JP2001098060A - Multifunctional polyester resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin capable of manufacturing and working in a same manner as a conventional saturated polyester resin, having a high content of functional groups, thus easy to attach functions by working after it is formed in a fiber, a film, and moldings, or excellent in flexibility, and usable as an adhesive, a paint, etc. SOLUTION: This multifunctional polyester resin contains, in its total acid component, not less than 2 mol% aromatic dicarboxylic acid component having at least a phenolic hydroxyl group, and has not less than 200 eq/106 g hydroxyl group in the resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyfunctional polyester resin having excellent productivity and processability.

[0002]

2. Description of the Related Art Polyethylene terephthalate (PET)
Polyester resin, which is abbreviated as), has excellent mechanical and chemical properties, and is used to form fibers for clothing and industrial use, as well as films or bottles for magnetic tapes, capacitors, etc. Widely used for goods. In addition, a copolymerized polyester resin in which a part of PET or polybutylene terephthalate is replaced with another component,
Since the melting point and the crystallinity can be changed depending on the copolymerization component and the copolymerization amount, the properties are changed depending on the application and used.

However, such polyester resins are:
Generally, since a functional group is provided only at the terminal of a molecule, when the degree of polymerization is increased, the content ratio of the functional group to the resin weight is reduced. Therefore, in the field of application of fibers and films using a polyester resin having a high degree of polymerization, when imparting a specific function by performing chemical processing or the like, the amount of functional groups contained in the resin is low, and the processability and the application efficiency are poor. Therefore, there is a problem that it is necessary to perform a surface treatment in advance with a medicine, energy rays, or the like. In the field of application of paints and adhesives, a polyester resin containing a large amount of terminal carboxyl groups and hydroxyl groups is used, and a cross-linking reaction is carried out with an epoxy resin or urethane compound that reacts with these functional groups, to achieve stable film dimensions. Improvement of heat resistance, heat resistance, chemical resistance and the like has been performed. However, increasing the amount of terminal functional groups decreases the degree of polymerization of the polyester resin,
In general, there has been a problem that the melt processability is significantly reduced, and the flexibility and flexibility of the resin are also reduced.

[0004] In order to solve such a problem, for example, Japanese Patent Application Laid-Open No. 1-165620 proposes a modified polyester resin in which an aliphatic dicarboxylic acid having an unsaturated bond is copolymerized. Such a polyester resin is capable of introducing a functional group by cleaving an unsaturated bond by a compound having an electrophilic attack ability after melt processing,
A product composed of a polyfunctional polyester resin having a high degree of polymerization can be obtained. However, compounds having an unsaturated bond are generally unstable in a molten state at a high temperature, and cause significant coloring during polymerization or melt processing,
There is a problem that the polymer is cleaved during polymerization to cause gelation.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and can be produced and melt-processed in the same manner as a conventional saturated polyester resin, and has a high functional group content. It is an object to provide a polyester resin having an amount.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and have reached the present invention. That is, the gist of the present invention is as follows. A polyester resin comprising a dicarboxylic acid and / or an ester-forming difunctional carboxylic acid component other than the dicarboxylic acid, and a diol component, wherein the content of the aromatic dicarboxylic acid component having at least one phenolic hydroxyl group is a total acid. A polyfunctional polyester resin having a content of 2 mol% or more based on components and a hydroxyl group content of 200 eq / 10 ⁶ g or more in the resin.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the polyfunctional polyester resin of the present invention, it is necessary that an aromatic dicarboxylic acid component having at least one phenolic hydroxyl group is copolymerized in an amount of 2 mol% or more of all acid components. Since the phenolic hydroxyl group does not form an ester bond with a normal carboxyl group, if an aromatic dicarboxylic acid having such a hydroxyl group is copolymerized in the polyester, the phenolic hydroxyl group remains in the side chain of the polyester, This results in a polyester resin having a high hydroxyl group content.

Specific examples of the aromatic dicarboxylic acid component having at least one phenolic hydroxyl group include 5-hydroxyisophthalic acid, 4-hydroxyphthalic acid, and 2,5-dihydroxy-1,4-benzenedicarboxylic acid. No. It is necessary that the copolymerization amount of such a component is 2 mol% or more based on all the acid components. If this amount is less than 2 mol%, it becomes difficult to contain a sufficient amount of hydroxyl groups to obtain a substantial modifying effect. The upper limit of the copolymerization amount is not particularly limited, but if the copolymerization amount increases, the melt viscosity of the polyester increases, and it may be difficult to increase the degree of polymerization during melt polymerization. It is preferable that the content be approximately 20 mol% or less.

The dicarboxylic acid component other than the above and / or the ester-forming bifunctional carboxylic acid other than dicarboxylic acid and the diol component may be appropriately selected according to the use. For example, in applications where a high melting point and high crystallinity are required, such as fibers and films, terephthalic acid (hereinafter abbreviated as TPA) is used as the aromatic dicarboxylic acid component.
And 2,6-naphthalenedicarboxylic acid and ethylene glycol (hereinafter abbreviated as EG) and 1,4-butanediol (hereinafter abbreviated as 1,4-BD) as an aliphatic diol component.

For applications such as binder fibers, adhesives and paints, TPA and isophthalic acid (hereinafter abbreviated as IPA) or adipic acid as dicarboxylic acid components are used.
By using an aliphatic dicarboxylic acid such as sebacic acid in combination, and using EG and 1,4-BD, neopentyl glycol and the like as an aliphatic diol component, physical properties such as melting point and crystallinity were controlled within a desired range. It can be a polyester resin.

In addition to the dicarboxylic acid component and the aliphatic diol component as described above, a bifunctional aromatic carboxylic acid such as an ethylene oxide adduct of p-oxybenzoic acid, ε-
Bifunctional aliphatic carboxylic acid derivatives such as caprolactone (hereinafter abbreviated as ε-CL) and δ-valerolactone; aromatic diols such as ethylene oxide adducts of bisphenol A and bisphenol S; 1,4-cyclohexanedimethanol; Can be used.

The polyfunctional polyester resin of the present invention needs to have a hydroxyl group content of 200 eq / 10 ⁶ g or more in the resin. If the hydroxyl content in the resin is less than 200 eq / 10 ⁶ g,
A substantial reforming effect cannot be obtained, which is not preferable. The upper limit of the hydroxyl group content is not particularly limited, but if the copolymerization amount of the aromatic dicarboxylic acid component having a phenolic hydroxyl group is increased to increase the hydroxyl group content, the physical properties of the polyester resin are reduced. Therefore, it is preferable that the concentration be approximately 2000 eq / 10 ⁶ g or less.

The polyfunctional polyester resin of the present invention preferably has an intrinsic viscosity of at least 0.45 in order to increase the strength of the product and improve the processability during melt molding.
The polyfunctional polyester resin of the present invention uses an aromatic dicarboxylic acid component having at least one phenolic hydroxyl group as a component for increasing the hydroxyl group content. Since the phenolic hydroxyl group does not form an ester bond with a normal carboxyl group, the aromatic dicarboxylic acid having such a hydroxyl group does not cause a cross-linking reaction in the course of being copolymerized in the polyester, and has a high degree of polymerization. It is possible to use a polyfunctional polyester resin.

The polyfunctional polyester resin of the present invention can be obtained, for example, by the following method. First, the temperature
Under a nitrogen gas control at 230 to 250 ° C., a mol of glycol component / acid component is added to an esterification reactor in which bis- (β-hydroxyethyl) terephthalate and / or a low polymer thereof (hereinafter abbreviated as PET oligomer) is present. EG with ratio 1.1-2.0
And a slurry of TPA and a residence time of 7-8 hours to obtain the esterification reaction. The esterification reaction product is transferred to a polymerization reactor, and 5-hydroxyisophthalic acid (hereinafter abbreviated as 5-HIPA) and a predetermined amount of a polymerization catalyst are added.
The esterification reaction is performed at a temperature of 0.5 to 2 hours. Thereafter, the temperature of the polymerization reactor is raised to 260 to 280 ° C., and the polycondensation reaction is performed under reduced pressure of 0.01 to 13.3 hPa until the intrinsic viscosity becomes 0.45 or more. The polycondensation reaction is usually performed in the presence of a polycondensation reaction catalyst, and conventionally used compounds of metals such as antimony, germanium, tin, titanium, and cobalt are preferably used.

Further, as long as the effects of the present invention are not impaired, additives such as antioxidants such as hindered phenol compounds, color compounds such as cobalt compounds, fluorescent agents and dyes, and pigments are contained. May be.

[0016] The polyfunctional polyester resin thus obtained has a higher hydroxyl group content than ordinary PET, so that after forming into a fiber or film, a phenolic resin is added to impart a specific function. When processed with a resin or chemical that reacts with a hydroxyl group, the processability is good and the efficiency of imparting a function is high. In addition, since the degree of polymerization of the resin is increased without being affected by the amount of the functional groups, the polyester resin can react with the curing agent even in adhesives and coatings, and has flexibility and flexibility. An excellent coating can be obtained.

[0017]

The present inventor believes that the polyester resin of the present invention is polyfunctional and has excellent productivity and processability as follows. In the polyfunctional polyester resin of the present invention, an aromatic dicarboxylic acid having a phenolic hydroxyl group is copolymerized. The phenolic hydroxyl group in this molecule does not form an ester bond with a normal carboxyl group, which is one of the components constituting the main chain of the polyester resin, but the dicarboxylic acid portion in the molecule forms the main chain of the polyester resin. Reacts with the diol which is another component to form an ester bond and is incorporated into the molecular chain of the polyester resin. For this reason, it can be produced by polymerization in the same manner as ordinary polyester.

The phenolic hydroxyl group remains as a side chain of the polyester molecule. However, since this hydroxyl group does not exist at the terminal of the polyester molecular chain as in the prior art, the hydroxyl group decreases even when the degree of polymerization of the polyester resin is increased. There is no. Therefore, since the degree of polymerization can be increased while having a hydroxyl group amount necessary for imparting a function or a curing reaction at the time of post-processing, a fiber or a film can be easily melt-processed and has high productivity, and the product Can be improved in strength. In addition, it is possible to make the coating excellent in flexibility and flexibility by using an adhesive or a paint.

[0019]

Next, the present invention will be described in detail with reference to examples. In addition, the measuring method of the characteristic value in an example was performed as follows. (a) Intrinsic viscosity ([η]) Using an equal weight mixed solvent of phenol and ethane tetrachloride,
It was measured at a temperature of 20 ° C. (b) Polyester composition and hydroxyl group content Measured by NMR JNM-LA4000 manufactured by JEOL Ltd.

Example 1 A slurry of TPA and EG (at a molar ratio of 1 / 1.6) was continuously supplied to an esterification reactor in which a PET oligomer was present, and the temperature was 250 ° C.
The reaction was carried out under the conditions of a temperature of 0.1 ° C. and a pressure of 0.1 MPaG, and a residence time of 8 hours was used to continuously obtain an esterified product having a conversion of 95%. Next, the esterified product was transferred to a polycondensation reactor so as to have the molar ratio shown in Table 1, 5-HIPA was added so as to have the molar ratio shown in Table 1, and antimony trioxide was used as a polycondensation catalyst. 2 × 10 ^-4 mol / mol of acid component, temperature 250 ° C, pressure
The esterification reaction was performed for 30 minutes while stirring under the conditions of 0.1 MPaG. Next, the temperature of the reactor was raised to 270 ° C. in 30 minutes, and the pressure in the reactor was gradually reduced to 1.2 hPa or less after 70 minutes. The polycondensation reaction was carried out for 2 hours while stirring under these conditions to obtain a polyester resin having the properties shown in Table 1.

Examples 2 to 4, Comparative Example 1 The composition ratio and type of the aromatic dicarboxylic acid having a phenolic hydroxyl group were changed as shown in Table 1, and the same as in Example 1 so as to obtain a predetermined intrinsic viscosity. went. Table 1 shows the properties of the obtained polyester resin.

Example 5 A slurry (molar ratio 1/3) of IPA and EG was charged into a reaction vessel equipped with a stirrer and a packed tower, and the reaction temperature was increased while stirring at normal pressure.
At 200 ° C, remove the generated water out of the reaction
The esterification reaction was performed for an hour to obtain an esterified product (A) having a conversion of 95%. In addition, a slurry (molar ratio 1 / 1.6) of TPA and EG was continuously supplied to the esterification reactor in which the PET oligomer was present, and reacted at a temperature of 250 ° C. and a pressure of 0.1 MPaG,
With a residence time of 8 hours, an esterified product (B) having a conversion of 95% was continuously obtained. Next, the esterified products (A) and (B) were transferred to the polycondensation reactor so that the molar ratios shown in Table 1 were obtained, and 5-HIPA was added so that the molar ratios shown in Table 1 were obtained. Antimony trioxide as polycondensation catalyst at 2 × 10 ^-4 mol /
The acid component mole was added, and the esterification reaction was performed for 30 minutes while stirring at a temperature of 250 ° C. and a pressure of 0.1 MPaG. Next, the temperature of the reactor was raised to 270 ° C. in 30 minutes, and the pressure in the reactor was gradually reduced to 1.2 hPa or less after 70 minutes. The polycondensation reaction was carried out for 3 hours while stirring under these conditions to obtain a polyester resin having the properties shown in Table 1.

Example 6 A slurry of TPA and EG (at a molar ratio of 1 / 1.6) was continuously supplied to an esterification reactor in which PET oligomers were present.
The reaction was carried out under the conditions of a temperature of 0.1 ° C. and a pressure of 0.1 MPaG, and a residence time of 8 hours was used to continuously obtain an esterified product having a conversion of 95%. This was transferred to a polycondensation reaction vessel, and 5-HIPA, ε-CL, and 1,4-BD were added thereto in the molar ratio shown in Table 1, and tetrabutyl titanate was used as a polycondensation catalyst at 2 × 10 5. ^-4 mol / mol of an acid component was added, and the esterification reaction was performed for 1 hour while stirring at a temperature of 200 ° C. and a pressure of 0.1 MPaG. Next, the temperature in the reactor was raised to 240 ° C. in 30 minutes, and the pressure in the reactor was gradually reduced to 1.2 hPa or less after 70 minutes. The polycondensation reaction was carried out for 3 hours while stirring under these conditions to obtain a polyester resin having the properties shown in Table 1.

Examples 7 to 9 and Comparative Example 2 The composition ratio and type of the carboxylic acid component and the composition ratio of the aromatic dicarboxylic acid having a phenolic hydroxyl group were changed as shown in Table 1 so as to obtain a predetermined intrinsic viscosity. In the same manner as in Example 6. Table 1 shows the properties of the obtained polyester resin.

[0025]

【table 1】

Reference Example 1 The polyester resin obtained in Example 1 was pelletized,
After drying by a conventional method, the resultant was melt-spun at a spinning temperature of 290 ° C. using a usual melt-spinning apparatus, and an undrawn yarn was wound up at a speed of 1400 m / min. This undrawn yarn was supplied to a drawing machine, preheated at 80 ° C., drawn 3.5 times while being in contact with a heat plate at a temperature of 150 ° C., heat-treated and wound up to obtain a 75d / 36f filament yarn. For the obtained fiber, using a Tensilon RTC-1210 model manufactured by Orientec, a 50 cm sample was subjected to a tensile test at a speed of 50 cm / min, and the strength and elongation were obtained from the stress-strain curve. 4.3
6g / d, elongation = 37.1%, showing good strength and elongation characteristics. Next, the obtained fiber is knitted in a tube and scoured at 60 ° C. for 20 minutes, and then a 10 wt% emulsion (O / W type) of an epoxy polyether-modified silicone compound (XF42-812, manufactured by Toshiba Silicone Co., Ltd.) And squeezed to remove excess emulsion. Next, this was heat-treated at 130 ° C. for 30 minutes, then washed with water to remove unreacted silicone compound, and air-dried. The content of Si atoms of this sample was measured with a fluorescent X-ray analyzer Systm3270 manufactured by Rigaku Corporation to determine the amount of silicone compound attached. as a result,
The adhesion amount of the silicone compound was 2.1 wt%, which was a sufficient adhesion amount to exhibit water repellency and antifouling properties.

Reference Example 2 10 g of the polyester resin obtained in Example 5 and 1 g of an epoxy resin (YD-128, manufactured by Toto Kasei Co., Ltd.) were added to 100 g of cyclohexanone.
And dried on a PET film with a length of 150 mm, a width of 22.5 mm, and a thickness of 12 μm, and then air-dried. = 180 ℃, pressure = 0.4MPaG, speed
= 0.5 m / min. Using a Tensilon RTC-1210 manufactured by Orientec, a peeling test was performed at a speed of 50 cm / min to evaluate the adhesive strength. as a result,
The peel strength was 3.2 Kg / cm, which was a good adhesive strength, and the film was excellent in flexibility without peeling between films even when bent.

As is clear from Table 1, the polyesters of Examples 1 to 9 are polyfunctional and can be produced by ordinary melt polymerization, and as shown in Reference Examples, fibers having excellent post-processability. In addition, it was possible to obtain an adhesive film having excellent adhesive strength and flexibility. Examples 1, 3 to 6,
In Nos. 8 and 9, since the intrinsic viscosity of the polyester was 0.45 or more, the spinnability and the like were particularly good and were suitable for use in melt processing. On the other hand, in Comparative Examples 1 and 2, since the copolymerization of the aromatic dicarboxylic acid having a phenolic hydroxyl group was small, the hydroxyl group content in the resin was insufficient.

[0029]

According to the present invention, it can be manufactured and processed by the same method as the conventional saturated polyester resin, and has a high functional group content, and can be used for fibers, films, molded products,
Alternatively, a polyfunctional polyester resin useful as an adhesive, a paint, or the like is provided.

Claims (2)

[Claims] 1. A polyester resin comprising a dicarboxylic acid and / or an ester-forming bifunctional carboxylic acid component other than a dicarboxylic acid, and a diol component, wherein the aromatic dicarboxylic acid component has at least one phenolic hydroxyl group. A polyfunctional polyester resin having a content of 2 mol% or more based on all acid components and a hydroxyl group content of 200 eq / 10 ⁶ g or more in the resin. 2. The polyfunctional polyester resin according to claim 1, wherein the intrinsic viscosity of the resin is 0.45 or more.