JPH0160060B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a treating agent composition for molded articles, and more particularly to a treating agent composition suitable as a surface treating agent or adhesive for polymer molded articles, particularly textile products. Conventionally, many attempts have been made to improve the surface properties of polyester molded articles, particularly their water absorption and antistatic properties. For example, a method in which a polyester molded article is treated with an aqueous dispersion of a so-called polyester polyether block copolymer consisting of a linear aromatic polyester segment and a hydratable polyoxyalkylene group (Japanese Patent Publication No. 1317/1983) Special Public Service 1977-
13197), a method of treating with a polyalkylene polyamine and a polyepoxy compound, etc. are known. However, in the former method, since the treated molded article and the treatment agent have the same crystalline repeating unit, the durability is improved compared to the case where the repeating units are different, but it is particularly difficult to wash when mechanical action is applied. The durability is insufficient, and the latter method can considerably improve durability by completely covering the surface with a three-dimensional polymer film formed by reaction using a large amount of treatment agent, but It has drawbacks such as causing a chemical reaction and being more likely to adsorb lipophilic stains. In addition, in the former method when the molded article to be treated is a textile product or in the latter method when a small amount of processing agent is used, the texture may feel slimy and cause discomfort to the wearer, or the molded article to be treated may be a film, etc. However, there were drawbacks such as tacking and blocking on the surface. The present inventors conducted extensive research to obtain a surface modifier free from the above-mentioned drawbacks, and as a result, they arrived at an aqueous dispersion of the treatment composition of the present invention. That is, the present invention provides a polyester polyether block copolymer (a) comprising an aromatic polyester segment and a polyoxyalkylene group having a molecular weight of 600 or more, and a sulfonic acid metal base-containing ester-forming compound with respect to the total acid component.
This is an aqueous dispersion of a treatment composition comprising a substantially water-insoluble polyester (b) containing 0.5 to 7.5 mol% or a polyurethane (c) using the polyester. The treatment agent composition according to the present invention is useful as a surface treatment agent for polymer molded products and textile products, and provides excellent hydrophilicity, antistatic properties, antifouling properties, and printing properties for polymer molded products with excellent durability. It is possible to add gender, etc.
It can also be used as a texture improver for textile products, as a binding agent for fibers, as a binder for non-woven fabrics, and as an adhesive between polymer molded products and other plastics, paper, metals, fabrics, wood, etc., as dyes and pigments, as magnetic particles, as polishing agents, etc. It is also useful as a bander for particles, etc. The processing agent composition of the present invention will be explained in more detail.
The polyester polyether block copolymer (a) in the present invention is a polyester polyether block copolymer consisting of an aromatic polyester segment mainly consisting of alkylene terephthalate repeating units and a polyoxyalkylene group. The aromatic polyester segment mainly contains alkylene terephthalate repeating units, but in some cases, copolymerized acid components include isophthalic acid,
Naphthalenedicarboxylic acid, P-oxyethoxybenzoic acid, diphenyldicarboxylic acid, adipic acid,
Examples include sepacic acid and azelaic acid. On the other hand, examples of glycol components include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. These acid components and glycol components can be used alone or in combination of two or more. The polyoxyalkylene group has the general formula
RO( _CnH2nO )lH [wherein R is hydrogen or an alkyl group, an aryl group, or a cycloalkyl group, n is a positive integer of 2 to 4, and l is a positive integer determined by the molecular weight]. polyoxyalkylene glycol or its monoether. The molecular weight of polyoxyalkylene units is usually
600 to 10,000, preferably 1,000 to 4,000. The weight percentage of the polyoxyalkylene component in the polymer is usually 20 to 90%, preferably
It is 50-80%. In addition, the polymer was prepared in a tetrachloroethane/phenol mixed solvent (40/60 weight ratio).
°C, relative viscosity measured in 1% solution is typically 1.1-3.0
and preferably 1.2 to 2.0. The softening temperature is usually preferably about 40 to 200°C. polyester(a)
is usually dispersible in water without a dispersant, but depending on the composition it can be easily made into a stable aqueous dispersion by using a small amount of a dispersion aid. The specific water-insoluble polyester (b) used in the present invention includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid, succinic acid,
Aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, dotecanedionic acid, dimer acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, oxybenzoic acid, Oxyacids such as oxyethoxybenzoic acid, oxybivalic acid, and ε-caprolactone or their ester-forming derivatives are used as acid components, and ethylene glycol, propylene glycol, butadiol, diethylene glycol, dipropylene glycol, neopentyl glycol, pentanediol, In the production of polyesters containing aliphatic glycols such as hexanediol, alicyclic glycols such as cyclohexanedimethanol, or ester-forming derivatives thereof as glycol components, sulfonic acid metal group-containing ester-forming components such as sulfosuccinic acid, sulfosuccinic acid, Dicarboxylic acids such as terephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5[4-sulfophenoxy]isophthalic acid as well as oxycarboxylic acids containing sulfonic acid metal groups. , the softening point obtained by copolymerizing glycols containing sulfonic acid metal bases, etc.
Examples include copolymerized polyesters that are heated at 40 to 200°C and contain 0.5 to 7.5 mol% of a sulfonic acid metal base-containing ester-forming compound based on the total acid component. Durability decreases when the softening point is less than 40℃, and
If it exceeds this amount, not only will water dispersibility become difficult, but also the film properties and processability of the film formed from the aqueous solution will deteriorate. In addition, if the content of the ester-forming compound containing sulfonic acid metal base is less than 0.5 mol%, the polyester itself will have difficulty dispersing, making it impossible to obtain stability of the aqueous treatment solution, while if it exceeds 7.5 mol%, the film formation properties and durability will deteriorate. , resulting in the disadvantage of reduced weather resistance. In addition, the molecular weight of polyester (b) is 2500
About 30,000, particularly preferably 5,000 to 25,000. In the production of the above polyester, crosslinking components such as trimethic acid, pyromellitic acid, trimethylolpropane,
Compounds with trimethylolethane, pentaerythritol, etc. having a 3-tube capacity or more may be copolymerized, and polyalkylene glycols with a molecular weight of 106 or less, usually 5% by weight or less based on the glycol component, may be copolymerized to the extent that water resistance and weather resistance are not impaired. ~500 polyethylene glycol, etc. may be used. Examples of metal salts include salts of Li, K, Na, etc., and particularly preferred is Na salt. As the acid component of polyester (b), aromatic dicarboxylic acid accounts for 40 to 40% of the total acid component.
100 mol %, and those in which the aromatic carboxylic acid content having a sulfonic acid metal base is 1 to 5 mol % are particularly preferred from the viewpoint of durability and weather resistance. Polyester (b) can be easily dispersed in fine particles into a stable aqueous dispersion with a particle size of 1 μm or less with the help of a water-soluble organic solvent such as lower alcohols, glycols, cellosolps, cyclic ethers, and ketones. As the water-soluble organic solvent, those having a solubility in water 1 at 20°C of 20 g or more and a boiling point of 50 to 200°C are usually used. Particularly preferred are ethyl cellosolp, n-butyl cellosolp, and isopropanol. The amount of water-soluble organic solvent used is preferably 2 to 50% by weight based on the total amount of water and water-soluble organic solvent. The water-soluble organic solvent can also be removed after dispersion. In such cases, it is preferable to use a dispersion aid and a protective colloid to an extent that does not impair stability. In addition, as the specific water-insoluble polyurethane (c) used in the present invention, the above-mentioned polyester
Examples include polyurethanes obtained by reacting an organic diisocyanate and optionally a low molecular chain extender with a sulfonic acid metal base-containing polyester (b)' preferably having a molecular weight of 500 to 5000, obtained in the same manner as in the production of (b). . Examples of organic diisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, m- or p-phenylene diisocyanate, toluylene-2,4- or 2,
Examples include 6-diisocyanate, dicyclohexylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate. Examples of the low molecular chain extender include ethylene glycol, butanediol, water, ethylenediamine, propylene diamine, monoethanolamine, hydrazine, and carbodihydrazide. A relatively large amount of sulfonate metal base is contained in the sulfonate metal base-containing polyester (b)′, and a polyester containing no sulfonate metal base and preferably having a softening point of 40 to 200°C is copolymerized during polyurethane production. Good too. In addition to polyester, high molecular weight bifunctional compounds such as polyalkylene glycol can also be copolymerized. In any case, the sulfonic acid metal base-containing component is 0.5 to 7.5 mol% based on the total acid component in the polyester in polyurethane (c).
Particularly preferably, it is necessary that 1 to 5 mol % of the polyester component be present as the main component. The softening point of polyurethane (c) is preferably 40 to 200°C. The polyester used for producing polyurethane preferably has an acid value of 20 equivalents/10 ⁶ g or less. The molecular weight of polyurethane (c) is preferably about 3,000 to 100,000. Polyurethane (c) can also be dispersed in substantially the same manner as polyester (b). In the present invention, "substantially water-insoluble" means that the solubility in hot water is 70% by weight or less. In addition, hot water solubility is determined by adding 20g of resin powder to 80ml of water at 70°C.
After stirring for 30 minutes, filter through a 1G glass filter,
Concentrate the filtrate to determine the amount of solids dissolved in water. Hot water solubility (%) Dissolved solid content g/20g x 100 The blending ratio of polyester polyether block copolymer (a) and polyester (b) and/or polyurethane (c) in the present invention is usually (a): (b) )or
(c)=5:95 to 90:10 weight ratio. If the blending ratio of (a) is less than this, antistatic properties, hydrophilicity, stain prevention properties, stain removability, etc. will decrease, and if the blending ratio of (a) is too high, durability will decrease and the target of treatment will be fibers. The product has the drawback of producing a slimy feel.
The preferred blending ratio of (a):(b) or (c) is
It varies depending on the purpose of treatment, but when used as a surface treatment agent, (a):(b) or (c) = 30:70 to 70:30
When used as an adhesive or a texture improver, the weight ratio is (a):(b) or (c) = 10:90 to 50:50. Further, washing durability, water resistance, etc. can be improved by using a crosslinking agent in the processing agent composition of the present invention, if desired. Examples of crosslinking agents that can be used include polyepoxy compounds, ethylene urea compounds, methylol crosslinking agents, blocked polyisocyanate, urethane prepolymers with blocked isocyanate groups, and polyepoxy compounds are particularly preferred. Polyepoxy compounds include di- or triglycidyl ether of glycerin;
Examples include oligomers of ethylene glycol diglycidyl ether, tricidyl isocyanurate, and allyl glycidyl ether, but polyglycidyl ethers of polyalkylene glycols or polyols having polyoxyalkylene chains are particularly preferred. The polyoxyalkylene chain usually has a repeating number of oxyalkylene units of about 2 to 20, especially 6.
~12 is preferable. The crosslinking agent is usually added to the processing agent composition, but it can also be applied to the article in a separate bath from the processing agent composition. The above treatment agent (a) + (b) +
The ratio of the combination of (c) and crosslinking agent varies depending on the type of crosslinking agent and treatment, but is usually preferably about 2:98 to 90:10. When a crosslinking agent is used in combination, it is also preferred to use a curing catalyst in the same bath or in a separate bath. A wide range of commonly known catalysts can be used as the catalyst, but it also varies depending on the type of crosslinking agent. For example, in the case of polyepoxy compounds, catalysts such as zinc borofluoride, magnesium borofluoride, zinc nitrate, aluminum chloride, and magnesium perchlorate are used. In addition to latent acid catalysts such as amine catalysts,
Examples include thiocyanate and polycarboxylic acid, but latent acid catalysts are particularly preferred. The processing method using the processing agent composition will be explained below. It is useful as a surface treatment agent or adhesive for polymer molded products, and examples of polymer molded products include fiber products, films, tapes, plate-like products, containers, leather-like products, and other molded products. be done. Examples of polymers include not only synthetic polymers such as polyester and polyamide, but also natural or recycled polymers such as cellulose and protein, semi-synthetic polymers such as acetate, and curable polymers such as unsaturated polyester. Especially polyester,
Effective when applied to polyamide. Examples of textile products include cotton, filament, tow, nonwoven fabrics, woven and knitted fabrics, synthetic paper, and rugs. The amount of treatment agent applied varies depending on the object to be treated and the purpose of treatment, but the total amount of (a) + (b) + (c) is usually the same for surface modification.
About 0.1 to 20% owf or 0.1 to 20 g/m ² is sufficient, and even larger amounts can be used for bonding polymer molded products to other objects. Processing methods include the pad method,
A treatment composition is applied by any method such as a spray method, a coating method, a coating method, a transfer method, etc., and after drying, it is preferably heat-treated. The heat treatment temperature is preferably 120 to 180°C, and may be wet heat or dry heat. When the object to be treated is textile products, etc., cleaning is performed as necessary to remove insufficiently fixed treatment agents, catalysts, etc. Alternatively, exhaustion treatment can also be carried out by heating at a high temperature in an aqueous solution containing a processing agent. In such cases, it is preferable to apply the crosslinking agent and catalyst in post-treatment. The treatment composition of the present invention may further include, if desired, an oxidation stabilizer, a light stabilizer, an antifungal agent, a fluorine-based oil repellent having a polyoxylalkylene group, a softener such as an organopolysiloxane/oxyalkylene block copolymer, and a wax. Inorganic fine powders such as colloidal silica, alumina, and other finishing agents can be suitably blended and treated, and depending on the case, they can be carried out as a separate step before or after the treatment of the present invention. Furthermore, durability can be further improved by subjecting the polymer molded product to alkali treatment, swelling treatment, etc. before treatment, and a modified texture can be imparted by subjecting it to weak alkali treatment after treatment with the treatment agent of the present invention. You can also. The present invention will be explained below with reference to Examples. In addition,
In the examples, parts and % simply refer to parts and % by weight unless otherwise specified. Evaluation of various properties was performed according to the following methods. (1) Molecular weight Molecular weight measuring device (Hitachi 115
Measurements were made using a (2) Softening point and crystal melting point Fully automatic melting point measuring device (manufactured by METTLER)
Measurement was carried out using MODELFP-1). (3) Particle size of aqueous dispersion Measured using a grindmeter and an optical microscope. (4) Viscosity Measured using a B-type viscometer at 25°. (5) Water absorption performance Wicking test (6) Antistatic performance In the crizzing test, the charged voltage of the test cloth after friction was measured using a Faraday gauge.
Friction cloth: nylon taffeta, atmosphere 40%RH, 20
℃. Example of manufacturing an aqueous dispersion of polyester (b) 1 300 parts of polyester (A-1) and 140 parts of n-butyl cellosolve were placed in a container and stirred at 150 to 170°C for about 3 hours to form a uniform and viscous melt. After getting
While stirring vigorously, 545 parts of water was gradually added, and after about 1 hour, a homogeneous pale blue-white aqueous dispersion (B-
1) was obtained. The obtained aqueous dispersion had good dispersibility and excellent storage stability. Similarly, aqueous dispersions (B-2) to (B-9) were obtained in the proportions shown in Table 2. Their dispersibility and dispersion stability are shown in Table 2. Production example of polyester (b) 1 95 parts of dimethyl terephthalate, 95 parts of dimethyl isophthalate, 71 parts of ethylene glycol, 110 parts of neopentyl glycol, 0.1 part of zinc acetate and 0.1 part of antimony trioxide were charged in a reaction vessel and the mixture was heated from 140 to
Transesterification reaction was carried out at 220°C for 3 hours.
Then 5-sodium sulfoisophthalic acid 6.0
The esterification reaction was carried out at 220-260°C for 1 hour, and then the
A polyester (A-
1) was obtained. Furthermore, polyesters (A-2) to (A-7) were obtained in exactly the same manner except that the raw materials shown in Table 1 were used. Their characteristic values were as shown in Table 1.

【table】

【table】

[Table] Disperse in water containing rufeate as an emulsifier and substantially remove the solvent.
Example 1 Polyester processed yarn fabric was padded (squeezing ratio 85%), dried, and heat treated (160%
℃, 60 seconds), soaping (soda ash, hydrosulfite each 1 g/, nonionic wetting agent 0.5
g/g for 5 minutes at 40°C), washed with hot water, and finished setting (170°C for 30 seconds). The water absorbency and antistatic properties of the obtained treated cloth were evaluated, and the results are shown in Table 4.

【table】

[Table] The treatment composition of the present invention provided good texture, excellent washing resistance, water absorption, antistatic properties, and stain removal properties. In particular, more favorable texture and durability were obtained by using a crosslinking agent in combination. Example 2 Using the same fabric as in Example 1, the same treatment was carried out using water-dispersible polyester dispersions B-2 to B-7 in place of B-1 in the recipe No. 6 of Table 3. Table 5 shows the performance of the processed fabric.

[Table] Example 3 Using the same fabric as in Example 1, the fabric was treated in the same manner as in Example 1, except that the ratio of polyester ether block copolymer and water-dispersible polyester in the recipe No. 6 of Table 3 was changed. The results are shown in Table 6.

[Table] Example 4 An oil agent was prepared in which a mixture of equal amounts (solid content) of the polyester/polyether block copolymer and water-dispersible polyester used in Example 1 was blended into a normal spinning oil agent at a polymer concentration of 3%. , the melt-spun polyester undrawn yarn was attached with a roller before being wound up, and then the hot plate temperature was 155℃ and the pin temperature was 100℃.
It was stretched to about 3.6 times and rolled up. The obtained yarn had good cohesiveness, and also had good durability in terms of water absorption and antistatic properties. Example 5 Terephthalic acid component 48 mol%, isophthalic acid component
48 mol%, 5-sodium sulfoisophthalic acid component 4 mol%, ethylene glycol component 50 mol%,
1000 parts of a polyester diol with a molecular weight of 2400 and a hydroxyl value of 45 consisting of 50 mol% neopentyl glycol component, 1280 parts of toluene, 850 parts of meral ethyl ketone, and hexamethylene diisocyanate.
64 parts were charged into a reactor and reacted at 70-80°C for 10 hours. Next, the solvent was distilled off from the reaction system to obtain polyester urethane. This polyester urethane was dispersed under the same conditions as in Table 2 B-3. The resulting dispersion was treated in the same manner as in Example 4, except that the water-dispersible polyester of Example 4 was replaced. As a result, the yarn had good cohesiveness, as well as excellent water absorption and antistatic properties with excellent durability.

【table】

Claims (1)

[Claims] 1. Aromatic polyester segment and molecular weight
A polyester polyether block copolymer (a) consisting of 600 or more polyoxyl alkylene groups and a substantially water-insoluble polyester ( b) or an aqueous dispersion of a treatment composition containing polyurethane (c) using the polyester. 2 Polyester polyether block copolymer
(a) and water-insoluble polyester (b) or polyurethane
The aqueous dispersion of the processing agent composition according to claim 1, wherein the ratio of (c) is (a):(b) or (c) = 5:95 to 90:10 by weight. 3. The aqueous dispersion of the processing agent composition according to claim 1 or 2, which contains a crosslinking agent as an additional component.