JPS63135447A - Heat-reactive, water-soluble or water-dispersible polyester urethane composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in adhesiveness to various bases, stability as a solution, etc., by reacting a urethane prepolymer comprising a specified compound, a component for introducing carboxyl groups and an organic polyisocyanate with a blocking agent. CONSTITUTION:A compound (a) having at least two active hydrogen atoms, comprising a polyester-polyol and, optionally, other compounds having at least two active hydrogen atoms is reacted with a component (b) for introducing carboxyl groups which is a compound having at least two hydroxyl or amino groups and at least one carboxyl group and an organic polyisocyanate (c) to obtain a urethane prepolymer (A) having 1.0-7.0wt% carboxyl groups and at least two free NCO groups in the molecule. Component A is reacted with a blocking agent (e.g., acetylacetone) (B) which can permit regeneration of NCO groups by heating and the carboxyl groups are neutralized with ammonia or an organic amine. The produce is dissolved or dispersed in water.

Description

[Detailed Description of the Invention] The present invention relates to various fiber materials, plastics, films,
It is a heat-reactive type that has good adhesion and adhesion to various materials such as glass and metals, and the resulting resin has improved physical properties such as strength, non-adhesiveness, ice resistance, solvent resistance, and solution stability. ,
The present invention relates to a water-soluble or water-dispersible polyester urethane composition.

In recent years, there has been increasing interest in water-based resins as an alternative to conventional organic solvent-based resins due to pollution and environmental pollution issues. Among them, water-based polyurethane resins are being used as treatment agents for artificial leather and textiles due to their excellent mechanical properties. It has been used in a wide range of fields as a substrate for other materials or as an mM agent for glass.

Conventionally, as water-based polyurethane resins, non-reactive high molecular weight types and relatively low molecular weight heat-reactive types that accommodate blocked isocyanate groups have been mainly used, and the former has a high molecular weight polyurethane skeleton. Therefore, it is necessary to introduce a large amount of hydrophilic groups for water-based formulation, and it is necessary to use a large amount of emulsifier for emulsion formulation, so deterioration of the water resistance of the resulting film is unavoidable. , inconveniences in use such as its stability and gum-up, and its basically linear structure and thermo-concave properties, the adhesiveness of the film surface at room temperature or high temperature and its resistance to solvents. Sexual deterioration was inevitable. On the other hand, the latter heat-reactive type having blocked isocyanate groups has the advantage of superior solvent resistance compared to the former, since the film formed after the heat reaction is highly crosslinked.

However, the blocking agents conventionally used in this product mainly include bisulfite, phenol, alkylphenol, etc., and when bisulfite is used, it is not possible to introduce a 7-ion group into the polyurethane skeleton. Although it is possible to easily obtain an aqueous product, thermally dissociated bisulfite remains inside the film, resulting in deterioration of water resistance and reduction in strength.
In addition, when used for textiles, especially clothing, bisulfite has reducing properties, which causes discoloration of polyester and cotton fabrics dyed with disperse dyes and reactive dyes, making it undesirable for practical use. Moreover, when applied to a metal surface, it causes rust, and its applications are also limited.

Similarly, when phenol, alkylphenol, etc. are used as blocking agents, they remain inside the film after thermal dissociation, resulting in deterioration of adhesion and strength.
In particular, when a polyester base material is treated using phenol, the strength of the polyester base material itself deteriorates due to residual phenol, which is undesirable. In view of the current situation, the present inventors have attempted to improve A) water resistance, solvent resistance, and film surface in the non-reactive high molecular weight type, which are the drawbacks of the conventional water-based polyurethane compositions and polyurethanes obtained therefrom. B) Gum-up property, solution stability A) Residual blocking agent in heat-reactive type with blocked isocyanate group B) Deterioration of film water resistance and transparency due to remaining blocking agent C) Blocking The present invention was developed as a result of intensive research with the aim of providing a urethane composition that is stable in water solubility or water dispersibility and that has improved adhesive deterioration due to residual agents and water-resistant adhesion. be.

That is, the present invention is a compound having two or more active hydrogen atoms comprising a polyester polyol as an essential component, a carboxyl group-introducing component, and an organic polyisocyanate, which has a carboxyl group in the molecule, and has an isocyanate group of 2
After forming a urethane prepolymer having at least 2 carboxyl groups, a blocking agent that regenerates isocyanate groups is reacted with the carboxyl group by heat treatment, and the carboxyl groups are neutralized with ammonia or an organic amine. Alternatively, a water-dispersible polyester urethane composition is provided.

In the heat-reactive, water-soluble or water-dispersible polyester urethane composition of the present invention, the functions and purposes of each structure and component are as follows.

A) As a result of examining the adhesion and adhesion properties with various base materials, we found that the introduction of polar groups is effective, and among them, polyester polyol having ester groups is essential as a compound component having two or more active hydrogen atoms as a starting material. It was found that it was suitable to use it as a component, and this was made a requirement.

B) For solution stability, a carboxyl group-introducing component containing a carboxyl group was required, since it is effective to introduce a parent group into the interior of the urethane skeleton rather than the end.

C) In order to neutralize the carboxyl group introduced into the resin skeleton with a basic substance to obtain a parent group, it is recommended to use ammonia or organic amines that can be dispersed by dry heat treatment after processing. Preferably, this was made a requirement.

One of the reasons for this is that the dry heat treatment causes the scattering of basic substances, which reduces the hydrophilicity of the urethane skeleton at once, improving the #aqueous property.Furthermore, the NGO groups that are dissociated from the blocking agent and regenerated during the heat treatment are Further improvement in physical properties such as water resistance was observed due to the disappearance of parent wood groups and promotion of crosslinked structure.

D) Conventionally, the mainly used blocking agents, such as bisulfite, phenol, and alkylphenols, remain in the film even after blowing and dissociation under normal heat treatment conditions, resulting in poor water resistance and adhesion. However, when acetylacetone, methyl acetoacetate, ethyl acetoacetate, methyl ethyl ketoxime, etc. are used as a blocking agent, even under normal heat treatment conditions, they can be released from the resin system after dissociation. We found that there was no scattering and that the problems caused by residual blocking agent could be solved, and we set this as a requirement.

Next, a method for producing a heat-reactive, water-soluble or water-dispersible polyester urethane composition according to the present invention will be explained.

Polyester polyols used in the production of the heat-reactive, water-soluble or water-dispersible polyester urethane composition of the present invention include polyhydric carboxylic acids such as adipic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid and dimer acid. Acid and ethylene glycol, dinylene glycol, propylene glycol, butylene gelicol,
Examples include polyester polyols such as fflfi synthesis products with polyhydric alcohols such as neopentyl glycol and trimethylolpropane, and lactone polyester polyols obtained by ring-opening polymerization of caprolactone. Other examples include polyester polyols which are polycondensation products of anhydrous acids such as succinic anhydride, maleic anhydride, and phthalic anhydride with the polyhydric alcohols.

Other compounds having two or more active hydrogen atoms that can be used in the present invention include the above-mentioned polyhydric alcohols commonly used in the production of urethane, and polyether polyols obtained by polyaddition of fullylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. , ethanolamine, jetanolamine, triethanolamine, etc., polyether polyols with fullylene oxide polyadded to tI amino alcohols, acrylic polyols, polybutadiene polyols, etc., but other than these Any compound having two or more active hydrogen atoms that is normally used in the production of urethane can be used.

The ratio of the polyester polyol and the other compound having two active hydrogen atoms is determined based on the adhesion of the final heat-reactive, water-soluble or water-dispersible polyester urethane composition of the present invention to various substrates. The proportion of polyether polyol is 10% of all compounds having 2 or more active hydrogen atoms in the starting materials, including polyether polyol.
It is preferable that the amount is at least % by weight.

Next, the carboxyl group-introducing component will be explained.

The carboxyl group-introducing component is a compound containing a 2m or more hydroxyl group, or an amino group and one or more carboxyl groups, and specific examples include 2.2-dimethylol acetic acid, 2.2-dimethylolpropionic acid, and 2.2-dimethylolpropionic acid. Examples include dihydroxycarboxylic acids such as 2-dimethylolbutyric acid and 2,2-dimethylolpentanoic acid, and diaminocarboxylic acids such as lysine and arginine, among which 2,2-dimethylolpropionic acid is particularly preferred.

The organic polyisocyanate used in the present invention includes:
Examples include aromatic isocyanates such as diphenylmethane diisocyanate and toluene diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate, alicyclic isocyanates such as inphorone diisocyanate, aromatic and aliphatic isocyanates such as xylylene diisocyanate, and furthermore, these isocyanates and trimethylolpropane. Examples include polyisocyanates obtained by preliminarily reacting low molecular weight polyols such as.

Next, a blocking agent that regenerates isocyanate groups by heat treatment will be exemplified.

In general, blocking agents that regenerate isocyanate groups by heat treatment include phenols, alkylphenols, active methylene compounds, oximes, bisulfites,
Examples include imidazoles and tertiary alcohols.

On the other hand, when applying resin processing etc. to various base materials, generally 2
Heat treatment conditions of 00°C or lower are performed. Therefore, from this point of view, we have found that when using a blocked isocyanate compound, it is preferable for the thermally dissociated blocking agent to scatter out of the film and the system at 200°C or less in order to improve the physical properties and adhesion of the film. That is, the blocking agent used in the present invention includes compounds having a boiling point of 200°C or less, and examples of the blocking agent used include acetylacetone, methyl acetoacetate, 8% ethyl acetate, and methyl ethyl ketoxime. . Blocking agents other than these are undesirable because they have a boiling point of 200°C or higher, so they remain inside the film under normal heat treatment conditions and cause deterioration of film strength and adhesion, which is undesirable and blocks bisulfites, etc. When used as a curing agent, the residual inorganic salt causes deterioration of the water resistance of the film and deterioration of adhesiveness when immersed in water, which is undesirable.

From these, the following steps are used to produce a heat-reactive, water-soluble or water-dispersible polyester urethane composition.

First, when the carboxylic acid introduction component is dihydroxycarboxylic acid, the polyester polyols (hereinafter referred to as component A) and other compounds having two or more active hydrogens (hereinafter referred to as component B) are used.
component) and the dihydroxycarboxylic acids (hereinafter referred to as component C)
and the above-mentioned organic polyisocyanates (hereinafter referred to as component
There is a method of neutralizing it with ingredients) and introducing it into the water system.

In addition, the A component and the B component and the E component and the X component may be reacted simultaneously or sequentially. 5 Then, the C component is added and the reaction is carried out until the isocyanate group disappears. After that, neutralization with the F component is carried out. Various methods can be used before neutralization and conversion to an aqueous system, such as conversion to an aqueous system.

Next, the carboxylic acid introduction component is diaminocarboxylic! I(
In the case of the following components), it is difficult to react with them in the bulk, so a blocked isocyanate urethane prepolymer is created by reacting component A with component B and component E with component X in advance to leave free isocyanate groups. synthesize,
There is a method in which a separately prepared aqueous source prepared by neutralizing component D with component F is reacted to lead to the target product.

In either method, if necessary, an isocyanate group and an inert organic solvent can be added to carry out the reaction at a stage before forming an aqueous system. In this case, there are cases in which it is better for the solvent not to remain in the product, and for that purpose it is necessary to distill off the solvent, so 8 points should be
Hydrophilic organic solvents that are azeotropic with water at temperatures below 100°C are preferred, and examples thereof include dioxane, acetone, tetrahydrofuran, ethyl acetate, and methyl ethyl ketone. In addition, there is no need to distill off unless the effect of the solvent is a problem for the purpose of the application. Alternatively, after the free isocyanate groups have disappeared, such as after making it aqueous, volatile alcohols such as methanol, ethanol, isopropanol, butyl cellosolve, etc. can be added for the purpose of improving cold resistance stability.

In either method, A, B, C, D, E components and
Regarding the equivalence relationship of components, A+B+C (and also 1fD
) + E ≦

Note that the reaction using isocyanate groups is normal.

This process is carried out at room temperature to 100°C, and if necessary, ordinary urethanization catalysts such as organic acids, n-free compounds, acid metals, and amine catalysts can be used. In addition to ammonia, examples of bases that neutralize carboxyl groups used in the present invention include trimethylamine, triethylamine, triinpropylamine, tributylamine, triethanolamine, methyljetanolamine, dimethylethanolamine, diethylethanolamine, etc. Examples include organic amines, but in order to improve the water resistance of the film during heat treatment, those that are water-soluble and easily dispersed by heat treatment are preferred, and ammonia, triethylamine, and triethylamine are particularly preferred.

Furthermore, during heat treatment, the ammonia, trimethylamine,
The carboxyl group after the triethylamine has been scattered reacts with the isocyanate group regenerated by the heat treatment, further reducing its action as a parent wood group and further improving the water resistance of the film.

Through the above steps, a heat-reactive type having an ester bond, a carboxyl group, and a blocked isocyanate group in the molecule,
A water-soluble or water-dispersible polyester urethane composition is obtained, but in this case, regardless of the order of synthesis, it has a carboxyl group in one molecule and a free isocyanate group.
Form of urethane prepolymer having two or more (A component + B
It is necessary to set the amount of carboxyl groups in the component (C and/or D component, X component) to be 1.0 to 7.0% by weight.

If it is less than 1.0% by weight, the film water resistance of the urethane composition of the present invention will be significantly improved, but the product stability will be lowered, making it unsuitable. A particularly preferable range of the carboxyl group content is 1.2 to 5.0% by weight, where the water resistance of the resulting film or the adhesive strength upon immersion in water is significantly unfavorable. The heat-reactive, water-soluble or water-dispersible polyester urethane composition of the present invention thus obtained can be used for various plastics such as vinyl chloride, nylon, polyester, and polyurethane, textile products, synthetic leather, metals such as aluminum and iron, paper, It has excellent adhesion to wood, glass, etc., and its film surface is non-adhesive.The film has excellent water and solvent resistance, and can be used as a treatment agent for FMM, synthetic leather products, and adhesion to various base materials. It can be widely used as a coating agent, an aqueous coating agent, or a sizing agent.

The heat treatment temperature of the heat-reactive, water-soluble or water-dispersible polyester urethane composition of the present invention is as follows.

In order to effectively dissociate the blocking agent, crosslink polymerize the regenerated isocyanate groups, and scatter the blocking agent out of the coating system, it is preferable to carry out the reaction at a temperature of 150 to 200°C.

The present invention will be explained below with reference to Examples.

(Part 1% indicates weight basis) Synthesis Example 1 70 parts of polybutylene adipate (molecular weight + 000),
Add 30 parts of polyether polyol (molecular weight of 1 ethylene oxide polyadduct + 000), 3.0 parts of rimethylolpropane, and add 50 parts of methyl ethyl ketone and dissolve. 45 parts of xylylene diisocyanate was added at a system temperature of 60°C, the system temperature was raised to 70°C, the reaction was carried out for 120 minutes at 70°C, and 8.0% of free isocyanate groups (polybutylene adipate, polyether polyol, trimethylolpropane, xylylene diisocyanate) to obtain a urethane prepolymer with 0-order dimethylolpropionic acid 7
．． 1 part was added and the reaction was carried out at 75°C for 180 minutes,
A urethane prepolymer having carboxyl groups in the molecule and 2.85% of free isocyanate groups was obtained.

Note that the carboxyl group content in the urethane prepolymer is 1.54%.

Next, add 8.8 parts of methyl ethyl ketoxime,
The reaction was carried out for 90 minutes at 0°C, and after confirming that the isocyanate group had disappeared, 5.4 parts of triethylamine was added and diluted with water to obtain a translucent urethane composition of the present invention with a solid content of 30%. Ta.

Next, at 80°C and 7,100 mmHg, twice the amount of water-methyl ethyl ketone mixed solvent as the methyl ethyl ketone used was distilled off over 120 minutes, and it was confirmed that there was no longer any methyl ethyl ketone odor in the system. Type 3
It was set to 0%.

Synthesis Example 2 100 parts of diethylene glycol adipate (molecular weight I
QOo), 5.0 parts of trimethylolpropane was added and the system temperature was 80°C, and 47.1 parts of hexamethylene diisocyanate) was added and the reaction was carried out at 85°C for 80 minutes to form free isocyanate. Group 6.80% (diethylene glycol adibate, trimethylolpropane,
A urethane prepolymer was obtained having (based on the total amount of hexamethylene diisocyanate).

Next, 50 parts of methyl ethyl ketone and 8.0 parts of dimethylolpropionic acid were added, and the reaction was carried out for 200 minutes at an internal temperature of 75°C. A urethane prepolymer having a solid content) was obtained.

Note that the carboxyl group content in the urethane prepolymer is 1.68%.

Next, 10.7 parts of methyl ethyl ketoxime was added,
The reaction was carried out for 80 minutes at a system temperature of 80°C, and after confirming that the isocyanate group had disappeared, triethylamine 8
．． After adding 0 parts, it was diluted with water to obtain a transparent urethane composition of the present invention with a solid content of 25%.

Next, the methyl ethyl ketone used in the same manner as in Synthesis Example 1 was distilled off, and the mixture was again corrected with water to make the solid content 25%.

Synthesis Example 3 70 parts of the polyester polyol used in Synthesis Example 2, 30 parts of polyether polyol (molecular weight of ethylene oxide polyadduct 8 + 000), 3.0 parts of rimethylolpropane were added, and the mixture was heated at an internal temperature of 50°C. , 2.4
-) Add 42.1 parts of luene diisocyanate,
The reaction was carried out at 0°C for 40 minutes, and free isocyanate groups 8
．． A urethane prepolymer having a content of 10% (based on the sum of polyester polyol, polyether polyol, trimethylolpropane, 2.4-)luene diisocyanate) was obtained.

Next, 70 parts of methyl ethyl ketone was added, and then 7.0 parts of dimethylolpropionic acid was added, and the system was heated to 70°C.
By reacting for 120 minutes under A polymer was obtained.

Note that the carboxyl group content in the urethane prepolymer is 1.58%.

Next, 1O09 parts of 7cetylacetone and 0.3 parts of sodium methylate were added, and the reaction was carried out at 70°C. After confirming that the isocyanate group had disappeared, 5.28 parts of triethylamine was added and the water was drained. Dilute to 15% solids
A translucent urethane composition of the present invention was obtained.

Next, the methyl ethyl ketone used in the same manner as in Synthesis Example 1 was distilled off, and water was corrected again to make the solid content 15%.

Synthesis Example 4 To 100 parts of the urethane prepolymer having 6.80 parts of free isocyanate groups used in Synthesis Example 2, 7.0 parts of methyl ethyl ketoxime was added and reacted at 80° C. for 60 minutes, resulting in 3.30 parts of free isocyanate groups. A blocked urethane prepolymer having % of

Next, at a system temperature of 50°C, 30 parts of methyl ethyl ketone was added to bring the system internal temperature to 35°C.
．． After adding 0 parts, the reaction was carried out at 35° C. to 45° C. for 90 minutes, and then diluted with water to obtain a translucent urethane composition of the present invention having a solid content of 15%.

Thereafter, methyl ethyl ketone was distilled off in the same manner as in Synthesis Example 1, and water was again corrected to bring the solid content to 15%.

Comparative Synthesis Example 1 1.54% carboxyl group in the molecule used in Synthesis Example 1
8.84 parts of Genol and 0.3 parts of triethylamine were added to 200 parts of a urethane prepolymer having 2.85% of free isocyanate groups (methyl ethyl ketone solution, solid content 74.75%), and the system internal temperature was The reaction was carried out at 70°C, and after confirming that the isocyanate group had disappeared, 5.17 parts of triethylamine was added by the same procedure as in Synthesis Example 1, diluted with water, and the methyl ethyl ketone used was distilled off, followed by water correction again. A urethane composition with a solids content of 30% was obtained.

Comparative Synthesis Example 2 As Comparative Synthesis 2, Elastron F-29 (@-manufactured by Kogyo Seiyaku Co., Ltd., polyether-based bisulfite blocked product)
was used.

Examples The physical properties of the heat-reactive, water-soluble or water-dispersible polyester urethane composition of the present invention were tested according to the following evaluation methods. The results are shown in Table 1.

Adhesion: After applying the sample to an aluminum plate at a solid content of 58.7rn'', heat treatment was performed at 100°C for 1 minute and 180°C for 2 minutes, and a peel test using cellophane tape was performed on the film obtained. The adhesion to the material was evaluated.

O: Very good adhesion, no change in appearance ΔD Partial film peeling ×: Full film peeling Water resistance: Adhesion was evaluated after immersion in 50°C warm water for 24 hours.

Blocking resistance: Paste coated surfaces together at 60°C18
Blocking property evaluation after standing for 24 hours under load loog/C112 in an atmosphere of 0% RH O: easily peeled off Δ: slightly adhered. However, no damage to the film surface ×: Adhesion. There is evidence of damage to the film surface.

Claims (4)

[Claims] (1) Compounds containing two or more active hydrogens of one or more types consisting of polyester polyol as an essential component, a carboxyl group-introducing component, and an organic polyisocyanate having a carboxyl group in the molecule and two or more free isocyanate groups. After forming a urethane prepolymer having a urethane prepolymer, a blocking agent that regenerates isocyanate groups is reacted with a heat treatment, and the carboxyl groups are neutralized with ammonia or an organic amine. Dispersible polyester urethane composition. (2) The heat-reactive type, water-soluble, or water-dispersible type according to claim 1, wherein the carboxyl group-introducing component is a compound containing two or more hydroxyl groups or amino groups and one or more carboxyl groups. polyester urethane composition. (3) The heat-reactive, water-soluble or water-dispersible polyester urethane according to claim 1, wherein the blocking agent is a compound selected from acetylacetone, methyl acetoacetate, ethyl acetoacetate, and methyl ethyl ketoxime. Composition. (4) A claim in which the content of carboxyl groups in the urethane prepolymer having carboxyl groups in the molecule and having two or more free isocyanate groups is 1.0 to 7.0% by weight. The heat-reactive, water-soluble or water-dispersible polyester urethane composition according to item 1.