a hydrocarbon group having 1 to 20 carbon atoms, a carboxylate, an alkylmaleate, an alkylthioglycolate or an alkylthiopropionate. Is an organic acid residue such as.) 5. R1, R2 and R3 in the general formula [1] have 4 carbon atoms.
Is a hydrocarbon group, R4 is a hydrogen atom or a methyl group, and X is a carboxylate having a hydrocarbon group having 1 to 20 carbon atoms, and a quaternary ammonium compound and an organotin represented by the general formula [3]. 5. A compound comprising a compound
The blocked polyisocyanate composition described. 6. A quaternary ammonium compound in which X in the general formula [1] is a tertiary carboxylate having a hydrocarbon group having 1 to 20 carbon atoms and an organotin compound represented by the general formula [3]. 6. The blocked polyisocyanate composition according to claim 5. 7. A carboxylate in which any one of R1 to R4 represented by the general formula [3] is a hydrocarbon group having 8 carbon atoms and the other has a hydrocarbon group having 1 to 20 carbon atoms, or The blocked polyisocyanate composition according to any one of claims 4 to 6, which is an organic acid residue such as alkyl malate, alkyl thioglycolate, or alkyl thiopropionate. 8. Any one of R1 to R4 represented by the general formula [3] is a hydrocarbon group having 8 carbon atoms, and the other is an acetyl group. One of
The blocked polyisocyanate composition according to the item. 9. The blocked polyisocyanate according to claim 1, wherein the curing catalyst is contained in a weight fraction of 0.3 to 10.0% with respect to the solid content of the blocked polyisocyanate. Composition.