JPS633913B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-dispersible or water-soluble polyester adhesive having excellent flame retardancy, hydrolysis resistance, adhesive properties, etc. In recent years, flame retardant performance has been required for various applications,
Flame retardant fibers have been developed accordingly. Examples include polyvinyl chloride fibers, modacrylic fibers, polyclar fibers, aramid fibers, and the like. Although each of these fibers has excellent flame retardancy, they are unsatisfactory in yarn quality, bulk, etc., and there is no flame-retardant fiber with balanced performance as a fiber. There has been a demand for flame retardant modification of polyamide fibers.
Polyester fibers have been successfully made flame retardant and are already commercially available. However, although this fiber itself has excellent flame retardancy and thread quality,
For example, they have the disadvantage of causing troubles such as improper selection of finishing agents or adhesives, or loss of flame retardancy due to compounding with other materials. At present, no excellent finishing agent or adhesive that can impart flame retardancy to such general-purpose thermoplastic fibers has yet been developed. Regarding water-dispersible or water-soluble polyester type finishing agents or adhesives,
It is disclosed in JP-A No. 40873, Japanese Unexamined Patent Publication No. 121336-1980, and the like. However, such a composition not only cannot impart flame retardancy to the fiber structure, but also has the disadvantage that depending on the amount used, the flame retardance of the flame-retardant modified fiber may be lowered. As a method of imparting flame retardance, a method of mixing or copolymerizing a phosphorus compound is generally known.
However, in the case of the mixing method, disadvantages such as separation from the aqueous dispersion or solution and reduction in adhesive properties occur, so that it cannot be practically used for adhesives.
On the other hand, in the case of a copolymerization method, the hydrolysis resistance of the phosphorus compound is usually poor, resulting in problems of poor solution stability and the accompanying decrease in adhesive strength. The present inventors have arrived at the present invention as a result of intensive research aimed at developing a flame-retardant polyester adhesive that is particularly effective for thermoplastic fiber structures. That is, the present invention provides a polyester comprising an aromatic dicarboxylic acid and/or an ester-forming derivative thereof and a glycol, wherein (1) 5-sodium sulfoisophthalic acid and/or 5-potassium sulfoisophthalic acid or 3 to 12 mol% of at least one of these ester-forming derivatives; (2) a small amount of a phosphorus-containing dicarboxylic acid compound represented by the following general formula [] in an amount corresponding to 500 to 10,000 ppm of phosphorus based on the polyester; and (3) a portion of the glycol is at least one polyalkylene glycol represented by the following general formula [], and the remainder is ethylene glycol, propylene glycol, tetramethylene glycol, and neopentyl glycol. A polyester adhesive having flame retardancy, which is at least one of the selected polyester adhesives and is obtained by copolymerizing 4 to 30% by weight of the polyalkylene glycol with respect to polyester. (However, R and R ¹ are the same or different groups such as a hydrogen atom, a halogen atom, or a hydrocarbon group having 6 or less carbon atoms, and R ² and R ³ are the same or different groups such as a hydrogen atom or a hydrocarbon group having 7 or less carbon atoms. represents a hydrocarbon group or a group represented by (R ⁴ O) rH. R ⁴ represents an ethylene, propylene or butylene group, and r represents 1 to 10
, l and m are 0 or an integer of 1 to 4, and n is 0, 1 or 2. ) HO (R ⁵ O) pH ... [] (However, R ⁵ is an ethylene, propylene or butylene group, and p is an integer from 2 to 90.) The polyester adhesive according to the present invention has stable and good flame retardancy. It also has good heat resistance and hydrolysis resistance, and can exhibit stable and excellent adhesion even when used in an aqueous medium. Furthermore, copolymerizing a specific amount of a specific phosphorus-containing compound has the advantage of improving adhesiveness.
Furthermore, the thermoplastic fiber structure to which the polyester is attached exhibits good flame retardancy and has the characteristic of adhering very strongly to other materials under a certain heat source. To explain the polyester adhesive of the present invention in more detail, aromatic dicarboxylic acids and/or ester-forming derivatives thereof include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, oxydiphenylene dicarboxylic acid, or esters thereof. Formative derivatives and the like may be mentioned, and one or more of these may be used.
However, in consideration of various physical properties of the resulting polyester, it is preferable to use terephthalic acid or its ester-forming derivative and isophthalic acid or its ester-forming derivative in combination. Although the ratio of the two used together varies depending on the application, it is mainly determined by the target flow start temperature of the polyester (described later). In the polyester adhesive of the present invention, an ester-forming sulfonic acid alkali metal salt compound is used as a copolymerization component in order to improve water dispersibility or water solubility. Examples of the alkali metal sulfonic acid salt compounds having ester-forming properties include 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 4-sodium sulfonaphthalene-2,7-dicarboxylic acid, and sodium sulfo-p-oxy. Examples include ethoxybenzoic acid or ester-forming derivatives thereof, particularly preferably 5-sodium (and/or potassium)
Sulfoisophthalic acid or its ester-forming derivative. The amount used varies depending on the application, but is preferably 3 to 12 mol%, preferably 5 to 12% by mole based on the total acid component.
~10 mol%. If the amount used is less than 3 mol %, the water dispersibility or water solubility of the resulting polyester will be low, making it difficult to use it as an aqueous medium.
Moreover, if it exceeds 12 mol%, not only will the heat resistance and adhesive strength decrease, but also the adhesive strength will greatly fluctuate due to humidity in the practical stage, making it unsuitable. As the glycol component in the polyester adhesive of the present invention, a compound represented by the above general formula [] is used. Specifically, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, polyethylene glycol,
Examples include polypropylene glycol and polybutylene glycol. The molecular weight of these polyalkylene glycols is preferably 4000 or less. These may be used alone or in combination of two or more. The amount of these polyalkylene glycols used is 4% by weight or more based on the polyester obtained. The upper limit that can be used is not particularly limited when the number of repeating units in general formula [] is 5 or less, but when it is 6 or more, it is 30% by weight based on the polyester from the viewpoint of heat resistance, adhesiveness, etc. of the polyester obtained. % or less, more preferably 20% by weight or less. Therefore, when low molecular weight and high molecular weight polyalkylene glycols are used together, it is desirable to adjust the amount of high molecular weight polyalkylene glycol to 30% by weight or less. In addition, as the remainder of the polyalkylene glycols represented by the general formula [] as the glycol component, alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, tetramethylene glycol, neopentyl glycol, etc. are used. It will be done. When considering the adhesive performance of the resulting polyester, it is preferable to use the above-mentioned alkylene glycol in combination with polyalkylene glycols, and polyester containing 3 mol % or more of alkylene glycol based on the total glycol components is more preferable. In the polyester adhesive of the present invention, it is important to further use a phosphorus-containing dicarboxylic acid represented by the following general formula [] as a copolymerization component. Specific examples of R and R ¹ include hydrogen atom, methyl,
These include hydrocarbon groups such as ethyl, propyl, and phenyl, and halogen atoms such as chloro and brome. R and R ¹ may be the same or different. R ² and R ³ are hydrogen atoms, methyl, ethyl, propyl, butyl, phenyl, benzyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxyethyloxyethyl, etc. These include a hydrocarbon group or a hydroxyl group-substituted hydrocarbon group. Particularly preferred compounds are or an ester-forming derivative thereof. By copolymerizing the phosphorus-containing compound, the resulting polyester itself exhibits flame retardancy, and when the polyester is attached to a thermoplastic fiber structure, the fiber structure also has flame retardancy. Can be done. Furthermore, copolymerization of the phosphorus-containing compound has the great advantage of improving adhesiveness. This is thought to be because the side chain of the phenanthrene structure containing a phosphorus atom has some influence on the adhesiveness, but the reason is not clear. Additionally, polyester copolymerized with a phosphorus compound usually has the disadvantage of poor hydrolysis resistance, but the polyester of the present invention copolymerized with a specific phosphorus compound is stable against hydrolysis, and its water The dispersion or aqueous solution can be stored in a sufficiently stable state, and can always exhibit stable and excellent performance when used in an aqueous medium. The amount of the phosphorus-containing compound used is an amount corresponding to 500 to 10,000 ppm of phosphorus based on the polyester obtained. If the amount of phosphorus is less than 500 ppm, flame retardancy will not be sufficient, and the effect of improving adhesion will not appear. The upper limit is 10,000 ppm, and even if it is used above that level, no particularly interesting improvement in performance will be observed, and on the contrary, it will have the disadvantage of lowering heat resistance, hydrolysis resistance, etc. The polyester adhesive of the present invention obtained from the above-mentioned compound preferably has a flow initiation temperature of 70 to 150°C from the viewpoint of ease of use as an adhesive. In addition, polyester has a relative viscosity determined by the method described below.
It is preferable that it is 1.13 or more. The method for producing polyester from the above compound is not particularly limited, and polyester can be produced by conventionally known polyester production methods.
For example, a method in which a dicarboxylic acid ester and a glycol are transesterified or polycondensed in the presence of a suitable catalyst, or a method in which a dicarboxylic acid and a glycol are subjected to a dehydration esterification reaction in the presence of a catalyst if desired, followed by a polycondensation reaction in the presence of a catalyst. A method such as condensation is used. In this case, better results can be obtained by adding the phosphorus-containing compound after the transesterification or esterification reaction is completed. The polycondensation reaction temperature is usually 285℃ or less, preferably
The temperature is below 275℃. The polyester thus obtained may be used in the form of powder, film, or fiber by adding additives such as stabilizers, colorants, and lubricants, if desired, but it is usually used in the form of an aqueous dispersion or solution. It is convenient to do so. The polyester is very stable against hydrolysis, but cannot be dispersed or dissolved in water below 100°C, preferably at 80°C.
Preferably, the storage temperature is 50°C or lower. A dispersion aid may be used if desired, but it is necessary that it not inhibit flame retardancy and adhesion, and a thermoplastic one is usually used. The amount used is preferably 30% by weight or less based on the polyester. Aqueous dispersions or solutions are used in particular as finishing agents, sizing agents, adhesives, etc. for textile structures. In order to effectively exhibit the effect, it is effective to use it on fibers obtained from thermoplastic resins, and it is especially effective when used on polyester or polyamide fibers or mixtures thereof. It is. There are no particular limitations on the fiber structure, including fabrics, nonwoven fabrics, warped sheets, threads, and the like. The amount of adhesion differs depending on the application, but the amount of polyester is 1 to 1% of the total of the fiber structure and polyester adhesive.
80% by weight, preferably 5 to 50% by weight. The fiber structure thus obtained exhibits excellent flame retardancy and is used for building interior parts, furniture furnishings, vehicle interior parts, electrical products, etc. Furthermore, since it easily adheres to various materials under heat and pressure, it is effective in streamlining the process in manufacturing composite material molded products for the above-mentioned applications. Of course, thermoforming alone is also possible. EXAMPLES Hereinafter, the effects of the present invention will be explained with reference to Examples, but the present invention is not limited thereto. Note that various characteristic values in the examples were measured by the methods described below. 1 Relative viscosity 100mg of polyester with phenol/1.1.
2,2-tetrachloroethane mixed solvent (3/2
Weight ratio) Dissolved in 25ml and measured at 30℃. 2 Adhesion A film with a width of 2 cm, height of 1.5 cm, and thickness of approximately 400μ was made from polyester. On the other hand, basis weight 300g/
A piece of fabric with a width of 3 cm and a length of 7 cm was made from a polyethylene terephthalate fabric of m ² .The above film was inserted between the two pieces of fabric, and the temperature was 150°C.
Pressure was applied for 8 seconds at a pressure of 1.5 kg/cm ² . After heating and pressurizing the sample again from the opposite side, conditioning it and using Tensilon to peel it off (at high temperatures, the force required for peeling due to cohesive force failure)
was measured. 3 Flame retardancy Measured by oxygen index (LOI) method according to JIS K-7021 1971 No. B1. Example 1 Dimethyl terephthalate 260g, dimethyl isophthalate 67.6g, 5-sodium dimethyl sulfoisophthalate 59.2g, ethylene glycol 62g, diethylene glycol 190g, titanyl potassium oxalate 0.025 mol%/total acid components, sodium acetate 0.25
The mol%/total acid components were placed in a reaction vessel, and the transesterification reaction was carried out until the theoretical amount of methanol flowed out. Then, 26 g of a phosphorus-containing compound having the following structure was added and stirred for 10 minutes. Put this in a polycondensation reaction vessel and
A polycondensation reaction was carried out under reduced pressure at °C to obtain a yellow polyester. The polyester has a relative viscosity of 1.215,
The flow initiation temperature was 115°C. This polyester is referred to as Polymer (A). Comparative Example In Example 1, the amount of dimethyl isophthalate was increased to 89.2 g instead of using the phosphorus-containing compound.
The obtained polyester was pale yellow and had a relative viscosity of 1.209.
The flow start temperature was 120°C. This polyester is referred to as Polymer (B). Example 2 Adhesion was measured using polymers (A) and (B), and the results are shown in Table 1. Polymer (A) showed improved adhesive strength due to copolymerization of phosphorus-containing compounds.

[Table] Example 3 Polymers (A) and (B) were each prepared into 20% by weight aqueous solutions at 60°C. These polymers become a slightly cloudy aqueous solution in about 1 hour. 200% by weight of the aqueous solution was applied to the polyester fabric used in the adhesion test, and dried at 120°C for 20 minutes. The fabric to which polymer (A) was attached had an oxygen index of 29%, indicating good flame retardancy. On the other hand, the fabric to which polymer (B) was attached had an oxygen index of 25%, which was inferior to the oxygen index of the untreated fabric, which was 26%. That is, while polymer (B) had decreased flame retardancy, polymer (A) showed greatly improved flame retardancy.

Claims (1)

[Scope of Claims] 1 The present invention provides a polyester comprising an aromatic dicarboxylic acid and/or an ester-forming derivative thereof and a glycol, wherein (1) 5-sodium sulfoisophthalic acid and/or 5-sodium sulfoisophthalic acid and/or 5-sodium sulfoisophthalic acid and/or - 3 to 12 mol% of at least one kind of potassium sulfoisophthalic acid or its ester-forming derivative; (2) 500 to 500 mol% of phosphorus based on polyester;
At least one phosphorus-containing dicarboxylic acid compound represented by the following general formula [] in an amount equivalent to 10,000 ppm, and (3) at least one polyalkylene glycol whose part of the glycol is represented by the following general formula [] seeds, the remainder being at least one selected from ethylene glycol, propylene glycol, tetramethylene glycol and neopentyl glycol, and 4 to 30% by weight of the polyalkylene glycol is copolymerized with respect to the polyester. Polyester adhesive with flame retardant properties. (However, R and R ¹ are the same or different groups such as a hydrogen atom, a halogen atom, or a hydrocarbon group having 6 or less carbon atoms, and R ² and R ³ are the same or different groups such as a hydrogen atom or a hydrocarbon group having 7 or less carbon atoms. represents a hydrocarbon group or a group represented by (R ⁴ O) rH. R ⁴ represents an ethylene, propylene or butylene group, and r represents 1 to 10
, l and m are 0 or an integer of 1 to 4, and n is 0, 1 or 2. ) HO (R ⁵ O) pH ... [] (However, R ⁵ is an ethylene, propylene or butylene group, and p is an integer of 2 to 90.) 2. A patent claim in which the flow start temperature is 70 to 150 °C A polyester adhesive according to scope 1. 3. The polyester adhesive according to claim 1, wherein the aromatic dicarboxylic acid is a mixture of terephthalic acid and isophthalic acid.