JPS5883046A - Aqueous polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. useful as a coating agent, a binder for fibers, etc. and capable of forming a flexible, tough film having resistance to water and dry-cleaning, by neutralizing a specified polyester resin with ammonia or a tert. amine. CONSTITUTION:A polyester resin having an acid value of 5-60 and contg. at least 0.1 equivalent of branched unit per kg of resin is used which is obtd. from 2-6mol% (based on the amount of the whole carboxylic acid component) of an alkali metal salt of an ester-forming sulfonic acid (A) such as sodium sulfoterephthalate, a carboxylic acid component (B) contg. at least 90mol% polycarboxylic acid component consisting of an arom. polycarboxylic acid such as terephthalic acid and an 8C or higher aliph. polycarboxylic acid such as suberic acid in a molar ratio of 95/5-40/60, and a polyol component (C) contg. at least 70mol/% ethylene glycol. The compsn. is obtd. by neutralizing said polyester resin with ammonia or a tert. amine such as triethanolamine.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel aqueous polyester resin composition, and more particularly to a flexible polyester resin composition having water spraying properties and dry cleaning resistance useful for various binders for textiles, coating agents, etc. The present invention relates to an aqueous polyester resin composition capable of forming a strong film with high elasticity.

In recent years, from the standpoint of environmental hygiene, STFR agent-based resins or water fiber resins that do not use organic solvents have been sought after in all processing processes such as impregnation, painting, adhesion, and printing, and the same is true in the above-mentioned textile processing field.

That is, processing agents for #iL fiber materials, such as non-#iL fiber materials. Cloth binders, floating binders, printing binders, waterproof coating agents, corrugating, wading, coloring, and other coating agents, packing agents, synthetic leather resins, etc. are all flexible enough to withstand large deformations of textile materials. A material that is highly elastic and forms a tough film is required. Conventionally, soft acrylic resins, ethylene-vinyl acetate copolymer resins, various synthetic rubber latexes, chlorosulfonated polyethylenes, urethane resins, etc. have been used for these purposes.

Acrylic resins, ethylene-vinyl acetate copolymer side fats, various synthetic rubbers, etc. have traditionally been used in the form of aqueous emulsions, but these emulsion-type resins inherently have poor dry cleaning resistance and contain emulsifiers. Generally, problems such as poor water resistance and poor color fastness to rubbing are common. In addition, urethane resin has good elastic properties and high strength, and although it is useful for these applications, it is still expensive and it is difficult to make it water-based while retaining its original good physical properties. In addition to rubber-based resins, urethane 11-based resins have a big problem of poor light resistance and increase in weight when yellowing. Furthermore, these resins have a problem in that they do not have sufficient adhesion to polyester, which is the main component of 81% of synthetic fibers, which have increased in recent years in the processing of fiber materials.

In view of this situation, the present invention was developed as a result of extensive research into a stable water-based fiber binder and coating agent that has excellent adhesion to polyester fibers, as well as excellent dry cleaning resistance, water resistance, light resistance, and dyeing abrasion fastness. The present invention was achieved by discovering an aqueous polyester resin composition that satisfies these requirements and is capable of forming a strong film that is flexible and rich in elasticity, which is essential for fiber applications.

Regarding polyester resins that can be dissolved in water,
-40875, JP-A No. 50-83497, JP-A No. 50-83497
6-5476 Temple is known to contain a sulfonate in its molecule and use this as a water-solubilizing component, but these resins are used as warp weft agents, hot melt binders for paper, and primers for photographic films. It is a scissors resin that is used for such purposes, and is not suitable for use as a binder or coating agent for flexible fiber materials, and is suitable for these applications. Furthermore, these resins are permanently water-decomposable and are easily reversibly dissolved in water, particularly hot water, even after use, and have poor water resistance.

Generally, in order to improve the water resistance of water-soluble resins, K is mixed with a crosslinking agent and crosslinked, but these water-disintegrable polyester resins are not intended to be crosslinked and therefore do not have the means to do so. Therefore, even if a crosslinking agent is added, the crosslinking performance is poor, and it is a national problem to sufficiently improve water resistance.

The aqueous polyester resin composition of the present invention is composed of a segmented polyester resin having flat crystalline hard segments and flexible soft segments, and also contains an alkali metal sulfonate and a carboxylic ammonium or carbonate group as hydrophilic groups. It contains an amine salt, and the film obtained therefrom has a relatively soft and elastic properties. In addition, it is water resistant even when used alone without being reversibly dissolved in water, and has excellent properties such as rack 4# performance.
It has different properties from conventional water-disintegrable polyester resins.

The present invention particularly relates to an aqueous polyester resin composition that can be used as various binders and coating agents for fibers,
η) The ester-forming alkali metal sulfonic acid salt compound is contained in an amount of 2 to 6 moles based on the total carboxylic acid component, (Cl aromatic polycarbonate) and (Cl ethylene glycol is 70 mole based on the total polyol component). containing 0.1 or more equivalents of branching units per 1 unit of produced resin, containing 5 to 5 to
60 polyester resin is ammonia or 317&
Aqueous polyester resin compositions neutralized with amines are provided.

kL as ester-forming sulfonic acid alkali metal chloride used in the aqueous polyester resin composition of the present invention
Sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfosuccij12.2-sulfo-1,4
Examples include alkali metal salts of sulfone compounds such as -bis(hydroxyethoxy)benzene and ester-forming derivatives thereof.

Among these, sodium sulfotereheptanoic acid and 5-sodiumsulfoisoheptanoate are more preferably used. The ester-forming alkali metal sulfonate compound, together with Toshinori's carboxylic acid ammonium salt or amine salt, is an essential ingredient for making polyester into aqueous resin. affect. In order to obtain sufficient water jetting properties, the sulfonic acid alkali metal chloride must be added with less violet than the violet which achieves water-based polyester w fat by itself, but it is necessary to add less violet to the total carbon enemy component. If the amount is less than 2 moles,
The resulting polyester resin lacks hydrophilicity and is difficult to make water-soluble, and if the amount is more than 6 moles, the hydrophilicity is too strong and sufficient water jetting properties cannot generally be obtained. More preferably, the cap used is 3 to 5 molar. The aromatic polycarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, and ester-forming derivatives thereof. Preferably, the aromatic polycarboxylic acid is one that forms a hard segment of the polyester resin and induces a segment with high crystallinity, and terephthalic acid, inphthalic acid, and ester-forming derivatives thereof are also preferable.

Examples of aliphatic polycarboxylic acids having an envy number of 8 or more include speric acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, and diY-
These aliphatic polycarboxylic acids contained in these ester-forming derivatives form the soft segment of the polyester resin, and the aliphatic chain between the carboxy groups is required to be long to some extent. If the number of carbon atoms is less than 8, the effect on the flexibility and elasticity of the polyester resin will be low, and the hydrolysis resistance will decrease, which is not preferable. More preferred aliphatic polycarboxylic acids include azelaic acid, sebacin 1llp, 1
．． 10-decanedicarboxylic acid and mixtures thereof.

The polyester resin composition of the present invention is capable of forming a soft and elastic skin particularly suitable for binding and coating of textile materials by the combination of the aromatic polycarboxylic acid component and the aliphatic polycarboxylic acid component. Is it possible, and depending on the combination ratio, it can range from relatively hard to soft? You can get it. Generally, the ratio of aromatic polycarboxylic acid to aliphatic polycarboxylic acid is 9515-40
/60 (molar ratio) is required; if the amount of aromatic polycarboxylic acid exceeds 95 mol, the flexibility required to adapt to the fiber material will be insufficient, and if it becomes less than 40 mol, the mechanical strength will decrease. It is insufficient in terms of A more conservative range is 80/20 to 50,150 (molar ratio). These polycarboxylic acids account for at least 90% of the total carboxylic components.
% or more.

Ethylene glycol is an essential component of the polyol component, and must account for at least 70 moles or more of the total polyol component. The polyol component reacts with the acid component to form a hard segment and a soft segment, respectively, and this polyol component greatly influences the crystallinity of the hard segment. That is, if other glycols are mainly used, the crystallinity of the hard segment will decrease and the mechanical properties of the polyester resin will become extremely poor, which is not preferable. Polyol components that improve crystallinity include ethylene glycol and 1,4
-Butanediol is an example, but the latter is not preferred because it tends to cause a slag reaction. In addition, examples of polyols that can be used in combination with ethylene glycol include diethylene glycol,
Triethylene glycol, neopentyl glycol, 1
．． 5-bentanediol, 1,6-butanediol, 1
．． Examples include diols such as 6-hexanediol.

Next, the introduction of branching involves the introduction of at least six functional groups (X
co-A of a compound having an acid group and/or a carboxyl group)
This is done by Such compounds include glycerin, trimethylolpropane, trimethylolethane,
Examples include pentaerythritol, trimellitic acid, pyromellitic acid, citric acid, tartaric acid, and dimethylolpropionic acid.

It is necessary that this branched component reacts in an amount of at least 11 moles per 1 kg of the produced polyester tree, that is, in the case of the above-mentioned trifunctional compound, it is necessary to react with at least 1 mole. This branching has an important meaning when crosslinking the polyester resin composition with a crosslinking agent. That is, the introduction of branching units improves crosslinking performance, and good curing can be achieved with a small amount of crosslinking agent.

If the branching units are less than α equivalent per hour of the produced polyester resin, sufficient performance cannot be obtained even by crosslinking, which is undesirable.

The synthesis of the polyester resin used in the aqueous polyester resin composition of the present invention is carried out by conventional methods.

Rather, the acid component and the glycol component are heated to 180 DEG C. to 260 DEG C. in the presence or absence of a catalyst, and the mixture is carried out under reduced pressure if necessary. When the acid component is a lower alcohol ester, it is preferable to transesterify it in advance with the glycol used. It is preferable that the molecular weight of such a resin is large, but it is better to preserve functional groups for crosslinking, and although the molecular weight is not limited to a numerical value, in general, 2000 to 2Q,000 is suitable.

Furthermore, the polyester resin used in the present invention is a polymer having an acid group so that it can be irreversibly water-based and not dissolved in water after processing, and can be effectively made into strips. This acid group is neutralized with ammonia or tertiary amines, thereby becoming a water group, and at this point, together with the water group of the ester-forming alkali metal sulfonate compound, the aqueous base of the polyester w-shield. It makes it possible to In addition, this carboxylic acid salt is decomposed by heating, resulting in insolubilization of the polyester resin and the liberated acid group is used as a crosslinking agent, such as aminoplus, oxidation, aziridine compound, etc.
These reactive groups also act as autocatalysts and enhance the redemptive properties of polyester resins.

It is preferable that the acid group size of polyester SaW is #15 to 600 mm, and it is smaller than 5&f water 1 m1.
-(Hikai inner distance and at the same time, the row lateral performance is poor, and 60
If it is larger, it will not be possible to sufficiently close the molecular cap of the polyester resin, which is also unfavorable in terms of physical properties. A more desirable acid value is 10-50.

This acid value can be adjusted by appropriately installing a side table for the acid component and the glycol component, and if necessary in the latter stage of the reaction, adding M, such as trimellitic anhydride, 7-talic anhydride, and cono-phosphoric anhydride
Anhydride or adipic acid, Azerai/#! The g4 adjustment can also be carried out by reacting the terminal hydroxyl group with , ce/< cynic acid, etc.

The polyester resin particles thus obtained are then neutralized with ammonia or 6th class amines and at the same time made water-soluble. Aqueousization is generally carried out by injecting the polyester resin and the base 'lk:fIi' into hot water. Such 6th-class amines include trimethylamine, triethylamine, triisopropylamine, triethanolamine, methyljetanolamine, dimethylethanolamine, diethylethanolamine, dimethylglobinolamine, diethylpropanolamine, morpholine, etc. %jlLEasy to volatilize, water storage, little odor, high safety, etc. should be taken into consideration.

The aqueous polyester superfat composition of the present invention that can be used in this manner forms a flexible and elastic film by heating it on a carrier, and the formed film is also easily resistant to hot water. does not dissolve. In addition, by using a cross-linking agent in combination, it is possible to cross-link and tear the film to form a tough film with excellent water resistance and solvent resistance. As described above, the aqueous polyester resin composition of the present invention is capable of forming extremely durable, flexible, elastic, and strong skin, and also has compositional properties that are difficult to obtain on the skin of textiles and buttocks. It also has good adhesion properties for polyester fibers, and since it does not use any additives or emulsifiers, it is excellent in terms of indigo arashi and jofun bonding properties for dyed products. Yes, processing agents for fiber materials, such as non-woven fabric binder, 70-layer binder, fiber agent, printing binder, glass fiber sizing agent, waterproof coating, shelling,
It is extremely useful as a resin for extrusion, colored coating agents, backing agents, synthetic leathers, etc.

Next, the present invention will be explained in detail with reference to Examples, but the present invention does not extend thereto. The inside part and the part are X
According to jjk standard.

Example 1 Dimethyl terephthalate 6492 parts, 5-sodium sulfodimethyl isophthalate aa, am, ethylene glycol 279s, diethylene glycol 53 parts, zinc acetate [13 parts mixed together'i11 under cumulative air flow under air flow from 0°C to 2
After heating methanol to 00°C and distilling off the transesterification, 616 parts of sebacic acid and 2 parts of trimellitic anhydride were added.
Add 8 parts of a, 199.2 m of isophthalic acid, 279 parts of ethylene glycol, and 15 parts of antimony trioxide,
The reaction was carried out at a temperature of 00 to 220°C, and almost the theoretical amount of water was distilled off. Then, the pressure inside the system was reduced, and the reaction was carried out at 240° C. until no glycol was released. At this point, the reaction system had an acid value of 4 and an OH value of 16. Here, 19.2 parts of anhydrous trimesin (trimesine) #1 was further added, and the mixture was reacted at 170°C for 60 minutes, and the produced am was taken out. This polyester resin has an acid value of 15
It was a transparent rubber-like substance. 1000 parts of this polyester resin is mixed in about 2500 parts of 80°C hot water,
Aqueous ammonia of 5- was added one after another to keep the pH at 7 to 9, and it took 1 hour to dissolve, resulting in an opalescent colloid #! I got the enemy.

Finally, this polyester resin aqueous solution had a domestic content of 28%.
, pH 7.5. This aqueous polyester resin solution was spread on a polyethylene terephthalate (PET) film and dried at 100° C. for 15 minutes, resulting in a transparent and slightly sticky coating. Cellophane tape was applied to this m-side and the cellophane tape was instantly peeled off, but the coating did not peel off from the PET film. Moreover, when this coating film was immersed in hot water at 50° C., it turned slightly white to almost no change in shape.

5 parts of trimethoxymethyl-type melamine JIM resin was mixed with the gtoo part of this water-based polyester resin bath, and the mixture was spread on a PET film, dried, and then heat-treated at 150°C for 5 minutes. It becomes a membrane to a certain strong one,
Moreover, it was not immersed in hot water at 90°C or organic solvents such as hyperkleen, toluene, and methanol. Table 1 also shows the results of using an aqueous polyester resin solution as a binder for flocking.

Furthermore, compared to conventional acrylic binders, the composition of the present invention has an excellent contact layer*t of 4C# in both dry, wet and dry cleaning resistance, and has a soft texture and is easy to wash. It was found that it was a good binder. In addition, a clear improvement in flocking strength was observed when used in combination with acrylic emulsion at 10%. By changing the carboxylic acid composition, polyol composition, and content of 5-sodium sulfodimethyl iso-7 tallate, etc., a valley water-based polyester street fat composition was obtained. The results are summarized in Table-2. In addition, Examples 1 to 5 were all stable colloidal solutions, and no reversibility such as dissolving the cast film in water was observed. In addition, when melamine + M resin, polyvalent epoxy compound, and aziridine compound are used together as a building agent, a crosslinked film is formed, resulting in an elastic, strong film with excellent water and solvent resistance, and can be used as a nonwoven fabric binder, flocked binder, For various plant coating synthetic leather! It was useful as M fat.

In addition, all of Comparative Examples 1 to 4 do not satisfy the requirements for non-invention, and Comparative Example 1 forms an extremely hard film with a reduced texture, so it is not bad as a binder for fiber materials. In addition, Comparative Example 2 had too little sulfonated alkali metal salt to be dispersed and dissolved in water, and Comparative Example 6
is not preferable because it has low monotony even after crosslinking. Furthermore, Comparative Example 4 not only has poor water spraying properties due to its strong water solubility, but also has low elasticity and strength due to the small amount of ethylene glycol.

Procedural amendment (voluntary) January 20, 1980 Commissioner of the Japan Patent Office Shima 1) Haruki Tono1, Indication of the case 1982 Patent Application No. 1796272, Name of the invention Aqueous polyester resin composition 3, Amendment Relationship with the case of a person who does

(2) Same book, page 6, line 5 Correct "2-6 mol%" to 12-8 mol%j.

(3) r70 on page 6, line 9 and page 10, line 8 of the same book
mol%" is corrected to r50 mol%J.

(4) The same book, page 8, line 1 Correct "6 mol%" to "8 mol%j."

(5) Page 8, line 3 of the same book Correct "3 to 5 mol%" to r3 to 6 mol%J.

(6) In the same book, page 11, line 6, [1,6-butanediol, 1,6-hexanediol, etc.] was replaced with [1,4-butanediol, 1,6-hexanediol, dihydroxyethoxybenzene, cyclohexane dimeta] Corrected to tool, hydrogenated bisphenol A, etc. 1.

Claims: (A) an ester-forming alkali metal sulfonic acid salt compound of 2 to 8 mol% based on the total carboxylic acid component; (B) an aromatic polycarboxylic acid and an aliphatic polycarboxylic acid having 8 or more carbon atoms; 1 kg of produced resin derived from a carboxylic acid component containing 90 mol % or more of a polycarboxylic acid in which the 111 ratio of Contains 0.1 equivalent or more of branching units per unit, and has an acid value of 5 to 60
An aqueous polyester resin combination acid product characterized in that the polyester resin is neutralized with ammonia or tertiary amines.

Claims (1)

[Claims] (A) 2 to 6 mol of the ester-forming sulfonic acid alkali metal salt compound relative to the total carbon range components; (B) N-
A carboxylic acid component containing 90 moles or more of polycarboxylic acid #2 in which the ratio of group F polycarboxylic acid to aliphatic polycarboxylic acid having an IR cumulative number of 8 or more is 9575 to 40/60 (molar ratio), and (C) ethylene. The resulting resin IKI
i-Il, containing 1 equivalent or more of branching units and having 5 acids;
~60 polyester resin is ammonia or 51M
An aqueous polyester resin composition whose percentage value indicates that it is neutralized with k-amine.