JPH0471424B2 - - Google Patents

Description

[Detailed description of the invention]

The present applicant has previously invented a polyester resin hot melt adhesive for textile fabrics that has excellent water resistance and dry cleaning resistance, and has filed a patent application. In other words, the adhesive has adhesive strength far superior to conventional products for natural fibers and textiles such as cotton, wool, silk, and linen, and its composition is as follows: (1) 40 mol% or more of the acid component is terephthalate; 70 to 97% by weight of a crystalline polyester resin in which 70 mol% or more of the glycol component is ethylene glycol and/or 1,4-butanediol, and has an intrinsic viscosity of 0.4 or more and a melting point of 90 to 180; (2) a melting point of an acid; It consists of 3 to 30% by weight of any one of carboxylic acid esters, biphenyl compounds, and sulfonamide compounds at a temperature of 25 to 150°C. However, the inventors of the present invention continued their studies, and based on the knowledge that the more uniform the mixing state of (1) and (2) is in this adhesive, the better the adhesive strength is, and conducted intensive research on the manufacturing method thereof. First, since (1) and (2) are both solid at room temperature, we attempted a method of melting them, mixing them uniformly, and then mechanically pulverizing them, but the result was a fine powder with a constant particle size. It is difficult to obtain a powder, and the resulting powder has the disadvantage of being prone to blocking. Furthermore, it was found that uniform mixing was difficult when (1) and (2) were mixed as powders, and in both cases, it was found to be impractical for implementation on an industrial scale. However, as a result of further research, the present inventors found that []
A mixture consisting of a good solvent that dissolves (A) a polyester resin and (B) one of carboxylic acid esters, biphenyl compounds, and sulfonamide compounds with a melting point of 25 to 150°C, and a poor solvent of (A). When a mixed solution is prepared by dissolving (A) and (B) in the mixed solvent using as a solvent, and solid-liquid separation is performed after preferentially distilling off the good solvent from the mixed solution, (A)(B) ) was found to be able to obtain a powder in which the powders were mixed extremely uniformly, and the present invention was completed. In the present invention, as (A) polyester resin,
A crystalline polyester resin in which 40 mol% or more of the acid component is terephthalic acid, 70 mol% or more of the glycol component is ethylene glycol and/or 1,4-butanediol, and has an intrinsic viscosity of 0.4 or more and a melting point of 90 to 180°C. When used, it has the highest practicality in terms of its use, but even with other polyester resins, according to the method of the present invention, resin and (B)
A powder in which the components are uniformly mixed can be easily obtained. To carry out the present invention, first, (A) a polyester resin and (B) a carboxylic acid ester having a melting point of 25 to 150°C,
Either one of the biphenyl compound and the sulfonamide compound is dissolved in a mixed solvent consisting of the good solvents (A) and (B) and the poor solvent (A). The solution does not necessarily have to be a homogeneous solution, and if a relatively large amount of poor solvent is used, a dispersion in which some powder is precipitated will be obtained, but this can of course also be used. However, in the case of a dispersion, it is necessary to go through a process in which (A) and (B) are uniformly dissolved during the preparation process. There is no difference whatsoever. There are no particular restrictions on the dissolution method, including a method of dissolving (A) and (B) in a mixture of a good solvent and a poor solvent, a method of dissolving (A) and (B) in a good solvent, and then adding a poor solvent. Method of adding a good solvent to a mixture of (A), (B) and a poor solvent, (A), (B)
A method of simultaneously mixing a good solvent and a poor solvent can be implemented. In order to prepare a solution in which (A) and (B) are completely and uniformly dissolved, the poor solvent must be used at a ratio of 60% by weight or less to the good solvent. Good solvents for (A) and (B) include chloroform (trichloromethane), methylene chloride (dichloromethane), dichloroethane,
Examples include halogenated hydrocarbons such as trichloroethane, trichloroethylene, and chlorobenzene, benzene, dioxane, and tetrahydrofuran. Among these, dichloroethane and benzene are preferred. On the other hand, examples of poor solvents for (A) include methanol, ethanol, propanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol,
tert-butyl alcohol, aluminum alcohol,
Fatty acid alcohols having 4 or more carbon atoms such as hexyl alcohol, heptyl alcohol, octyl alcohol, and n-hexane, n-heptane, n-
Examples include fatty acid hydrocarbons having 6 or more carbon atoms such as octane, esters such as methyl acetate, and water. Note that the poor solvent (B) does not necessarily have to be a poor solvent. In the present invention, it is usually referred to as (A).
Mixing ratio with (B) is (A) 70-97% by weight, (B) 3-30% by weight
Since (B) and (B) are in relatively small amounts, (B) is almost uniformly mixed in (A) and is hardly affected by the solvent during precipitation. In the present invention, when a good solvent and a poor solvent are combined, it is necessary that the boiling point of the good solvent is lower than the boiling point of the poor solvent, and unless such a combination is used, the good solvent cannot be preferentially distilled off. Appropriately, the melting point difference is about 5°C or more. Also, if the solvent forms an azeotrope,
It is of course necessary to take care to form an azeotropic composition containing 50% or more of the good solvent so that the good solvent can be distilled off preferentially. In the present invention, (A) and (B) are stirred and dissolved in the mixed solvent at room temperature or under heating to a concentration of 10 to 50% by weight. When the concentration is 50% by weight or more, the particle size of the powder tends to increase and the particle size distribution tends to widen. Next, by preferentially distilling off the good solvent, a powder consisting of a mixture of (A) and (B) begins to precipitate. By heating the above dispersion above the boiling point of the good solvent, the good solvent is gasified and distilled off.
The composition of the system gradually becomes excessive in the poor solvent, and powder begins to precipitate. By the time the good solvent is distilled off, the precipitation of the powder is almost complete. Since the poor solvent remains in the system, there is no concern that the precipitated powder will cause blocking. After the precipitation is completed, solid-liquid separation is performed according to a conventional method, followed by heating and drying. Any dryer that is commonly used for drying powder may be used. At the precipitation stage or drying stage, known antiblocking agents, antioxidants, etc. which are usually added to powders can also be added. Also, the recovered solvent can be reused. In the present invention, the powder obtained varies depending on the solution concentration of (A) and (B), the ratio of good solvent to poor solvent, type of solvent, temperature, stirring speed, etc.
It is a powder in the range of 400 mesh, and is almost spherical in shape with a smooth texture. Moreover, in this powder, components (A) and (B) are mixed very uniformly in any particle size distribution range.
Although any polyester resin may be used as the object of the present invention, the present invention is particularly advantageously carried out in the production of hot melt adhesives for textile fabrics.
The components constituting this adhesive will be explained below. The polyester resin (A) in the above contains 40 mol% of terephthalic acid (including its derivatives) as an acid component.
It must include the above. That is, the molar ratio of terephthalic acid and other dicarboxylic acids is 100:0 ~
It's 40:60. If the amount of other dicarboxylic acids is 60 moles or more, the melting point will be low and the dry cleaning resistance will also be decreased. Also, the glycol component is 70 mol%.
The above must be ethylene glycol and/or 1,4-butanediol. Of course, other diols may also be used in combination, but from the viewpoint of dry cleaning resistance, the amount used must be 30 mol% or less. The intrinsic viscosity of the resin (phenol/1.1.2.2-tetrachloroethane (3/2) mixed liquid, measured at 30℃) is
It must be 0.4 or more; if it is less than 0.4, the resin will be brittle and the adhesive strength will be low. In addition, it is necessary that the melting point is between 90 and 180°C. If the melting point is higher than 180°C, the adhesion strength will be low, and if the melting point is lower than 90°C, it may cause seepage to the back side if the adherend is textile. do not have. Examples of dicarboxylic acids other than terephthalic acid include malonic acid, succinic acid, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, sebacic acid, azelaic acid, and other dicarboxylic acids other than ethylene glycol and 1,4-butanediol. Other diols include 1,3-propanediol, 1,4-
Cyclohexane dimethanol, neopentyl glycol, 1,2-propylene glycol, 1,3
-butyl glycol, 1,2-butylene glycol, diethylene glycol, triethylene glycol and the like. In the resin of the present invention, the diol component is used in a ratio of 1.1 to 2.5 moles per mole of the dicarboxylic acid component, and this is combined with a polycondensation catalyst such as zinc acetate or other esterification reaction catalyst and antimony trioxide. Alternatively, it is produced using an alkyl ester of titanic acid as a catalyst for esterification reaction and polycondensation. The carboxylic acid ester of component (B) is a phthalic acid ester compound and a fatty acid ester having about 4 to 20 carbon atoms. Typical examples of such phthalate ester compounds include dilauryl phthalate, dicyclohexyl phthalate, diphenyl phthalate, disellosolve phthalate, ethyl phthalyl ethyl glycolate, and tetrahydrophthalic acid propylene oxide adduct. Examples of the fatty acid of the fatty acid ester include palmitic acid, lauric acid, stearic acid, succinic acid, sebacic acid, octylic acid, and adipic acid. As the ester, an alkyl ester is used, but of course not only an alkyl group but also any substituted alkyl group cyclic ester, phenyl group, etc. can be used. Representative examples of such fatty acid esters include methyl cellosolve palmitate, glycerol monolaurate, glycerol monostearate, dibenzyl succinate, dimethyl sebacate, dibenzyl sepacate, and the like. Sulfonamide compounds include O-toluenesulfonamide, P-toluenesulfonamide,
N-ethyl-P-toluenesulfonamide etc.
Examples of biphenyl compounds include O-nitrobiphenyl and hexachlorinated biphenyl. The blending ratio of (A) polyester resin and (B) the above compound is 70 to 97% by weight of the former, preferably 80 to 95% by weight,
The latter accounts for 3 to 30% by weight, preferably 5 to 20% by weight. If the amount of (B) is less than 3% by weight, sufficient adhesion to natural fibers will not be exhibited, while if it is more than 30% by weight, problems will occur such as a decrease in adhesion and ester leaching. Next, the present invention will be specifically explained with reference to Examples. In the examples, "parts" are "parts by weight" unless otherwise specified. Example 1 0.72 mol of terephthalic acid, 0.28 mol of adipic acid,
85 parts of a polyester resin (intrinsic viscosity: 0.75, melting point 125°C) consisting of 0.34 mol ethylene glycol and 0.66 mol 1,4-butanediol and 15 parts methyl cellosolve palmitate (melting point 46°C) are mixed with methylene chloride.
It was added to a mixed solvent of 70 parts and 30 parts of methanol, heated to 70°C, and dissolved under pressure. This solution was heated to 40 to 70° C. under normal pressure to 50 torr to drive off methylene chloride while stirring. Eventually, powder began to form, and methylene chloride continued to be removed. Subsequently, methanol was also distilled off, and the resulting wet powder was vacuum-dried in a dryer.
The particle size of the obtained powder was 40% by weight of 80-200 mesh and 55% of 200-400 mesh.The analytical values of methyl cellosolve palmitate by particle size were 15.4% for 80 mesh and 15.4% for 80-120 mesh.
15.0% and 14.9% for 200 mesh under, making it clear that polyester resin and methyl cellosolve palmitate were uniformly mixed in both powders. Examples 2 to 4 Experiments were conducted in accordance with Example 1 by changing the component (B) and the solvent. The results are shown in the table.

[Table] Comparative Example 1 The polyester resin of Example 1 and methyl cellosolve palmitate were continuously melt-blended in a co-kneader at a weight ratio of 85/15, and pelletized. The mixture was then cooled with liquid nitrogen and pulverized using a turbo mill. The obtained powder was temporarily caked and further pulverized using a coarse pulverizer. Particle size distribution is 80 mesh 38
%, 80-200 mesh 35%, 200 mesh under
It was 27%. Control Example 2 85 parts of a polyester resin with a ratio of 80 mesh on/80 to 200 mesh/200 mesh under of 10/50/40 and 15 parts of flaky methyl cellosolve palmitate were blended in a Henschel mixer. Analysis of the composition of the obtained powder revealed that the powder with a particle size of 80 to 200 mesh contained the largest amount of methyl cellosolve palmitate, and its content varied widely, ranging from 15 to 25%, and its adhesive properties were not sufficient. .

Claims (1)

[Claims] 1 [] (A) a polyester resin and (B) a melting point of 25 to
Add (A), (B) to the mixed solvent using a mixture of a good solvent that dissolves one of the carboxylic acid esters, biphenyl compounds, and sulfonamide compounds at 150°C and a poor solvent of (A). 1. A method for producing a polyester resin powder, which comprises preparing a mixed solution in which the following compounds are dissolved, preferentially distilling off a good solvent from the mixed solution, and then performing solid-liquid separation. 2 (A) As a polyester resin, 40 mol% or more of the acid component is terephthalic acid, and 70 mol% or more of the glycol component is ethylene glycol and/or 1,4
- butanediol, and has an intrinsic viscosity of 0.4 or more,
The manufacturing method according to claim 1, characterized in that a crystalline polyester resin having a melting point of 90 to 180°C is used.