JPH0826256B2 - Resin composition for polyester fiber coating - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition for coating polyester fibers.

[0002]

2. Description of the Related Art Conventionally, acrylic resins, polyvinyl chloride resins, polyurethane resins, etc. have been known as polyester fiber coating resins.

[0003]

However, in the conventional case, when a polyester fiber cloth dyed with a disperse dye is coated, the dye in the fiber migrates to the coating resin layer, so that the dark-colored coated cloth and the light-colored or white-colored cloth are used. When the coating surface of the coating fabric of No. 1 comes into contact with the coating surface, the dye on the dark side is further transferred to the coating surface of light color or white, and there is a problem that it is significantly contaminated.

[0004]

The present inventors have arrived at the present invention as a result of intensive studies to obtain a resin composition for coating polyester fibers, which does not have the problem of contamination due to dye transfer. That is, the present invention is a hydroxyl group and a carboxyl group
A resin composition for coating a polyester fiber, which comprises a film-forming resin having neither of the above, an organic metal coordination compound in an amount of 0.5 to 30% by weight based on the resin, and a solvent if necessary. is there.

In the present invention, examples of the film-forming resin include polyurethane resin (1), acrylic resin (2), polyvinyl chloride resin (3), polyvinyl acetate resin (4) and silicone resin. (5), a fluororesin (6), and a mixture or copolymer of two or more kinds of these. Of these, preferred are polyurethane resins and / or acrylic resins.

Examples of the polyurethane resin (1) include a polyurethane resin containing an organic diisocyanate (a), a polymer diol (b) having a molecular weight of 500 to 5000, and a chain extender (c) having a low molecular weight.

Examples of the organic diisocyanate (a) include aromatic diisocyanates (4,4'-diphenylmethane diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate, etc.), aliphatic diisocyanates (hexamethylene diisocyanate, lysine diisocyanate). Etc.), alicyclic diisocyanates (isophorone diisocyanate, dicyclohexylmethane 4,4′-diisocyanate, etc.), and the like, and mixtures thereof.

Polymer diol (b) having a molecular weight of 500 to 5000
Examples thereof include polyether diol (a), polyester diol (b), polycarbonate diol (c), polybutadiene diol (d), hydrogenated polybutadiene diol (e), and mixtures thereof having the above-mentioned molecular weights.

As the polyether diol (a), a low molecular weight diol (for example, ethylene glycol, propylene glycol, 1,4-butanediol, etc.) and alkylene oxide (alkylene oxide having 2 to 4 carbon atoms: ethylene oxide, propylene oxide, 1, 2-butylene oxide, etc.), cyclic ethers (tetrahydrofuran, etc.) obtained by ring-opening polymerization or ring-opening copolymerization (block and / or random), for example, polyethylene glycol, polypropylene glycol, polyethylene-polypropylene (block or random) Mention may be made of glycols, polytetramethylene glycols, polytetramethylene-ethylene (block or random) glycols and the like and mixtures of two or more thereof.

The polyester diol (b) may be a condensed polyester diol obtained by reacting a low molecular diol and / or a polyether diol having a molecular weight of 1000 or less with a dicarboxylic acid, or a polycaprolactone diol obtained by ring-opening polymerization of a lactone. And so on. Examples of the low molecular diol include the same low molecular diols as exemplified in the item (a). Examples of the polyether diol having a molecular weight of 1000 or less include the polyether diols exemplified in the item (a) and having a molecular weight of 1000 or less. Examples of the dicarboxylic acid include an aliphatic dicarboxylic acid (eg, succinic acid, adipic acid, sebacic acid, etc.), an aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, etc.), and a mixture of two or more thereof. Examples of the lactone include ε-caprolactone. Specific examples of these polyester diols include polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, poly (tetramethylene ether) adipate, polycaprolactone diol, and the like, and mixtures of two or more thereof.

Examples of the polycarbonate diol (c) include polybutylene carbonate diol and polyhexamethylene carbonate diol.

As the low molecular weight chain extender (c),
Low molecular weight diols, aliphatic diamines (ethylenediamine, etc.), alicyclic diamines (isophoronediamine, etc.), aromatic diamines (4,4'-diaminodiphenylmethane, etc.), aromatic-aliphatic diamines (xylene) exemplified in (a). Diamines), alkanolamines (such as ethanolamine), hydrazines, and the like, and mixtures of two or more thereof.

The polyurethane resin (1) can be produced by a usual method, for example, a one-shot method in which (a), (b) and (c) are simultaneously reacted, or (a) and (b) are reacted. A prepolymer method in which an NCO-terminated prepolymer is produced and then reacted with (c).

The polyurethane resin (1) can be produced in the presence or absence of a solvent. Such solvents include amide-based solvents (dimethylformamide, dimethylacetamide, etc.), sulfoxide-based solvents (dimethylsulfoxide, etc.), ketone-based solvents (methyl ethyl ketone, etc.), ether-based solvents (dioxane, tetrahydrofuran, etc.), ester-based solvents (ethyl acetate). Etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.) and the like, and mixtures of two or more thereof.

In the production of the polyurethane resin (1), the reaction temperature may be the same as the temperature usually employed in the polyurethane-forming reaction, usually 20 to 100 ° C. when a solvent is used, and usually 20 to 220 when no solvent is used. ℃.

In order to accelerate the reaction, a catalyst usually used in polyurethane reaction [for example, amine-based catalyst (triethylamine, triethylenediamine, etc.), tin-based catalyst (dibutyltin dilaurate, etc.)] can be used if necessary.

If necessary, a polymerization terminator [eg monohydric alcohol (ethanol, butanol, etc.), monovalent amine (methylamine, butylamine, etc.)] can be used.

The acrylic resin (2) includes (meth)
Acrylic acid or its derivatives [eg methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic) Acid amide, etc.] One or more polymers or copolymers of these with other vinyl monomers.
Aromatic vinyl hydrocarbon monomer (eg styrene),
Olefin hydrocarbon monomer (ethylene, propylene,
Butadiene, isoprene, etc.), vinyl ester monomers (eg vinyl acetate, etc.), vinyl halide monomers (vinyl chloride, vinylidene chloride, etc.) and the like.

The acrylic resin (2) can be manufactured by heating a solution in which each of the constituent monomers is dissolved in a suitable solvent to a suitable temperature. At this time, if a suitable polymerization catalyst is added, not only the temperature required for the polymerization can be lowered, but also the time required until the acrylic resin (2) having a desired molecular weight is obtained can be shortened. You can

As the solvent used for producing the acrylic resin (2), hydrocarbon solvents (n-hexane etc.), aromatic hydrocarbon solvents (toluene, xylene etc.), ester solvents (ethyl acetate) Etc.), ketone solvents (such as methyl ethyl ketone), and mixtures of two or more thereof.

The reaction temperature for producing the acrylic resin (2) is usually 50 to 150 ° C. Examples of the polymerization catalyst include azo compounds (azobisisobutyronitrile and the like), peroxides (benzoyl peroxide and the like) and the like. The amount used is, for example, usually 0.1 to 10% by weight based on the total weight of the constituent monomers.

In the present invention, as the organometallic coordination compound, an organoaluminum coordination compound such as aluminum trisacetylacetonate, aluminum triisopropoxide, aluminum trisethylacetonate, ethyl acetoacetate aluminum diisopropylate, zirconium tetrakis (Acetylacetonate), organic zirconium coordination compounds such as diisopropoxyzirconium bisacetylacetonate, titanium tetrakisacetylacetonate, organic titanium coordination compounds such as diisopropoxytitanium bisacetylacetonate, and two or more of these A mixture may be mentioned. Among these, preferred are organoaluminum coordination compounds and / or organozirconium coordination compounds.

In the present invention, the amount of the organometallic coordination compound is usually 0.5 to 3 relative to the weight of the solid content of the film-forming resin.
It is 0%, preferably 1 to 20%. If it is less than 0.5%, the effect of suppressing dye transfer is poor, and if it exceeds 30%, it deposits on the surface of the coating and the appearance becomes poor.

The composition of the present invention may optionally contain a solvent. Examples of the solvent include those used in the step of producing the coating film-forming resin. For example, in the case of the polyurethane resin (1) and the acrylic resin (2), the same solvents as those mentioned above as the solvent used in each production step can be used. Also, alcohol solvents (methanol, ethanol, isopropyl alcohol, etc.), water, etc. can be used.

In the resin composition of the present invention, if necessary, various stabilizers for improving weather resistance and heat deterioration, crosslinking agents such as polyfunctional isocyanates, colorants, inorganic fillers, organic modifiers,
Other additives and the like can be included.

The resin composition of the present invention is usually a solution or dispersion containing the above-exemplified components. However, when the coating film-forming resin has a low viscosity, a mixture of the components containing no solvent may be used, and the above-exemplified solvents may be mixed if necessary. The concentration of the resin composition is usually 5 to 50% by weight, preferably 10 to 45%.

The composition of the present invention may be mixed by ordinary stirring alone, or by a dispersion mixing device (ball mill, kneader,
It can also be obtained by dispersing and mixing using a sand blaster, a roll mill, etc.).

The polyester fiber to be coated with the composition of the present invention is not particularly limited, and examples thereof include woven fabrics, knitted fabrics and non-woven fabrics made of a single polyester fiber, as well as mixed spinning, mixed fiber and mixed weaving which essentially require polyester fiber. It is also useful for both mixed knitting and the like. Further, the composition of the present invention is a coating material capable of preventing dye migration of a dyed polyester fiber base material, but this dyed base material requires a particularly limited disperse dye or special dyeing conditions. However, the composition of the present invention has the above-mentioned preventive effect even if it is dyed with a usual disperse dye such as carrier dyeing or high temperature dyeing. Further, the composition of the present invention has the above-mentioned preventive effect even if the polyester fiber base material is heat-treated in advance with a calender roll or is treated with a silicone-based or fluorine-based water repellent.

The method for coating the resin composition of the present invention on the polyester fiber substrate may be a usual method. For example, a direct coating method of directly coating on a polyester fiber base material and drying, or after forming a resin film on release paper, applying an adhesive, bonding with a polyester fiber base material, drying and peeling from the release paper Transfer A coating method and the like can be mentioned.

The film thickness of the coating resin layer is usually 1 to 200 μm, preferably 10 to 100 μm as resin solid content.
If the film thickness is less than 1 μm, the effect of suppressing dye transfer is insufficient and the waterproof property is insufficient, and if it exceeds 200 μm, the texture of the coated fabric becomes hard, which is not preferable.

The coating resin layer may be a single layer or a multilayer structure. In the case of a multilayer structure, at least one layer may be the resin composition coating layer of the present invention. An example of this multi-layer structure is a multi-layer structure having an acrylic resin layer between polyester fibers and a polyurethane resin layer for the purpose of a sealing effect of suppressing impregnation of the polyurethane resin.

[0032]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Parts in the examples and comparative examples are parts by weight, and% is% by weight. The abbreviations in the examples have the following meanings.

(Organic Metal Coordination Compound) Al-AA: Aluminum Trisacetyl Acetate Zr-AA: Zirconium Tetrakisacetylacetonate

The dye transfer stain fastness in the examples was evaluated according to the following method. Coating surface of test piece (5 cm x 5 cm) and white cloth attached to polyester (15% polyurethane resin and 85% dimethylformamide on the same cloth as the test piece)
Coated with the solvent solution from No.3, immersed in water to solidify, then washed with water and dried, sandwiched between two glass plates so that the coating surface of 5 cm x 5 cm) comes into contact, 1k
Each sample was left for 2 hours in a constant temperature dryer of 80 ° C. ± 3 ° C. under a load of g and allowed to cool, and then the state of dye transfer from the test piece to the attached white cloth was evaluated with a gray scale for contamination.

Examples 1 and 2, Comparative Example 1 In a four-neck flask, 226 g of polyethylene adipate having an average molecular weight of 2000, 9.2 g of ethylene glycol, 66 g of 4,4'-diphenylmethane diisocyanate and 66 g of dimethylformamide 70 were used.
Charge 0 g and toluene 500 g, and in a dry nitrogen atmosphere.
The reaction was carried out at 70 ° C. for 10 hours to obtain a polyurethane resin solution (a) having a resin concentration of 20% and a viscosity of 100 poise (20 ° C.). Using this solution, a solution having the composition shown in Table 1 was prepared.

[0036]

Table 1 | Example-1 | Example-2 | Comparative Example-1 | ----------------------- Solution (a ) | 100 parts | 100 parts | 100 parts | Al-AA | 1 part | − | | − | Zr-AA | − | 1 part | − | −−−−−−−−−−−−−−−−−− −−−−−−−−−−−−

Then, a plain woven fabric using polyester filament yarn of warp yarn 50 denier and weft yarn 75 denier was used as a disperse dye Resoline Blue FBL 3% OWf at a temperature of 130 ° C.
After dyeing for one minute and washing, heat setting was performed at 180 ° C. The dyed polyester fabric was coated with each of the adjustment liquids shown in Table 1 by a knife coater to a thickness of about 100 μm and dried at 100 ° C. for 5 minutes to obtain a coated fabric. The film thickness of the resin layer of the resulting coated fabric is approximately 20μ.
It was m.

Example 3, Comparative Example 2 200 g of ethyl acrylate, 800 g of butyl acrylate and 1000 g of toluene were placed in a four-necked flask having a stirrer, a reflux condenser, and a nitrogen inlet, and heated while stirring and nitrogen was passed through. When the temperature reached 70 ° C, a solution of 20 g of azobisisobutyronitrile dissolved in 80 g of toluene was gradually added over 1 hour, and stirring was continued for another 7 hours. After the polymerization was completed, 3000 g of toluene was added to dilute and
A solution (b) having 20% and a viscosity of 90 poise (20 ° C.) was obtained. A solution having the composition shown in Table 2 was prepared using this solution.

[0039]

[Table 2]

On the same polyester fabric as in Example 1, Table 2
Each of the prepared preparations was coated with a knife coater to a thickness of about 70 μm and dried at 100 ° C. for 5 minutes to obtain a coating cloth.
The coating film thickness of the resin layer of the obtained coated fabric is about 15
μm.

Test Example 1 Table 3 shows the results of evaluation of the dye transfer stain fastness of each coated fabric obtained in Examples 1 to 3 and Comparative Examples 1 and 2.

[0042]

[Table 3] As is apparent from Table 3, the coated fabrics of Examples 1-3 exhibited high migration stain fastness. On the other hand, the coated fabrics of Comparative Examples were inferior in practicality due to poor migration stain fastness.

[0043]

EFFECT OF THE INVENTION The polyester fiber coated cloth obtained from the resin composition of the present invention has suppressed dye transfer compared with the conventional one, and the stain prevention performance is remarkably improved. The polyester fiber-coated cloth coated with the resin composition of the present invention has a soft texture and good water resistance. Since the resin composition of the present invention exhibits the above effects, it is useful as a resin for coating processing of polyester fibers for clothes, umbrellas, canvas, tents and the like.

Claims (3)

[Claims] 1. Having both a hydroxyl group and a carboxyl group
No coating film forming resin, 0.5 to 30 relative to this resin
A resin composition for coating a polyester fiber, which comprises an organometallic coordination compound in a weight percentage, and optionally a solvent. 2. The resin composition according to claim 1, wherein the organometallic coordination compound is an organoaluminum coordination compound and / or an organozirconium coordination compound. Wherein said film-forming resin is a polyurethane resin and / or an acrylic resin according to claim 1 or 2 resin composition.