JPH0730161B2 - Heat-reactive aqueous composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat treatment containing a blocked isocyanate compound in which an isocyanate group of a tetramethylxylylene diisocyanate compound is blocked with an oxime compound, an aqueous auxiliary agent and water. It relates to a reactive aqueous composition.

(Prior Art) Isocyanate compounds are useful as cross-linking agents and modifiers, and elastomers obtained from them are flexible,
Widely used because of its flexibility and adhesiveness.

On the other hand, since these isocyanate compounds exist or are used in water, isocyanate compounds obtained by blocking these isocyanate groups with a blocking agent are considered to be useful and used.

The blocked isocyanate compound, toluene diisocyanate, those blocked aromatic isocyanate compounds such as diphenylmethane diisocyanate,
Examples thereof include isocyanate compounds obtained by blocking an isocyanate compound such as hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, which are aliphatic, alicyclic, araliphatic, and the like.

The former has an advantage that the blocking agent is dissociated in a low temperature region, but has a drawback that it turns yellow due to heat, light, etc., and its use is limited. On the other hand, the latter has the advantage that it is resistant to heat, light, etc. and hardly discolors, and is particularly useful for clothing applications and other applications in which discoloration is not allowed, but dissociation of the half-face blocking agent requires high temperature. Therefore, the processing conditions are limited, and the application or the material that gives them is also limited.Because the dissociation of the blocking agent is high, depending on the processing conditions, it may be used as a cross-linking agent or a modifying step. However, there is a problem that sufficient characteristics cannot be obtained for use in.

Therefore, under the present circumstances, there is a demand for a material that is resistant to heat, light, etc., exhibits almost no discoloration, and exhibits properties such as dissociation of a blocking agent in a low temperature range.

(Problems to be solved by the present invention) As a result of intensive studies, the present invention has resistance to heat, light, etc.,
A specific tetramethylxylylene diisocyanate compound among araliphatic compounds that hardly discolor is allowed to exist stably in water as an aqueous composition, and compared with the conventionally used aliphatic, alicyclic, araliphatic, etc. Therefore, it is an object of the present invention to solve the problems that the blocking agent dissociates in a low temperature range, the treatment conditions and the range of materials used are limited, and sufficient properties as a crosslinking agent and a modifier cannot be obtained. is there.

(Means and Actions for Solving the Problem) The heat-reactive aqueous composition of the present invention comprises (A) an isocyanate group of 12% by weight (hereinafter abbreviated as%).
The gist of the present invention is to contain a blocked isocyanate-based compound obtained by blocking the isocyanate group of the tetramethylxylylene diisocyanate-based compound contained with an oxime-based compound, (B) an aqueous hydration aid, and (C) water. .

As the tetramethylxylylene diisocyanate compound containing 12% or more of isocyanate groups used in the present invention (hereinafter, abbreviated as a specific TMXDI compound), tetramethylxylylene diisocyanate (hereinafter, abbreviated as TMXDI), the TMXDI and carbon Examples thereof include compounds containing 12% or more of isocyanate groups obtained by reacting with a glycol component of several 6 or less.

When the isocyanate group content in the TMXDI-based compound is less than 12%, the finally obtained heat-reactive aqueous composition of the present invention has insufficient performance when used as a crosslinking agent or a modifier, Not preferable.

Specific examples of the glycol component having 6 or less carbon atoms include:
For example, ethylene glycol, propylene glycol, 1.4 or 1.3-butanediol, pentanediol,
Examples include hexanediol.

These heat-reactive aqueous compositions of the present invention in which the glycols having 6 or less carbon atoms are finally obtained can be used, for example, as water-soluble or water-dispersible synthetic polymers, water-soluble natural polymers and their derivatives. When mixed to improve water resistance, solvent resistance, adhesiveness, heat resistance, etc. as a cross-linking agent or modifier,
It is preferable from the viewpoint of imparting flexibility to the cross-linked portion, preventing an excessive increase in hardness of the modified surface, and contributing to improvement of wear resistance. For example, when the number of blocked isocyanate groups per molecule exceeds 2, for example, when it is 3, the water resistance, solvent resistance, heat resistance, adhesiveness, etc. are improved, but the flexibility of the crosslinked portion is improved. Property tends to be insufficient, the hardness of the modified surface may be excessively increased, and the abrasion resistance may be insufficient, which is not preferable for some applications.

A specific TMXDI-based compound obtained by reacting TMXDI with a glycol component having 6 or less carbon atoms has a molar ratio of an isocyanate group of TMXDI and a hydroxyl group of a polyhydric alcohol in an excess of isocyanate group and in a reaction product. Solvents that do not react with isocyanate groups in a proportion such that the isocyanate group content is 12% or more, such as methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, dioxane, cellosolve acetate, toluene, dimethylformamide, N-methylpyrrolidone, etc. It is usually produced by reacting in a solvent of room temperature to about 100 ° C.

The blocked isocyanate compound used in the present invention is
It contains substantially no free isocyanate group, and is produced by blocking the isocyanate group of the specific TMXDI compound as described above with an oxime compound.

Examples of the oxime-based compound include butanone oxime, acetone oxime, cyclohexanone oxime, and the like, butane oxime and acetone oxime are particularly preferable.

In the present invention, the oxime-based compound as described above is used as a blocking agent in the finally obtained heat-reactive aqueous composition of the present invention, which is usually used when crosslinking or modifying other resin or the like. Since the heat treatment is performed in the range of 120 to 180 ° C, the blocking agent dissociated at that stage scatters and hardly remains in the modified base material, and the performance deterioration due to the residual impurities hardly occurs. Because.

However, for example, when a phenolic compound is used as the blocking agent instead of the oxime compound, the dissociated phenolic compound remains in the modified base material under the heat treatment conditions, resulting in performance deterioration. In some cases, the base material to which these are applied or applied, such as polyester, becomes brittle, which is not preferable.

The production of the blocked isocyanate compound used in the present invention is carried out without solvent or under an organic solvent which is inert with the isocyanate group as described above, in the range of room temperature to 100 ° C, preferably room temperature to 6
Basically, it is carried out in the range of 0 ° C in the absence of a catalyst, but if a reaction rate is desired to be increased, a basic catalyst such as triethylamine or sodium methylate or a metal catalyst such as dibutyltin dilaurate may be used. good.

Further, the ratio of active hydrogen of the oxime compound to 1 mol of the isocyanate group is preferably 1.0 to 1.2 mol.

Furthermore, two or more types of blocked isocyanate-based compounds,
When they are used in combination, they may be mixed after being blocked, or they may be mixed and blocked at once before blocking.

Examples of the hydration aid used in the present invention include block partially saponified polyvinyl alcohol, or a combination of the block partially saponified polyvinyl alcohol and a nonionic activator.

Examples of the nonionic activator include ethylene oxide addition polymers such as phenol, alkylphenol, and aralkylphenol, and ethylene oxide-propylene oxide addition copolymers, fatty acids, and aliphatic amines.
Examples thereof include ethylene oxide addition polymers such as aliphatic alcohols and ethylene oxide-propylene oxide addition copolymers.

The amount of the hydration aid used is, with respect to the specific blocked isocyanate compound of the present invention, from the viewpoint of improving performance as a crosslinking agent or a modifier, such as water resistance and solvent resistance. It is preferably 1 to 30%, more preferably 1 to 20%, particularly preferably 1 to 15%.

The heat-reactive aqueous composition of the present invention is prepared by emulsifying or dispersing the above-mentioned specific blocked isocyanate compound in water using an aqueous aid.

The blocked isocyanate-based compound used for the production of the aqueous composition may be supplied in a state in which the organic solvent used in the reaction is removed and taken out, while being dissolved in the organic solvent. May be.

In the production of the aqueous composition of the present invention, ordinary emulsification methods, dispersion methods and the like can be adopted.

The heat-reactive aqueous composition of the present invention has a specific blocked TMXD
I-based compound is preferably 10 to 60%, more preferably 20
% To 50%, preferably 0.1 to 18%, more preferably 0.1 to 12%, particularly preferably 0.1 to 9%, and a balance of water.

Incidentally, when an organic solvent solution of a specific blocked isocyanate compound is subjected to emulsification and / or dispersion, it may contain an organic solvent used in addition to the above components,
After the aqueous composition is prepared, it may be distilled off.

For producing the heat-reactive aqueous composition of the present invention, a commonly used emulsifying device or dispersing device such as a homomixer or a homogenizer is preferable. The heat-reactive aqueous composition thus prepared usually has a solid content of about 10 to 78%.

The heat-reactive aqueous composition of the present invention is, for example, an impregnating resin,
Improving water resistance, solvent resistance, adhesiveness, etc. of coating resins, various water-soluble or water-dispersible synthetic polymers used for adhesion, etc., such as polyvinyl alcohol, various acrylic emulsions, various synthetic latexes, etc. , And various water-soluble natural polymers and their derivatives are added and compounded to improve the water resistance and adhesiveness, etc.
The effect is exhibited by heat treatment at 0 to 180 ° C. Furthermore, the heat-reactive aqueous composition of the present invention is useful in applications (fields) where color change is not easily affected by heat, light, and the like.

(Example) Hereinafter, the composition of the present invention will be described based on Examples.
The present invention is not limited to the examples below.

Example 1. 100 parts of TMXDI was dissolved in 50 parts of methyl ethyl ketone, and then 74.8 parts of butanone oxime was added in the range of 40 to 45 ° C.
It dripped over time. System temperature after dropping butanone oxime 50
It was confirmed that the free isocyanate group was completely disappeared by carrying out the reaction at 1 ° C. for 1 hour.

Next, 8.7 parts of ethylene oxide (13 mol) addition polymer of nonylphenol was added and mixed sufficiently, and then Kuraray PVA-217EE (Kuraray Co., Ltd., 10% aqueous solution of block partially saponified polyvinyl alcohol, the same below. ) 170 parts was added, and the rotation speed was 2000 using a homomixer at room temperature.
After stirring at rpm for 30 minutes, 100 parts of water was added little by little over 20 minutes and then stirred for 2 hours to obtain a low viscosity, cloudy, heat-reactive aqueous composition having a solid content of 40%.

Example 2. After dissolving 100 parts of TMXDI in 70 parts of methyl ethyl ketone, 18 parts of 1.4 butanediol was gradually added dropwise at a system temperature of 70 ° C. over 2 hours. Then, the mixture was reacted at the same temperature for 2 hours to obtain a reaction product containing 14.3% of isocyanate groups.

Finally, 39 parts of butanone oxime, in the range of 40-45 ℃,
It was added dropwise over 2 hours, and then the reaction was carried out at 50 ° C. for 1 hour, and it was confirmed that the free isocyanate group was completely disappeared. Next, nonylphenol ethylene oxide (13
Mol) 8.0 parts of addition polymer was added and mixed thoroughly,
Add 160 parts of Kuraray PVA-217EE and stir at room temperature using a homomixer at a rotation speed of 2000 rpm for 30 minutes, then add 233 parts of water little by little over 30 minutes, then stir for 2 hours Then, a low-viscosity, heat-reactive aqueous composition having a solid content of 28% was obtained.

Comparative Example 1. 50 parts of methyl ethyl ketone was added to 100 parts of isophorone diisocyanate, and after dissolution, 83 parts of butanone oxime were added dropwise over 40 to 45 ° C., and then at 40 ° C. in the system temperature of 50 ° C.
It was confirmed that free isocyanate groups were completely disappeared by carrying out a minute reaction. Next, 9.0 parts of ethylene oxide (13 mol) addition polymer of nonylphenol was added and thoroughly mixed, then 146 parts of Kuraray PVA-217EE was added, and the mixture was stirred at room temperature for 30 minutes at 2000 rpm using a homomixer. ,
Then add 129 parts of water little by little over 20 minutes and then add 2
After stirring for a time, a viscous, cloudy, heat-reactive aqueous composition having a solid content of 4% was obtained.

Comparative Example 2. 100 parts of xylene diisocyanate was dissolved in 100 parts of dimethylformamide, then 97 parts of butanone oxime, 40 parts
After dropwise addition at ˜45 ° C., the reaction was carried out at a system temperature of 50 ° C. for 30 minutes, and it was confirmed that the free isocyanate group was completely disappeared. Next, 7.9 parts of ethylene oxide (13 mol) addition polymer of nonylphenol was added and mixed well, then 158 parts of Kuraray PVA-217EE was added, and the mixture was stirred for 30 minutes at a rotation speed of 2000 rpm using a homomixer at room temperature. Then, 89 parts of water was added little by little over 20 minutes, and then the mixture was stirred for 2 hours to obtain a viscous, cloudy, heat-reactive aqueous composition having a solid content of 40%.

(Evaluation of reforming performance-1) The heat-reactive aqueous compositions of the present invention obtained in Examples 1 and 2 and the heat-reactive aqueous compositions obtained in Comparative Examples 1 and 2 were treated with Kuraray.
PVA-217 (Kuraray Co., Ltd., block partially saponified polyvinyl alcohol) was mixed with a 10% aqueous solution so that the solid content was 10%, and an organotin compound (curing catalyst) was added.
What was mixed at 10% with respect to the above mixed solution was collected in a Teflon-coated petri dish, air-dried overnight, and further dried at 60 ° C for 3 hours, and modified under the following curing conditions. A thick film was formed, and the obtained film was immersed in boiling water for 2 hours, and the area swelling ratio was measured.

As a comparison, the same procedure was carried out when Kuraray PVA-217 was used alone.

The results are shown in Table-1.

As described above, the compositions to which the aqueous compositions of Examples 1 and 2 of the present invention were added were cured at 120 ° C. to improve the reformability, while those of Comparative Examples 1 and 2 of the prior art. It was confirmed that the one to which the aqueous composition was added did not exhibit the modifying property unless a high temperature of 150 ° C. cure was applied.

(Modification Performance Evaluation-2) The heat-reactive aqueous compositions of the present invention obtained in Examples 1 and 2 and the heat-reactive aqueous compositions obtained in Comparative Examples 1 and 2 were treated with a water-soluble polyether polyol (glycerin). Ethylene oxide-propylene oxide polyaddition product, ethylene oxide / propylene oxide = 50/50% ratio, molecular weight 300
0) and the following proportions.

Mixing ratio; Regenerated isocyanate group mol / hydroxyl group mol = 1.2 /
1.0 (Note) Regenerated isocyanate group moles: Number of moles of blocked isocyanate groups in each heat-reactive aqueous composition (Note) Hydroxyl group moles: Number of moles of hydroxyl groups of the water-soluble polyether polyol A mixture of the compound (curing catalyst) so as to be 10% with respect to the mixed solution was dispensed into a Teflon coating chalet, air-dried and dried in the same manner as in the modification performance evaluation-1. Then, heat treatment was performed under each of the following curing conditions to confirm the film formation state.

The results are shown in Table-2.

<Explanation of film formation state> x: No film is formed in a sticky state at all. Δ: There is stickiness, but a film is formed in partial droplets. ◯: No surface tack, and a uniform film is formed overall. As described above, when the aqueous compositions of the present invention and Examples 1 and 2 are used, the blocking agent is dissociated at 120 ° C. because a uniform film is formed by curing at 120 ° C. On the other hand, when the aqueous compositions of Comparative Examples 1 and 2 of the prior art were used, a uniform film could not be formed without curing at 150 ° C. It was confirmed that the dissociation of the agent did not occur.

(Effects of the Invention) The heat-reactive aqueous composition of the present invention is resistant to heat, light and the like and hardly causes discoloration, and the dissociation of the blocking agent occurs in a low temperature range. It has the characteristic that the range of materials becomes wider.

Similarly, for example, various aqueous solutions and water-dispersible synthetic polymers used for impregnating resins, coating resins, adhesives, etc., such as polyvinyl alcohol, various acrylic emulsions, various synthetic rubber latexes, etc. It has a feature that it can improve solvent resistance and adhesiveness.

Claims (1)

[Claims] 1. A blocked isocyanate compound obtained by blocking an isocyanate group of (A) a tetramethylxylylene diisocyanate compound containing 12% by weight or more of an isocyanate group with an oxime compound, (B) an hydration aid, and C) In a heat-reactive aqueous composition containing water, the tetramethylxylylenediisocyanate-based compound containing 12% by weight or more of the isocyanate group is tetramethylxylylenediisocyanate and the tetramethylxylylenediisocyanate having 6 or less carbon atoms. Of one or both of a compound containing an isocyanate group obtained by reacting a glycol component of 12% by weight or more, the hydration aid, the block partially saponified polyvinyl alcohol alone, or the block partially saponified polyvinyl alcohol And non-io Thermal reaction type aqueous composition comprising the active agent.