JPS63225349A - Aqueous composition of thermal reaction type - Google Patents

Abstract

PURPOSE:To obtain an aqueous composition of thermal reaction type improving water resistance, solvent resistance and adhesiveness of synthetic high polymer useful as impregnating resin and adhesive, containing a blocked isocyanate compound, an aquosity forming auxiliary and water. CONSTITUTION:10-60wt.% blocked isocyanate compound obtained by blocking isocyanate group of a diphenylmethane diisocyanate compound containing >=12% isocyanate group with an oxime compound is blended with 0.1-18% aquosity forming auxiliary and the rest of water to prepare the aimed substance. An ordinary emulsifying device or dispersing device is used in the preparation and average particle diameter is <=10mu. The blocked isocyanate compound is obtained by reaction of isocyanate group in an inert solvent at normal temperature - 100 deg.C.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a thermally reactive aqueous compound containing a blocked isocyanate compound in which the isocyanate group of a diphenylmethane diisocyanate compound is blocked with an oxime compound, a water-containing auxiliary agent, and water. Regarding the composition.

[Prior Art] Diphenylmethane diisocyanate (hereinafter referred to as MDI) is an isocyanate compound useful as a raw material for urethane elastomers.

However, because MDI has strong hydrophobicity and a high melting point, it is often used in the production of solvent-based urethane elastomers manufactured in factories, but even if it is a solvent-based product, it can be processed as a crosslinking agent or modifier. It is rarely used in the stage because there are many inconveniences in its use. Furthermore, there is no concept of using MDI alone or something similar to it as a water-based product.

This is due to the high reactivity of MDI despite its high melting point, and the fact that phenolic compounds have been used as blocking agents for isocyanate groups, which are necessary to allow highly reactive MDI to exist in water where it reacts with isocyanate groups. This is because only fragmentary proposals have been made regarding the use of such compounds, and their properties have not been improved enough to be used as crosslinking agents or modifiers in processing stages.

[Problems to be Solved by the Invention] The present invention allows an MDI compound, which is an isocyanate compound having high reactivity, to exist stably in water as an aqueous composition with few inconveniences in use, and a crosslinking agent and a modifier. This was done to solve the problem that it is difficult to supply such materials for use in the processing stage.

[Means for solving the problems] The present invention provides (A) isocyanate groups in an amount of 12% (wt%,
The same applies hereinafter) Regarding a thermally reactive aqueous composition comprising a blocked isocyanate compound in which the isocyanate group of the diphenylmethane diisocyanate compound containing the above is blocked with an oxime compound, (B) a water-forming aid, and (C) water. .

[Example] MDI compound containing 12% or more of isocyanate groups used in the present invention (hereinafter referred to as specific MDI compound)
As a specific example, for example, MDI, MDI and carbon number 6
Examples include MDI compounds containing 12% or more of isocyanate groups, which can be obtained by reacting with the following glycol components.

If the content of isocyanate groups in the MDI-based compound is less than 12%, the performance of the finally obtained heat-reactive aqueous composition of the present invention when used as a crosslinking agent, a modifier, etc. is undesirable.

Specific examples of the glycol component having 6 or less carbon atoms include:
For example, ethylene glycol, propylene glycol,
Examples include 1, 4- or 1,3-butanediol, bentanediol, hexanediol and the like.

The heat-reactive aqueous composition of the present invention, in which these glycols having 6 or less carbon atoms are finally obtained, is blended into, for example, water-soluble or water-dispersible synthetic polymers, water-soluble natural polymers, or derivatives thereof. However, when used as a crosslinking agent or modifier to improve water resistance, solvent resistance, adhesion, heat resistance, etc., it imparts flexibility to the crosslinked part and prevents excessive hardness of the modified surface. It is preferable because it contributes to improving wear resistance and wear resistance. For example, if the number of blocked isocyanate groups per molecule exceeds 2, for example 3, water resistance, solvent resistance, heat resistance, adhesiveness, etc. will improve, but the crosslinked portion will be Flexibility tends to be insufficient, the hardness of the modified surface tends to increase too much, and wear resistance tends to be insufficient, making it undesirable for some uses.

A specific MDI compound obtained by reacting MDI with a glycol component having 6 or less carbon atoms is a system in which the molar ratio of the isocyanate group of MDI to the hydroxyl group of the polyhydric alcohol is such that the isocyanate group is in excess, and the reaction product In a solvent that does not react with isocyanate groups, such as methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, dioxane, cellosolve acetate, toluene, dimethylformamide, etc., in a proportion such that the isocyanate group content is 1226 or more, usually at room temperature to It is produced by reacting at about 100°C.

The blocked isocyanate compound used in the present invention does not substantially contain free isocyanate groups, and is produced by blocking the isocyanate groups of the above-mentioned specific MD compound with an oxime compound.

Examples of the oxime compounds include butanone oxime, acetone oxime, and cyclohexanone oxime, but the butanone oxime and acetone oxime are particularly preferred.

In the present invention, the above-mentioned oxime compound is used as a blocking agent in order to crosslink or modify other resins in the finally obtained heat-reactive aqueous composition of the present invention. Since heat treatment is usually performed in the range of 130 to 180°C, the blocking agent dissociated at that stage scatters and hardly remains in the modified base material, so there is almost no performance deterioration due to residual impurities. It is from.

However, when a phenolic compound is used instead of an oxime compound as a blocking agent, for example, the phenolic compound dissociated under the heat treatment conditions remains in the modified base material, resulting in performance deterioration. In some cases, the substrate to which they are applied or coated, such as polyester, may become brittle, which is undesirable.

The production of the blocked isocyanate compound used in the present invention is usually carried out in the presence of an isocyanate group as described above and an inert organic solvent at room temperature to about 100°C, basically without a catalyst. In such cases, a basic catalyst such as triethylamine or sodium methylate or a metal catalyst such as dibutyltin dilaurate may be used. Further, the ratio of active hydrogen in the oxime compound to 1 mol of isocyanate group is preferably 1.0 to 1.2 mol. Furthermore, when two or more types of blocked isocyanate compounds are used together, they may be mixed after each block is formed, or they may be mixed before blocking to form blocks at once.

Examples of the aqueousization aid used in the present invention include commonly used emulsifiers and dispersants, such as salts of aromatic sulfonic acids and higher fatty acids or derivatives thereof; cationized products of alkylamines; phenols, alkylphenols,
Ethylene oxide addition polymers and ethylene oxide-propylene oxide addition copolymers such as aralkylphenol; ethylene oxide addition polymers and ethylene oxide-propylene oxide addition copolymers such as fatty acids, aliphatic amines, and aliphatic alcohols; Examples include, but are not limited to, salts of higher alcohols, alkylphenols, aralkylphenols, and their alkylene oxide adducts such as phosphoric acid esters and sulfuric esters. These may be used alone or in combination of two or more. Among these, ethylene oxide addition polymers of alkylphenols and aralkylphenols are particularly preferred.

The amount of the emulsifier and/or dispersant used as the water-based auxiliary agent is determined to improve the performance of the specific blocked isocyanate compound as a crosslinking agent or modifier, such as water resistance and solvent resistance. From the viewpoint of increasing the carbon content, the content is preferably 1 to 30%, more preferably 1 to 20%, and particularly preferably 1 to 15%.

Furthermore, in order to improve the storage stability of aqueous compositions, protective colloids commonly used as aqueousization aids may be used in combination with the emulsifiers and/or dispersants; PVA
, Partially saponified PVA, Block partially saponified PVA,
Examples include, but are not limited to, polyvinylpyrrolidone, methylcellulose, hydroxyethylcellulose or hydroxypropylcellulose, methylhydroxypropylcellulose, carboxycellulose, gelatin, starch paste, acrylic acid polymer, methacrylic acid polymer, and the like.

The heat-reactive aqueous composition of the present invention is prepared by emulsifying or dispersing the blocked isocyanate compound in water using an emulsifier and/or a dispersant, and if necessary a protective colloid.

The blocked isocyanate compound used in the production of the aqueous composition may be supplied after removing the organic solvent used in the reaction, or may be supplied in a state dissolved or dispersed in the organic solvent. It's okay.

In producing the aqueous composition of the present invention, a conventional emulsification method,
A dispersion method etc. may be adopted.

The heat-reactive aqueous composition of the present invention has a specific blocked MD.
Contains preferably 10 to 60%, more preferably 20 to 50%, of I-series compounds, and preferably 0.1 to 18%, more preferably 0.1 to 18%, of emulsifiers and/or dispersants.
12%, particularly preferably 0.1 to 9%, and furthermore 0 to 2%, more preferably 0 to 1% of said protective colloid.
% and the rest is water. Note that when an organic solvent solution of a specific blocked isocyanate compound is subjected to emulsification and/or dispersion, it may contain organic solvents used in addition to the above components, and after preparing the aqueous composition. It may be distilled off.

To produce the heat-reactive aqueous composition of the present invention, a commonly used emulsifying device or dispersing device, such as a homomixer, ball mill, bead mill, homogenizer, colloid mill, etc., is used, and the average particle size is preferably 10 μm or less, More preferably, the thickness is 5μ or less.

The heat-reactive aqueous composition thus prepared usually has a solid content concentration of about 10 to 78%.

The heat-reactive aqueous compound/acid of the present invention can be used for various water-soluble or water-dispersible synthetic polymers used for applications such as impregnating resins, coating resins, and adhesives, such as polyvinyl alcohol, various acrylic polymers, etc. Additions and formulations to improve the water resistance, solvent resistance, and adhesion of products made of emulsions and various synthetic latexes, and to improve the water resistance and adhesion of products made of various water-soluble natural polymers and their derivatives. The effect is brought out by heat treatment at 130 to 180°C after application.

The present invention will be described in detail below based on Examples, but the present invention is not limited to the following Examples.

Example 1 and Comparative Example 1 1100 parts of X was added to 200 parts of ethyl acetate at a system temperature of about 50°C.
After dissolving 73 parts of butanone oxime in
The mixture was added dropwise at 5°C over 3 hours. After the butanone oxime dropwise addition was completed and it was confirmed that crystals had precipitated, the system temperature was cooled to 30° C. and stirred at the same temperature. After separating the precipitated crystals, the solvent was distilled off at 60° C./lOmmHg.

Through the above operations, a butanone oxime blocked MDI having a melting point of about 141"C is produced as a powder having a melting point of about 141"C.
was obtained with a yield of 95%.

Next, for the above-mentioned blocking, 700 parts of DI, 70 parts of emulsifier Neugen IEA-87 (manufactured by Dai-ichi Kogyo Seiyaku ■, non-ionic activator) and Nougen E^-177 (manufactured by Dai-ichi Kogyo Seiyaku Ami, non-ionic activator) were added. A mixture of 35 parts of glass peas (particle size: 1.0-1.
5+u) appears to be 2f filled to 80% capacity! A dispersion operation was carried out at a discharging liquid rate of 1j2/■In and a residence time in the pot of 60 minutes to prepare a cloudy, heat-reactive aqueous composition with an average particle size of 1.0 .mu.m and a low viscosity.

The storage stability of the obtained heat-reactive aqueous composition at 20° C. and 50° C. and the property of modification by the following method were investigated. The results are shown in Table 1.

For comparison of modification evaluation, Kuraray PVA-217
(manufactured by Kuraray ■, partially saponified polyvinyl alcohol) was similarly evaluated. The results are also shown in Table 1.

In addition, ◎ in Table 1 indicates stability, 0 indicates that a small amount of sediment is precipitated or the upper layer is slightly separated, Δ indicates that the sediment is precipitated or the upper layer is separated, and X indicates that the sediment is precipitated or the upper layer is clearly separated. .

(Modification properties) A heat-reactive aqueous composition was mixed with a 10% aqueous solution of Kuraray PVA-217 so that the solid content was 10%, and then Elastron Catalyst-32 (Daiichi Kogyo Seiyaku ■
After applying a mixture of 10% solids of a curing catalyst (made by a manufacturer) to the mixed solution, the mixture was air-dried overnight.
It was further dried at 70°C for 3 hours and then cured at 150°C for 2G to form a modified film.The obtained film was immersed in boiling hot water, and the area swelling rate was measured after 2 hours.

Example 2 After 100 parts of MDI was dissolved in 100 parts of methyl ethyl ketone at a system internal temperature of about 50°C, 16 parts of propylene glycol was gradually added dropwise over a period of 2 hours at a system internal temperature of about 50°C. Thereafter, the reaction was carried out at the same temperature for about 2 hours to obtain a reaction product containing 14.2% (based on the total amount of MDI and propylene glycol) of isocyanate groups.

Next, 34.5 parts of butanone oxime was added to the system at a temperature of about 40
After dropping at ~45°C over 1 hour, the mixture was reacted at the same temperature, and it was confirmed that the isocyanate group had disappeared.

In this way, a viscous solution of a butanone oxime-blocked MDI compound in methyl ethyl ketone having a solid content of 60% was obtained.

After adding 8 parts of Neugen E^-8710 and 1777 parts of Neugen EA to 200 parts of the methyl ethyl ketone solution of the blocked MDI compound, Kuraray PVA-217 was added.
8B (manufactured by Kuraray ■, 10% polyvinyl alcohol
Add 24 parts of aqueous solution), stir at approximately 40°C using a homomixer at 2000 rpm for 80 minutes, and add 35 parts of water.
8 parts were added over 30 minutes and then stirred for 2 hours to obtain a heat-reactive aqueous composition with an average particle size of 5 μm, low viscosity, and cloudy white.

The storage stability and modification properties of the obtained heat-reactive aqueous composition at 20°C and 50°C were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 3 100 parts of dimethylformamide was added to 100 parts of MDI and dissolved at a system internal temperature of about 50°C.
-18 parts of butanediol was gradually added dropwise over 2 hours at an internal temperature of about 50°C. After that, leave it at the same temperature for 1 hour,
A reaction product containing 14.0% (based on the total amount of MDI and 1,4-butanediol) of isocyanate groups was obtained. Next, 34 parts of butanone oxime was added to the system at a temperature of about 4.
After dropping at 0 to 45°C over 1 hour, the mixture was reacted at the same temperature, and it was confirmed that the isocyanate group had disappeared. In this way, a translucent butanone oxime-blocked MDI compound dimethylformamide solution with a solid content of 80% was obtained.

Next, a mixture of 10 parts of Neugen EA-87, 9 parts of Neugen EA-177, and 400 parts of water was added to 200 parts of the methylformamide solution of the blocked MDI compound, and a mixture was applied to a ball mill and subjected to fine dispersion operation for 24 hours. A heat-reactive aqueous composition with an average particle size of 6 μm, low viscosity, and cloudy white was obtained.

The storage stability and modification properties of the obtained heat-reactive aqueous composition at 20°C and 50°C were examined in the same manner as in Example 1. The results are shown in Table 1.

Margins below c] From the results in Table 1, it can be seen that the heat-reactive aqueous composition of the present invention has storage stability that can be supplied to the market. Also,
By adding the heat-reactive aqueous composition of the present invention, PV
It can be seen that the water resistance of A was improved.

[Effects of the Invention] The heat-reactive aqueous composition of the present invention can be used, for example, as an impregnating resin,
Water resistance, solvent resistance, and adhesive properties of various water-soluble and water-dispersible synthetic polymers used for coating resins and adhesives, such as polyvinyl alcohol, various acrylic emulsions, and various synthetic latexes. It has the characteristic that it can improve the following.

Procedural Amendment Order Seal April 20, 1988 fE Commissioner of the Patent Office Mr. Akio Kuroda [Ki 1 Indication of Case Patent Application No. 57715 of 1988 2 Name of Invention Heat Reactive Aqueous Composition 3 Amendment Person Case Related Patent Applicant Address 55 Nishi-shichijo Higashikubo-cho, Shimogyo-ku, Kyoto-shi, Kyoto Prefecture Name (150) Dai-Kogyo Seiyaku Co., Ltd. Representative Takahiko Miura 4 Agent Address 540 5 Subject of amendment (1) Inventions in the description Contents of amendment in Column 6 “Detailed explanation of
This is because there are many disadvantages to making it water-based due to its high temperature and strong hydrophobicity.

Also,” he corrected.

(2) On page 11, line 13, "It shall be so." shall be amended to "It shall be so arranged."

(3) Delete "manufactured" in line 2 on page 12.

(4) Delete "manufactured" in line 4 on page 12.

(5) "Improvement, etc." in line 4 on page 12 is corrected to "improvement."

(6)　Page 13, line 2 and correct it.

that's all

Claims (1)

[Scope of Claims] 1 (A) a blocked isocyanate compound obtained by blocking the isocyanate groups of a diphenylmethane diisocyanate compound containing 12% by weight or more of isocyanate groups with an oxime compound, (B) an aqueousization aid, and (C) A heat-reactive aqueous composition containing water.