JPH1180334A - Polyester resin and solution composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin capable of being advantageously used for producing a composite sheet with a fibrous base material and to form a tough film, having excellent solubility in a polar solvent, and Another object of the present invention is to provide a polyester resin capable of providing a stable solution, and also to provide a solution composition comprising the polyester resin and a polar solvent. SOLUTION: While using a polyester resin containing terephthalic acid and naphthalenedicarboxylic acid as main acid components, while using ethylene glycol and polyoxyalkylene glycol as main alcohol components, the above description is wonderful. The task has been reached.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new and useful polyester resin and a solution composition containing the same. More specifically, the present invention relates to a specific polyester resin which uses terephthalic acid and naphthalenedicarboxylic acid as main acid components, while using ethylene glycol and polyoxyalkylene glycol as main alcohol components. And a solution composition containing the same.

[0002] The present invention provides a polyester resin and a solution composition containing the polyester resin, respectively. The present invention provides a stable solution having excellent solubility in a polar solvent, The present invention provides a polyester resin that gives a film or various molded products having excellent mechanical strength, heat deterioration resistance and wet heat deterioration resistance, and a solution composition comprising the polyester resin and a polar solvent. Is also provided.

[0003] This kind of polyester resin is
It can be used as a film, as a molded product, or as an adhesive. And such polyester resin, as a solution composition, respectively, clothing,
It can be used for production of a composite sheet with a fibrous base material, which is suitable as a skin material for shoes, bags or chairs, furniture or interior decoration, or preparation of an adhesive.

[0004]

2. Description of the Related Art A natural leather substitute material called artificial leather or synthetic leather is a composite material of a resin and a fibrous base material, and a polar solvent solution of a polyurethane resin is widely used in the production thereof. ing.

[0005] Artificial leather refers to a composite sheet formed by filling or laminating a resin with a nonwoven fabric. Synthetic leather refers to a method of filling a woven or knitted fabric with a resin. It refers to a composite sheet in a laminated form.

As a method for producing artificial leather, a so-called wet process is generally used, in which a resin solution is impregnated or applied to a nonwoven fabric, coagulated in a liquid containing water as a main component, and then washed and dried. is there.

[0007] Synthetic leather is manufactured by using a woven or knitted fabric as a base material and performing the above-mentioned wet processing to produce a wet synthetic leather and a resin film on a woven or knitted fabric. And dry synthetic leather manufactured by a so-called direct coating method in which a resin solution is applied to a woven or knitted fabric and dried.

[0008] An artificial leather or a synthetic leather using a urethane resin can make the texture very similar to that of natural leather, and can also give a material having good durability and moisture permeability. It is also known.

However, polyurethane resins are, inter alia,
It has problems in chemical resistance and discoloration resistance, and also has an environmental or safety problem that hydrogen cyanide or the like originating from urethane bonds is generated during combustion.

[0010] As a material similar to synthetic leather, so-called PVC leather, which is a composite sheet of polyvinyl chloride and a fibrous base material, or a polystyrene-based elastomer or a polyolefin-based elastomer is laminated on various base materials. And others.

[0011] Even if these can be made to resemble natural leather in appearance, it is extremely difficult to bring functions such as moisture permeability close to natural leather. Further, PVC leather has an environmental or safety problem of generating hydrogen halide or the like upon combustion.

Further, suede-like and nubuck-like fiber products made of ultra-fine fibers are also used as a substitute for natural leather, and some are made of only polyester fibers. However, they have the disadvantage that they are significantly more expensive than other natural leather substitutes.

Various studies have been made to obtain a composite sheet using a polyester resin instead of a polyurethane resin by the same manufacturing method as that for artificial leather or synthetic leather using a urethane resin as described above. Have been. However, the polyester resin itself has a lower solubility in a solvent than the polyurethane resin,
The reality is that the processing method itself has many restrictions.

JP-B-51-2943 discloses a solution obtained by dissolving a polyester elastomer in a mixed solvent of dioxane or tetrahydrofuran and dimethylformamide and the like and having a small change in viscosity to obtain a synthetic leather by wet processing. There is disclosed a technology that is used for the production of sapphire.

JP-A-51-129466 discloses that a crystalline polyester is mixed with a solution of a polyester elastomer in a non-homogeneous state, and the resulting mixture is coated or impregnated on a fibrous base material. A method for producing synthetic leather, artificial leather, or the like, in which a wet film is formed by wet coating, is disclosed.

Further, Japanese Patent Application Laid-Open No. Hei 8-31233 discloses a porous film in which a solvent solution of a polyester elastomer is applied onto a substrate while heating, solidified by cooling, and then subjected to wet film formation. Is disclosed.

Since the polyester resin essentially does not contain a nitrogen atom, a halogen atom, or the like, there is no danger that a toxic gas due to each of these atoms will be generated during combustion.

However, the known techniques as described above are:
Manufacture of composite sheets where the resin solution contains solid powder, the solution must be warmed during manufacture, or the use of a mixed solvent interferes with solvent recovery from the liquid in the coagulation bath However, there is a problem that it becomes complicated and costly.

[0019]

However, in view of the above-mentioned various disadvantages in the conventional techniques, the present inventors have developed a composite sheet of a polyester resin and a fibrous base material. Like the various conventional techniques described above, it is cumbersome, and can be advantageously manufactured without employing expensive steps, and furthermore, has mechanical strength, heat deterioration resistance and As a polyester resin that forms a film having excellent resistance to wet heat degradation, it has excellent solubility in polar solvents, and in addition, to provide a resin that gives a stable solution, the polyester resin and a polar solvent In order to provide a solution composition having excellent stability, the research has been started earnestly. This is the problem to be solved by the present invention.

[0020]

Means for Solving the Problems Accordingly, the present inventors have:
Focusing on the problem to be solved by the invention as described above, as a result of diligent and intensive studies, terephthalic acid and naphthalenedicarboxylic acid as main acid components, on the other hand, ethylene glycol and polyoxyalkylene A specific polyester resin obtained by using glycol as a main alcohol component has excellent solubility in a polar solvent, and in addition, the resulting solution composition has excellent stability. It can be used to advantage in the production of composite sheets with materials, and more particularly, to form a film having excellent mechanical strength, heat and heat and moisture and heat resistance. Thus, the present invention has been completed.

The term "excellent in stability" as used herein means that the prepared resin solution does not cause resin precipitation or change in viscosity even when left at room temperature for 24 hours or more, that is, one day. As described above, the resin solution is maintained in a state where it can be used for producing a composite sheet with a fibrous base material without taking measures such as heating.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention basically comprises, as one component, terephthalic acid and naphthalenedicarboxylic acid as main acid components, while ethylene glycol and polyoxyalkylene glycol as main alcohol components. It is intended to provide a polyester resin obtained by using as

Secondly, the ratio of the number of moles of terephthalic acid residues to the number of moles of naphthalenedicarboxylic acid residues is 95:
It is also intended to provide a polyester resin having a content of polyoxyalkylene glycol unit of 5 to 70:30 and a content of 60 to 90% by weight based on the solid content of the obtained polyester resin. To do

Thirdly, it is intended to provide a polyester resin prepared using polyoxytetramethylene glycol having a number average molecular weight in the range of 500 to 3,000 as the polyoxyalkylene glycol. And

Fourth, a polyester resin obtained by using terephthalic acid and naphthalenedicarboxylic acid as main acid components, ethylene glycol and polyoxyalkylene glycol as main alcohol components, a polar solvent and To provide a solution composition comprising:

Fifth, the ratio of the number of moles of terephthalic acid residues to the number of moles of naphthalenedicarboxylic acid residues is 95:
A polyester resin having a polyoxyalkylene glycol unit content of 5 to 70:30 and a content of polyoxyalkylene glycol units of 60 to 90% by weight based on the solid content of the obtained polyester resin; It is also intended to provide a solution composition consisting of

Sixth, the polyoxyalkylene glycol contains a polyester resin prepared using a polyoxytetramethylene glycol having a number average molecular weight in the range of 500 to 3,000, and a polar solvent. And to provide a solution composition consisting of

Seventh, a solution composition containing N, N-dimethylformamide as a polar solvent and having a polyester resin content of 5 to 50% by weight will be provided. It is assumed that.

Hereinafter, the present invention will be described in detail.

In the present invention, a composite sheet of a resin and a fibrous base material is a composite sheet in which a resin is filled or laminated on a fibrous base material such as a nonwoven fabric, a woven fabric or a knitted fabric. It refers to a body in a sheet form.
Among them, particularly typical ones are generally called artificial leather or synthetic leather, but the names are not limited at all.

In the present invention, the polyester resin in which terephthalic acid and naphthalenedicarboxylic acid are the main acid components, while ethylene glycol and polyoxyalkylene glycol are the main alcohol components, the ethylene resin is the main component. A polyester obtained using a low-molecular-weight diol component and a dicarboxylic acid component having terephthalic acid and naphthalenedicarboxylic acid and ester-forming derivatives such as these as main components is referred to as a hard segment. This is a so-called thermoplastic elastomer in which oxyalkylene glycol is used as a soft segment.

[0032] Only low-molecular-weight diol components other than ethylene glycol used in the production of the polyester resin according to the present invention will be exemplified. Glycol, 1,2-butylene glycol, 1,3-
Butylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, butylethylpropanediol, diethylene glycol, triethylene glycol, dipropylene glycol, ethylene oxide or propylene oxide addition of bisphenol-A Body.

One or more of these can be used in addition to ethylene glycol. However, the amount of these may be in such a range that the crystallinity of the polyester component serving as a hard segment is not excessively reduced. Must be kept within. That is, the usage ratio of ethylene glycol should be set within the range of 70 to 100 mol%, preferably within the range of 80 to 100 mol% of the total low molecular weight diol component.

When the low molecular weight diol component is, for example, 1,
In the case of 2-propylene glycol or neopentyl glycol or the like, the obtained polyester resin film becomes very soft,
Further, when the low molecular weight diol component is mainly composed of, for example, 1,4-butylene glycol, the stability of the solution composition becomes poor.

The ratio of the number of moles of terephthalic acid residues to the number of moles of naphthalenedicarboxylic acid residues in the polyester resin according to the present invention is suitably from 95: 5 to 70:30, and preferably from 95: 5 to 70:30. , 95: 5 to 80:20 are suitable.

Here, only particularly typical examples of the above-mentioned naphthalenedicarboxylic acids are exemplified, and 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, Examples thereof include 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid, and it is particularly preferable to use 2,6-naphthalenedicarboxylic acid.

In the case where the ratio of the number of moles of terephthalic acid residues to the number of moles of naphthalenedicarboxylic acid residues is smaller than 95: 5, the resulting polyester In some cases, the resin becomes difficult to dissolve in the solvent, and the stability of the solution composition becomes poor.

The ratio of the number of moles of terephthalic acid residues to the number of moles of naphthalenedicarboxylic acid residues is 7
When the ratio of the naphthalenedicarboxylic acid residue is larger than 0:30, the resulting polyester resin may not be able to form a tough film.

As typical examples of dicarboxylic acid components other than terephthalic acid and naphthalenedicarboxylic acid and their ester-forming derivatives, such as isophthalic acid, o-phthalic acid and diphenyldicarboxylic acid, are mentioned. Various aromatic dicarboxylic acids represented by, succinic acid, adipic acid, sebacic acid, various aliphatic or alicyclic dicarboxylic acids represented by such as decanedicarboxylic acid or cyclohexanedicarboxylic acid, and further, These ester-forming derivatives and the like.

One or more of these can be used in addition to terephthalic acid and naphthalenedicarboxylic acid and their ester-forming derivatives, but the amount of their use becomes a hard segment. It must be kept within a range where the crystallinity of the polyester component is not lost. In addition, polyester resins in a form containing a large amount of aliphatic dicarboxylic acid component often have poor heat and moisture resistance, and in particular, in many cases, therefore, it is never desirable to increase the use ratio too much. Absent.

The use ratio of terephthalic acid, naphthalenedicarboxylic acid and ester-forming derivatives such as them is in the range of 70 to 100 mol%, preferably in the range of 80 to 100 mol% of the total dicarboxylic acid component. Should be set to

As the polyoxyalkylene glycol used in the production of the polyester resin according to the present invention, only typical ones are exemplified, and polyoxyethylene glycol, polyoxypropylene glycol or polyoxytetramethylene glycol may be used. And further, a block copolymer or a random copolymer thereof, and further, a polydioxolane or the like. These may be used alone or in combination of two or more.

As these polyoxyalkylene glycols, those having a number average molecular weight in the range of 500 to 3,000 are desirably used. In the case where the polyoxyalkylene glycol having a number average molecular weight of less than 500 is used, the chain length of the polyester component serving as a hard segment is liable to be shortened, and the resulting polyester resin has a high toughness. May not be able to form a film.

On the other hand, when a polyoxyalkylene glycol having a number average molecular weight exceeding 3,000 and being too high is used, the chain length of the obtained polyester component is liable to be long, and as a result, Since the solubility of the obtained polyester resin in a solvent is reduced, and thus the stability of the obtained solution composition may be inferior, it is preferable in any case. Absent.

The polyester resin according to the present invention contains the polyoxyalkylene glycol unit in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on the polyester resin. That is.

When the content of the polyoxyalkylene glycol unit is less than 60% by weight, the solubility of the obtained polyester resin in a solvent is liable to be reduced, and the resulting solution composition is inevitably reduced. In some cases, the stability may be poor. The content of the polyoxyalkylene glycol unit is 90% by weight.
If the number is too large, the obtained polyester resin may not be able to form a tough film.

As the polyoxyalkylene glycol used in the polyester resin according to the present invention, among the various polyoxyalkylene glycols described above, the use of polyoxytetramethylene glycol is particularly desirable. Such a polyoxytetramethylene glycol is particularly excellent in heat resistance and the like as compared with other polyoxyalkylene glycols, and thus the obtained polyester resin also has good heat deterioration resistance. It is.

The polyester resin according to the present invention is represented by, as raw materials, glycerin, trimethylolpropane, pentaerythritol and the like, in addition to the above-mentioned low molecular weight diol component, dicarboxylic acid component and polyoxyalkylene glycol, respectively. Various trivalent or higher polyhydric alcohols, various trivalent or higher polyvalent carboxylic acids represented by trimellitic acid, pyromellitic acid or butanetetracarboxylic acid, and the like. May be prepared using a small amount of the ester-forming derivative of

Here, the above-mentioned small amount means that the obtained polyester resin does not gel at the time of its production, and is linked by an ester group (ester bond) in the polyester resin. At most, up to about 5 mol% of all residues.

By using these trivalent or higher components, the polyester resin according to the present invention can shorten the reaction time, lower the reaction temperature, or reduce the vacuum in preparing the resin. Even if the degree is lowered, it may be preferable in some cases, such as a polyester resin which can form a tough film to be aimed.

The production of the polyester resin according to the present invention comprises:
It can be carried out according to conventionally known various methods (known and commonly used various methods). For example, a low-molecular-weight diol and a dicarboxylic acid component or an ester-forming derivative thereof or the like are subjected to esterification or transesterification with an excess of the diol component to obtain a low-molecular-weight ester compound serving as an intermediate. Then, at a temperature at which the transesterification reaction easily occurs, the mixture in the form in which the intermediate and the polyoxyalkylene glycol coexist is allowed to evaporate the excess low-molecular-weight diol component out of the system by depressurization. , A polymerization reaction of a polyester segment, and a polyoxyalkylene glycol,
It can be produced by simultaneously performing the bond formation reaction with the polyester segment by the ester group. The subsequent step of distilling off the low molecular weight diol component is called a polycondensation reaction.

The polyoxyalkylene glycol may be added just before the start of the polycondensation reaction, or may be present in the system during the esterification reaction or the transesterification reaction. You may leave. Even when a part of the polyoxyalkylene glycol is incorporated into an ester compound that becomes an intermediate by esterification or transesterification during the synthesis of the intermediate, the composition or structure of the polyester resin that is ultimately produced Means that it has essentially no effect.

In producing the polyester resin according to the present invention, various known and commonly used catalysts each suitable for esterification or transesterification and polycondensation can be used. Among them, particularly typical ones are exemplified. Antimony trioxide, barium oxide, zinc acetate, manganese acetate, cobalt acetate, zinc succinate, zinc borate, cadmium formate, lead monoxide, calcium silicate , Dibutyltin oxide, butylhydroxytin oxide, tetraisopropyl titanate,
Examples thereof include tetrabutyl titanate, magnesium methoxide, and sodium methoxide. Of course, they may be used alone or in combination of two or more.

In producing the polyester resin of the present invention, various known antioxidants can be used in order to suppress the thermal oxidative decomposition of the polyoxyalkylene glycol during the reaction. . Hindered phenol-based compounds and the like are particularly effective examples of such antioxidants, and such hindered phenol-based compounds are particularly effective.

The polyester resin according to the present invention comprises phenol / 1,1,2,2-tetrachloroethane (weight ratio =
6/4) with a concentration of 0.4
g / deciliter (dl)
It is desirable that the reduced viscosity measured in the above is not less than 1.0. More preferably,
As the reduced viscosity, a range of 2.0 to 5.0 is appropriate.

Regarding the strength of the obtained film,
As the polyester resin, it is preferable that the molecular weight is large, but too much, in the case of a polyester resin having a large molecular weight, the solubility in a solvent is likely to be poor, and thus the viscosity of the obtained solution composition becomes high. It is not preferable because it becomes too long.

The solution composition according to the present invention is produced by dissolving the polyester resin as described above in its polar solvent. However, if only typical representative examples of such polar solvents are given, If
N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone or dioxane.

Among these, it is particularly desirable to use N, N-dimethylformamide. This N, N-dimethylformamide has excellent solubility in the polyester resin according to the present invention. As a solvent for a synthetic resin used in the preparation of synthetic leather, artificial leather, and the like, it is a general solvent and particularly desirable.

Incidentally, it is particularly desirable that the solution composition according to the present invention contains 5 to 50% by weight of the polyester resin described above. The concentration of the solution composition may be appropriately adjusted according to the purpose of use. However, when the concentration is less than 5% by weight, the amount of resin adhering to the fibrous base material is low. If it becomes too much, and if it exceeds 50% by weight, the viscosity tends to be very high, which may hinder the production of the composite sheet. In any case, it is not preferable.

Here, this polyester resin is
The method for preparing the solution composition according to the present invention by dissolving in a polar solvent is not particularly limited. For example, this solid of polyester resin,
It can be obtained by adding to a polar solvent and heating while stirring, or by heating and melting this polyester resin and adding it to a polar solvent, furthermore, the polyester in a molten state The fact that a polar solvent is introduced into the resin also means that the solution composition according to the present invention can be produced.

Thus, the heating temperature required for preparing the solution composition according to the present invention is suitably from about 50 ° C. to 180 ° C., and preferably from 80 ° C. to 150 ° C. If the temperature is lower than 50 ° C., it is not preferable because a very long time is required for the dissolution, or in some cases, it may not be possible to achieve uniform dissolution.

On the other hand, a high temperature exceeding 180 ° C. is not necessary for dissolving the polyester resin according to the present invention.
If the temperature is higher than 180 ° C., it is not preferable because the molecular weight is rather lowered due to decomposition.

The solution composition thus obtained is a transparent and viscous liquid which does not cause a change in viscosity or resin precipitation for at least 24 hours even when cooled to room temperature. This is suitable for producing a composite sheet of a polyester resin and a fibrous base material by performing operations such as impregnation.

[0064]

Now, the present invention will be described in further detail with reference to Examples, Comparative Examples, Reference Examples and Application Examples. However, the present invention is by no means limited to only these Examples. It is not something to be done. In the following, all parts and percentages are by weight unless otherwise specified. Each operation was performed in the following manner.

(1) Measurement of reduced viscosity

With a mixed solvent having a composition of phenol / 1,1,2,2-tetrachloroethane (weight ratio = 6/4), the concentration was adjusted to 0.4 g / dl, and
° C, and the unit is dl / g
(Deciliter / gram).

(2) Measurement of flow start temperature

The test was carried out by using a die having a diameter of 1 millimeter (mm) and a length of 1 mm under a load of 98 N (Newton) using an advanced type flow tester.

(3) Measurement of 25% DMF solution viscosity

Immediately after preparing the N, N-dimethylformamide solution of the polyester resin, it was immersed in a constant temperature water bath at 25 ° C. for 2 hours, and then performed with a BM type rotational viscometer. , The unit is mPa
s (millipascal seconds).

(4) Preparation of Film for Characteristic Evaluation Each solution composition obtained in each Example and each Comparative Example was applied on release paper with a thickness of 0.2 mm, and then Preliminary drying was performed for 4 minutes in hot air of 80 ° C., and thereafter, in hot air of 140 ° C.
Heating and drying were performed for minutes. Thereafter, curing was performed at room temperature for one week. The thickness of each film thus obtained is about 40 μm (micrometer)
Met.

(5) Measurement of strength and elongation of the coating film Each test piece having a width of 5 mm and a test length of 20 mm was subjected to elongation deformation at a speed of 300 mm per minute. . The unit of the breaking strength is MPa (megapascal), and the unit of the elongation is% (percent).

Example 1 Determination of 136.4 parts of ethylene glycol, 174.6 parts of dimethyl terephthalate, 24.4 parts of dimethyl 2,6-naphthalenedicarboxylate and 704.2 parts of terminal group Polyoxytetramethylene glycol having a number average molecular weight of 2,000, and 0.04 parts of zinc acetate 2
Hydrate, 0.08 parts of tetraisopropyl titanate, and 3.5 parts of 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene was introduced into a reaction vessel equipped with an electric stirrer, a reflux condenser and a thermometer, and was added at a rate of 4 / min.
While passing 0 ml of dry nitrogen, the mixture was heated to 180 ° C. and heated.

The temperature at the upper end of the reflux condenser reached 60 ° C., and distillation of methanol started. For 30 minutes
After the stirring was continued at the same temperature, the temperature was raised to 200 ° C. over 60 minutes. After the reaction at the temperature of 200 ° C. for 30 minutes,
The temperature was raised to 220 ° C. over 60 minutes. Part 220
10 minutes after the temperature reached ° C, the temperature at the upper end of the reflux condenser began to decrease. After 30 minutes, the temperature reached 45 ° C, and methanol distillation was stopped. Here, the amount of the recovered methanol was 57.6 parts.

The reflux condenser was removed from the reaction vessel and, instead, a pressure reducing pipe having a small vessel for recovering the glycol was attached. At the same time, the pipe for dry nitrogen was also removed and the pressure was reduced. I put on the meter. While the internal temperature was kept at 220 ° C., the pressure inside the reaction vessel was gradually reduced to 2 mmHg over 60 minutes.

Thereafter, the temperature was raised to 240 ° C. over 30 minutes. The pressure in the reaction vessel was gradually lowered, and after 30 minutes from reaching 240 ° C., 0.8 mmHg
It became. The reaction was allowed to continue for another 30 minutes, and then nitrogen was blown into the reaction vessel to stop the reaction at atmospheric pressure, and the reaction was stopped in a molten state on a Teflon resin plate. And allowed to cool in the air. The ethylene glycol recovered here was considered to contain methanol and other by-products, and the total weight was 91.4 parts.

In this case, the composition of the polyester resin is such that the molar ratio of terephthalic acid residues: naphthalenedicarboxylic acid residues is 90:10 and the content of polyoxytetramethylene glycol is from the ratio of the raw materials charged. 8
It is calculated to be 0% by weight. The polyester resin thus obtained is a translucent solid that exhibits a slight yellow color, and has elastic properties. The reduced viscosity of the polyester resin is 2.83.
And the flow start temperature was 140 ° C.

Examples 2 and 3 In the same manner as in Example 1 except that the ratio of each component in the resulting polyester resin was changed as shown in Table 1,
The respective polyester resins for Examples 2 and 3 were prepared. Table 1 shows the composition, reduced viscosity, and flow start temperature of each of these polyester resins, together with the case of Example 1.

[0079]

[Table 1]

<< Footnotes to Table 1 >> EG: abbreviation for ethylene glycol TPA: NDCA PTMG representing the ratio of the number of moles of terephthalic acid residues: 2,6-naphthalenedicarboxylic acid residues (%): Indicates the content of polyoxytetramethylene glycol units in the polyester resin

Comparative Examples 1 to 4 In the same manner as in Example 1 except that the kind and ratio of each component in the produced polyester resin were changed as shown in Table 2, the components of Comparative Examples 1 to 4 were replaced. The respective polyester resins were prepared. The composition and reduced viscosity of each of these polyester resins and the flow start temperature are summarized,
It is shown in Table 2.

As far as the composition of Comparative Example 2 was based, no polyester resin in which the polyester component and the polyoxyalkylene glycol were homogeneously copolymerized was obtained. When based on, the polyester resin obtained there is very soft,
The flow start temperature could not be measured.

[0083]

[Table 2]

<< Footnotes in Table 2 >> EG: abbreviation of ethylene glycol PG: abbreviation of 1,2-propylene glycol BG: 1. Abbreviation for 4,4-butylene glycol

TPA: NDCA… terephthalic acid residue:
It represents the ratio of the number of moles of 2,6-naphthalenedicarboxylic acid residue.

PTMG (%): Indicates the content of polyoxytetramethylene glycol units in the polyester resin.

“×”: polyester resin could not be prepared.

[0088]

[Table 3]

Example 4 The polyester resin obtained in Example 1 was cut into about 1 cm square, and 50 parts were put into 150 parts of DMF, and heating and stirring were continued at 120 ° C. for 1 hour. By letting go, the solid content concentration is 25%,
In addition, a solution composition having a viscosity of 8,000 mPa · s at 25 ° C. was obtained.

Next, this solution composition was directly used as 2
After being allowed to stand at a temperature of 5 ° C., the change in viscosity was examined, and it was confirmed that the composition had good stability. In addition, the rupture strength of the film produced from this solution composition was 25 MPa, and the rupture elongation was 900%. Table 3 summarizes the results of these evaluation determinations.

Examples 5 and 6 Using the resin obtained in Example 2, the solution composition of Example 5 was replaced with the resin obtained in Example 3 by Example 6.
Were prepared respectively. After that,
In the same manner as in Example 4, each solution composition was evaluated and evaluated. The results are summarized in Table 3. In the case of this example, all of them are
The solution composition had good stability, and in addition, a tough film was formed.

[0092]

[Table 4]

<< Footnote to Table 3 >> The unit of the viscosity of each solution composition is mPa · s (millipascal second).

Comparative Examples 5 to 8 Each of Comparative Examples 5 to 8 was prepared using the resin obtained in Comparative Example 1.
Using the resin composition obtained in Comparative Example 2 as the solution composition for Comparative Example 6, the solution composition for Comparative Example 6 was used as the solution composition for Comparative Example 7 using the resin obtained in Comparative Example 3. The composition and
Using the resin obtained in Comparative Example 4, a solution composition for Comparative Example 8 was prepared. Thereafter, evaluation and judgment were performed for each solution composition in the same manner as in Example 5. The results are summarized in Table 4.

In the case of the product of the present example, the solution composition of Comparative Example 5 already showed a significant increase in viscosity after 24 hours. In the case of Comparative Example 6,
The desired solution composition itself could not be prepared. Furthermore, the film obtained from the solution composition in Comparative Example 7 was very soft, and the strength could not be measured. Furthermore, in the case of Comparative Example 8,
Although the preparation of the solution composition was possible,
After hours, it had already solidified.

[0096]

[Table 5]

<< Footnote to Table 4 >> The unit of the viscosity of each solution composition is mPa · s (millipascal second).

"X" in the column of film properties indicates that the solution composition itself could not be prepared.

Example 7 A film prepared using the solution composition obtained in Example 4 was allowed to stand in a hot-air dryer at 120 ° C. for 50 hours, after which the film was broken after a heat deterioration test. The strength was 25 MPa, and the breaking strength after a humidity and heat resistance deterioration test was performed by leaving it in a thermo-hygrostat at 75 ° C. and 95% Rh for one week. Was 28 MPa. Table 5 summarizes the results of these observations.

Example 8 A film prepared using the solution composition obtained in Example 6 was left in a hot-air dryer at 120 ° C. for 50 hours, and the film was broken after a heat deterioration test. The strength was 27 MPa, and the breaking strength after the humidity and heat deterioration test was conducted by leaving it in a thermo-hygrostat at 70 ° C. and 95% Rh for one week. Was 26 MPa. The results of these observations are shown in Table 5.

Comparative Example 9 "Chrisbon MP-145" (trade name of N, N-dimethylformamide solution of polyurethane resin manufactured by Dainippon Ink and Chemicals, Inc.) having a thickness of 40
After the film having a thickness of μm was cured at room temperature for one week, the breaking strength was 60 MPa.

Next, the cured film was allowed to stand in a hot-air dryer at 120 ° C. for 50 hours to obtain a breaking strength of 15 after a heat deterioration test.
MPa and at 75 ° C. and 95% Rh
The rupture strength after the moist heat degradation test, which was performed by allowing the sample to stand for one week in a thermo-hygrostat at a constant humidity, was 19 MPa. Table 5 summarizes the results of these observations.

[0103]

[Table 6]

Reference Example In this example, the composite sheet prepared by using each polyester resin prepared in each of the examples is compared with a composite sheet which has been obtained conventionally. The purpose is to verify whether there are any differences.

That is, the purpose is to verify whether the obtained resin is equivalent to or completely different from that obtained by using a polyurethane resin as a conventional resin.

Using "Chris Bon MP-145",
The composite sheet produced as follows has a thickness of 1.
27 mm, and 100 parts of the original nonwoven fabric was filled with 58 parts of the polyurethane resin.

[Preparation of Composite Sheet of Resin and Nonwoven Fabric]

First, a polyester (manufactured by Manufacture Co., Ltd.) having a thickness of about 1.1 mm was added to a solution diluted with N, N-dimethylformamide so that the resin content was 15% by weight.
The solution was fully impregnated by soaking the nonwoven.

Next, the resin was squeezed with a stainless steel mangle roll having a roll interval of 1.0 mm, and then immersed in water at room temperature for 10 minutes to solidify the resin. Inside, 30
After soaking for a minute, they were washed.

Thereafter, the water was squeezed out with a rubber mangle roll and then dried in a hot air drier at 100 ° C. for 30 minutes.
Let dry for minutes.

Application Example 1 A composite sheet prepared using the solution composition obtained in Example 5 in the same manner as in the Reference Example had a thickness of 1.22 mm and was 100 parts of the original nonwoven fabric. The sheet was filled with 66 parts of a polyester resin, and had an appearance and texture very similar to those of the composite sheet of the reference example.

Application Example 2 A composite sheet produced using the solution composition obtained in Example 7 in the same manner as in the Reference Example had a thickness of 1.21 mm and was 100 parts of the original nonwoven fabric. Further, it was a form filled with 64 parts of a polyester resin, and had an appearance and texture very similar to those of the composite sheet of the reference example.

[0113]

The polyester resin according to the present invention is excellent in solubility in polar solvents. In addition, it provides a solution having excellent stability, and particularly, it has excellent mechanical strength, heat resistance and heat resistance. It is also excellent in wet heat deterioration resistance, etc., to form an extremely practical film, and as a solution composition in which the polyester resin is dissolved in a polar solvent, mainly, a fibrous base material and And can be effectively used and applied as various adhesives or coating agents for the production of the composite sheet.

Further, the polyester resin of the present invention is also used by itself mainly as a film or various molded articles, or as an adhesive. It is extremely practical, and can be applied.

Claims (7)

[Claims] 1. A polyester resin obtained by using terephthalic acid and naphthalenedicarboxylic acid as main acid components, and using ethylene glycol and polyoxyalkylene glycol as main alcohol components. 2. The ratio of the number of moles of terephthalic acid residues to the number of moles of naphthalenedicarboxylic acid residues is from 95: 5 to 7
A polyester resin having a ratio of 0:30 and a polyoxyalkylene glycol unit content of 60 to 90% by weight based on the solid content of the obtained polyester resin. 3. The polyester resin according to claim 1, wherein the polyoxyalkylene glycol is a polyoxytetramethylene glycol having a number average molecular weight of 500 to 3,000. 4. A polyester resin obtained by using terephthalic acid and naphthalenedicarboxylic acid as main acid components, and further using ethylene glycol and polyoxyalkylene glycol as main alcohol components, and a polar solvent. Solution composition. 5. The ratio of the number of moles of terephthalic acid residues to the number of moles of naphthalenedicarboxylic acid residues is from 95: 5 to 7
0:30, and further comprising a polyester resin having a polyoxyalkylene glycol unit content of 60 to 90% by weight based on the solid content of the obtained polyester resin, and a polar solvent. Solution composition. 6. The polyoxyalkylene glycol is a polyoxytetramethylene glycol having a number average molecular weight of 500 to 3,000.
Or the solution composition according to 5. 7. The method according to claim 4, wherein the polar solvent contains N, N-dimethylformamide, and the content of the polyester resin is 5 to 50% by weight. A solution composition as described.