JP4139991B2 - Polyester resin composition and method for producing the same - Google Patents

Description

【００３７】
（参考例４、５、６）
表２に記載した層状複水酸化物２部、エチレングリコール１２４部、テレフタル酸１６６部、反応触媒としてテトラブチルチタネート０．０６８部を、温度計、攪拌機、留出用冷却管を具備した反応容器に仕込み、加圧下でエステル化反応を実施した。その間に温度は２３０℃まで上げた。温度が２００℃を越える頃から溶融物は透明になった。その後系内を徐々に減圧し、最終的に０．５ｍｍＨｇに達した。その時の温度は２７０℃を保持させた。このようにして層状複水酸化物を１重量％含有する高粘度のポリエチレンテレフタレート（ＰＥＴ）組成物を得た。
【００３８】
得られた組成物をフェノール／テトラクロロエタンに溶解し、還元粘度を測定した。また、熱プレス法（ヒートプレスでポリエステル樹脂組成物を280℃に加熱溶融し、０．２ｍｍ厚のフッ素系樹脂フィルムの間で圧力をかけて薄くした後、水で急冷固化し厚み約２５μmのフィルム状樹脂組成物を得る方法）によって得られたフィルムの酸素バリア性を測定した。層状複水酸化物による酸素バリア効果を、層状複水酸化物含有による酸素透過量の減少比として表２に記載した。
【００３９】
（比較例６、７、８）
表２に記載した層状複水酸化物２部、ビス（β−ヒドロキシエチル）テレフタレート２５４部、反応触媒としてテトラブチルチタネート０．０６８部を、温度計、攪拌機、留出用冷却管を具備した反応容器に仕込み、系内の温度を２３０℃まで上げた。その後系内を徐々に減圧し、最終的に０．５ｍｍＨｇに達した。その時の温度は２７０℃を保持させた。このようにして層状複水酸化物を１％含有する高粘度のポリエチレンテレフタレート（ＰＥＴ）組成物を得た。ただし、層状複水酸化物は分散不良で、肉眼でも観察できる塊になっていた。実施例４と同様に評価した。結果を表２に示す。なお、実施例５と比較例６、実施例６と比較例７、実施例７と比較例８はそれぞれ同じ層状複水酸化物を用いた。
【００４０】
【表２】

【００４１】
表１、２より明らかなように、ポリエステルの重縮合時に層状複水酸化物を添加した実施例１〜３は、層状複水酸化物を含まない比較例１や重縮合が終了してから単に配合しただけの比較例２、層状複水酸化物含有量が特許請求の範囲外の比較例３、４、エチレングリコールを使わない比較例５、６、７、８に比べて、外観、強度、弾性率、ガスバリア性が飛躍的に向上していることがわかる。
【００４２】
【発明の効果】
本発明により機械的強度、硬度、剛性、ガスバリア性等が改善されたポリエステル樹脂組成物を得ることが出来る。この組成物は、ガスバリア性が向上し、包装材料として使用できる。また硬化剤と配合し、剛性を増すことにより、接着性に優れた接着剤を得ることができる。また、硬化剤と配合し鋼板へ塗布すれば、硬度が増すことにより耐擦傷性等に優れた塗装鋼板を得ることが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester resin composition having improved mechanical strength, hardness, rigidity, gas barrier properties and the like.
[0002]
[Prior art]
Typical polyesters such as polyethylene terephthalate and polybutylene terephthalate are used in the fields of fibers, films, bottles, molding materials, etc. because of their excellent mechanical strength, heat resistance, and hygiene. In response to the demand for upgrading these polyesters, various functions are performed by combining fillers and resins. For example, improved functions such as weather resistance, flame retardancy, antistatic properties, colorability, slidability, surface properties, antibacterial properties, crystallinity, transparency, impact resistance, blocking resistance, conductivity, gas barrier properties, etc. Therefore, it is blended with a filler.
[0003]
In recent years, nylon / clay (montmorillonite, etc.) hybrids utilizing intercalation into layered compounds have been actively studied and put into practical use as automobile composites as nanocomposites. With this nanocomposite, effects such as high elastic modulus, improved heat resistance, and improved gas barrier properties are obtained even when the filler has a filling rate of only a few percent. Examples of the filler used in the nanocomposite include clay minerals such as smectites such as montmorillonite and saponite, kaolins such as kaolinite, and silicate compounds.
[0004]
As such layered inorganic particles, layered double hydroxides typified by hydrotalcite are known. Layered double hydroxides or hydrotalcite compounds are particles having a layered structure with an anion between layers, and are used as a heat stabilizer for polyvinyl chloride. Moreover, in order to have a heat storage effect, it is added to an olefin film and used for an agricultural film, or it is dissolved in an acid and has a pH control function, so that it is also used for a pharmaceutical antacid. WO 01/42335 discloses the use of hydrotalcites as a polyester polymerization catalyst. Further, Japanese Patent Publication No. 2002-500253 and Japanese Patent Publication No. 2002-500254 disclose nanocomposites using at least 20% of anions having compatibility and / or reactivity with a polymer matrix.
Although a composite system with layered inorganic particles has been studied for polyester resins, polyester resins such as polyethylene terephthalate have not been obtained with satisfactory characteristics.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a polyester resin composition having improved mechanical strength, hardness, rigidity, gas barrier properties and the like in a composite system of a polyester resin and layered inorganic particles.
[0006]
[Means for Solving the Problems]
As a result of intensive studies on the above problems, the present inventors have reached the present invention. That is, this invention is the polyester resin composition manufactured by the manufacturing method of the following polyester resin compositions, and its method.
(1) In the manufacturing method of the composition which consists of 0.1-10 weight part layered double hydroxide with respect to 100 weight part of polyester resins and polyester resin, it swollen with ethylene glycol by heating in ethylene glycol beforehand . A method for producing a polyester resin composition, comprising blending a layered double hydroxide at an arbitrary stage until polycondensation is completed in a polymerization step of a polyester resin, and then completing polycondensation of the polyester resin.
(2) A polyester resin composition produced by the method described in (1).
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The layered double hydroxide used in the present invention is a layered compound represented by the general formula [M 2 ⁺ _1−x M ³⁺ _x (OH) ₂ ] [A ⁿ⁻ _{x / n} · zH ₂ O]. When the divalent metal (M ²⁺ ) is replaced by the trivalent metal (M ³⁺ ), the layer is positively charged, and a structure in which an anion (A ⁿ⁻ ) exists between the layers is formed. Examples of the divalent metal include magnesium, nickel, and zinc, and examples of the trivalent metal include aluminum, iron, and chromium (n is 1 to 1).
An integer of 3, x is a numerical value of 0.15 to 0.5, and z is a numerical value of 5 or less). In addition to divalent and trivalent metals, monovalent metals such as lithium and tetravalent metals such as titanium may be included.
The method for producing the layered double hydroxide used in the present invention is not particularly limited, but, for example, the method described in S. Miyata, Clays Clay Miner., Vol. 28, page 50 (issued in 1980) is simple and preferable.
The layered double hydroxide may be fired in the range of 300 to 800 ° C.
[0008]
The polyester resin composition of the present invention is obtained by blending a layered double hydroxide swollen with ethylene glycol at any stage until polycondensation is completed in the polyester polymerization process, and then completing the polycondensation. . In order to sufficiently disperse and peel the layered double hydroxide, it is desirable to add the layered double hydroxide before or during the esterification reaction or transesterification reaction.
[0009]
The purpose of the present invention is to swell the layered double hydroxide with ethylene glycol and widen the layer interval when blending the layered double hydroxide at any stage until the polycondensation is completed in the polyester polymerization process. Essential to achieve. The swelling of the layered double hydroxide with ethylene glycol is performed by heating in ethylene glycol. A temperature of 50 ° C. or more and 200 ° C. or less, more preferably a temperature of 100 ° C. to 180 ° C. is suitable. The swelling of the layered double hydroxide with ethylene glycol may be performed in the polyester polymerization step or in advance. The dibasic acid of the polyester raw material may be present when the layered double hydroxide is swollen with ethylene glycol.
[0010]
By using a layered double hydroxide swollen with ethylene glycol, the layered double hydroxide can be efficiently dispersed in the polyester resin, and delamination can be promoted. As a result, molecular reinforcement at the nanometer size can be achieved. The object of the present invention is considered to be achieved.
[0011]
The surface area of the layered double hydroxide used in the present invention is preferably from 5 to 200 m ² / g. If the surface area is less than 5 m ² / g, the transparency of the resin itself may be lowered. On the other hand, if it exceeds 200 m ² / g, the melt viscosity at the time of polymerization rises rapidly, so that a resin having the desired molecular weight may not be obtained.
[0012]
In the present invention, the layered double hydroxide is blended in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the polyester resin. If it exceeds 10 parts by weight, the melt viscosity becomes too high, it becomes difficult to increase the molecular weight of the polyester resin, and the resulting composition may become very brittle. On the other hand, if it is 0.1 parts by weight or less, the effect of adding the layered double hydroxide is reduced.
[0013]
The dibasic acid component of the polyester resin used in the present invention includes terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid and other aromatic dibasic acids, succinic acid, adipine Examples thereof include aliphatic dibasic acids such as acid, azelaic acid, sebacic acid, dimer acid, and cyclohexanedicarboxylic acid.
[0014]
As glycol components, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol , Triethylene glycol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide of bisphenol A Examples include adducts, propylene oxide adducts of bisphenol A, or polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
[0015]
Furthermore, lactones such as ε-caprolactone and δ-valerolactone, and oxycarboxylic acids such as p-hydroxyethoxybenzoic acid are also examples of raw materials for the polyester resin. Trifunctional or higher functional components such as trimethylolpropane, pentaerythritol and trimellitic anhydride may be used in combination.
[0016]
In order to improve the dispersibility and delamination of the layered double hydroxide, it is preferable to introduce a sulfonic acid metal base into the polyester resin. Examples of raw materials for introducing the sulfonic acid metal salt into the polyester resin include 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, sodium sulfoterephthalic acid, 2-sodium sulfo-1,4-butanediol, 2,5 -Dicarboxylic acid or glycol such as dimethyl-3-sodium sulfo-2,5-hexanediol, and 5-sodium sulfoisophthalic acid and 5-potassium sulfoisophthalic acid are particularly preferable.
The amount of the sulfonic acid metal base introduced into the polyester resin is preferably 0.5 mol% to 20 mol% of the total dicarboxylic acid component. If it is less than 0.5 mol%, the effect of improving the dispersibility and delamination of the layered double hydroxide cannot be obtained remarkably, and if it is 20 mol% or more, the thermal stability of the polyester resin tends to deteriorate.
[0017]
For the production of the polyester resin, a usual polymerization method of high molecular weight polyester can be used. That is, the presence of a metal catalyst such as antimony, titanium or germanium after esterification of dibasic acid and glycol or transesterification of methyl ester compound of dibasic acid and glycol under excessive glycol conditions Examples thereof include a melt polymerization method for deglycolization under high temperature and high vacuum and a solid phase polymerization method for polymerization at high vacuum below the melting point of the resin.
[0018]
【Example】
Hereinafter, the present invention will be specifically illustrated by examples. In the examples, “parts” means “parts by weight”. The present invention is not limited by these examples. The characteristics shown in the examples are measured and evaluated by the following methods.
[0019]
(Reduced viscosity)
The reduced viscosity was measured at 30 ° C. with phenol / tetrachloroethane (6/4 weight ratio) as a solvent and a composition concentration of 0.4 g / dl.
(Glass transition temperature; Tg)
The sample was subjected to DSC measurement under the following conditions, and the glass transition temperature Tmg was determined based on JIS K7121.
Device name: DSC6200 manufactured by Seiko Instruments Inc.
Bread: Aluminum bread (non-airtight type)
Sample weight: 5 mg
Temperature rise start temperature: -100 ° C
Temperature increase rate: 20 ° C / min.
Atmospheric gas: Nitrogen [0020]
(Distance between layered double hydroxides)
The interlayer distance was measured by a powder X-ray diffraction method using an X-ray diffraction apparatus Rigaku Corporation Geiger Flex RAD-II type.
[0021]
(Polyester resin composition)
The composition of the polyester was measured by ¹ H-NMR under the following conditions.
Apparatus name: Nuclear magnetic resonance apparatus (AVANCE500 manufactured by BRUKER)
Measurement solvent: deuterated chloroform / trifluoroacetic acid = 9/1 (v / v)
Resonance frequency: 500MHz
Integration count: 512 times Measurement temperature: room temperature
(50% modulus)
The elastic modulus at 50% elongation was measured under the following conditions.
Device name: UYM-I-2500 manufactured by Toyo Baldwin
Measurement temperature and humidity: 20 ° C, 50% RH
Tensile speed: 200 mm / min Sample shape: 15 mm x 30 mm strip (thickness: approx. 25 μm)
[0023]
(Storage modulus)
The dynamic storage elastic modulus at −10 ° C. was measured under the following conditions.
Device name: DVA-200 manufactured by IT Measurement & Control Co.
Temperature rise start temperature: -100 ° C
Temperature increase rate: 20 ℃ / min.
Atmospheric gas: Nitrogen measurement frequency: 110Hz
Measurement style: Tensile deformation [0024]
(Dispersity of hydrotalcite: solution stability)
The polyester resin composition obtained for examining the degree of dispersion of hydrotalcite was dissolved in methyl ethyl ketone / toluene (= 1/1 weight ratio) at a solid content concentration of 10%, and the solution stability after 1 week storage at room temperature was observed. Evaluation was made with ◯ when no hydrotalcite sedimentation and with x when sedimentation.
[0025]
(Water vapor barrier property)
30 cc of water was placed in a 100 cc cylindrical glass bottle with an inner diameter of 2 cm, the inlet of the bottle was sealed with the film of Example and Comparative Example (thickness: about 25 μm), and left in an atmosphere of 20 ° C. and 50% RH for one day. The weight loss of water was measured. The reduction amount of water in the film containing no layered double hydroxide of Comparative Example 1 was used as a standard, and the ratio was shown. It shows that water vapor | steam barrier property is so favorable that a numerical value is small.
[0026]
(Oxygen barrier properties)
The oxygen permeation amount of the 25 μm film was evaluated by calculating the ratio when the oxygen permeation amount of the polyester resin having the same composition containing no layered double hydroxide was 1. The smaller the number, the higher the barrier property. The oxygen transmission rate was measured according to JIS K7126.
Measurement temperature and humidity: 20 ℃, 50% RH
[0027]
(Example 1)
Hydrotalcite (Hydrotalcite manufactured by Toda Kogyo Co., Ltd., average particle size 0.15 μm, Mg / Al molar ratio 2.7, BET surface area 18 m ² / g) as a layered double hydroxide in a glass reaction vessel with a stirrer 20 And 80 parts of ethylene glycol were added and the contents were heated at 130 ° C. for 10 minutes. The ethylene glycol solution containing hydrotalcite became a highly viscous paste. The interlaminar distance of hydrotalcite was increased from 7.5 to 8.4 mm by heating in ethylene glycol, as measured by X-ray diffraction.
[0028]
In a reaction vessel equipped with a thermometer, a stirrer and a distillation condenser, 194 parts of dimethyl isophthalate, 236 parts of 3-methyl-1,5-pentanediol and the above hydrotalcite / ethylene glycol solution (2/8 weight ratio) ) 24.8 parts, 0.068 part of tetrabutyl titanate was charged as a reaction catalyst, and the temperature was raised to 180 ° C. The transesterification reaction was completed while the temperature was raised to 230 ° C. while continuing to distill methanol through the transesterification reaction. Thereafter, the pressure inside the system was gradually reduced and finally reached 0.3 mmHg. The temperature at that time was maintained at 260 ° C. In this way, a polyester resin composition containing 2% by weight of hydrotalcite was obtained.
[0029]
The composition of the polyester was analyzed by ¹ H-NMR. The obtained composition was dissolved in phenol / tetrachloroethane (6/4 weight ratio), and the reduced viscosity was measured. Further, the obtained composition was dissolved in methyl ethyl ketone / toluene (= 1/1 weight ratio), applied and dried on a biaxially stretched polypropylene film, peeled off from the propylene film, and a coating film of the resin composition itself was obtained. It was. The reduced viscosity, glass transition temperature, 50% modulus, storage modulus, solution stability, and water vapor barrier property of the coating film were evaluated. The results are shown in Table 1.
[0030]
(Example 2)
As in Example 1, except that the hydrotalcite / ethylene glycol (2/8) solution used in Example 1 is used in an amount of 6.2 parts and ethylene glycol in 15 parts and contains 0.5% by weight of hydrotalcite. A polyester resin composition was obtained. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
[0031]
(Example 3)
19.8 parts of hydrotalcite and 40 parts of ethylene glycol used in Example 1 were charged into a reaction vessel equipped with a thermometer, a stirrer, and a distillation condenser, and stirred at 150 ° C. for 10 minutes. Further, 194 parts of dimethyl isophthalate, 236 parts of 3-methyl-1,5-pentanediol, and 0.068 part of tetrabutyl titanate as a reaction catalyst were added, and a transesterification reaction and a polycondensation reaction were carried out in the same manner as in Example 1 to 8 weights. A polyester composition containing% hydrotalcite was obtained. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
[0032]
(Comparative Example 1)
A polyester resin having the same composition as in Example 1 was obtained without using hydrotalcite. Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.
[0033]
(Comparative Example 2)
Hydrotalcite was mixed with the polyester resin solution of Comparative Example 1 (solvent: methyl ethyl ketone / toluene = 1/1 weight ratio) at a ratio of 100 to 2 in a solid ratio, glass beads were added, and the mixture was shaken and dispersed for 6 hours with a paint shaker. went. A dry coating film was obtained from this dispersion in the same manner as in Example 1. Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.
[0034]
(Comparative Examples 3 and 4)
As in Example 1, except that the concentration of hydrotalcite / ethylene glycol dispersion was changed to obtain polyester compositions having different hydrotalcite contents. In Comparative Examples 3 and 4, the hydrotalcite content falls outside the scope of the present invention. Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1. In Comparative Example 4, the obtained coating film was very brittle, and the 50% modulus and water vapor barrier property could not be measured.
[0035]
(Comparative Example 5)
19.8 parts of hydrotalcite and 40 parts of 3-methyl-1,5-pentanediol used in Example 1 were charged in a reaction vessel equipped with a thermometer, a stirrer, and a distillation condenser, and the mixture was charged at 150 ° C. for 10 minutes. Stir. Further, 194 parts of dimethyl isophthalate, 236 parts of 3-methyl-1,5-pentanediol, and 0.068 part of tetrabutyl titanate as a reaction catalyst were added, and a transesterification reaction and a polycondensation reaction were carried out in the same manner as in Example 1 to obtain 2 weights. A polyester composition containing% hydrotalcite was obtained.
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
[0036]
[Table 1]

[0037]
( Reference Examples 4, 5, 6)
Reaction container equipped with 2 parts of layered double hydroxide described in Table 2, 124 parts of ethylene glycol, 166 parts of terephthalic acid, 0.068 part of tetrabutyl titanate as a reaction catalyst, thermometer, stirrer, and condenser for distillation The esterification reaction was carried out under pressure. During that time, the temperature rose to 230 ° C. From the time when the temperature exceeded 200 ° C., the melt became transparent. Thereafter, the pressure inside the system was gradually reduced and finally reached 0.5 mmHg. The temperature at that time was kept at 270 ° C. Thus, a highly viscous polyethylene terephthalate (PET) composition containing 1% by weight of layered double hydroxide was obtained.
[0038]
The obtained composition was dissolved in phenol / tetrachloroethane, and the reduced viscosity was measured. In addition, the polyester resin composition was heated and melted to 280 ° C. by heat pressing (heat pressing, thinned by applying pressure between 0.2 mm-thick fluororesin films, and then rapidly cooled and solidified with water to a thickness of about 25 μm. The oxygen barrier property of the film obtained by the method of obtaining a film-like resin composition was measured. The oxygen barrier effect by the layered double hydroxide is shown in Table 2 as the reduction ratio of the oxygen permeation amount due to the layered double hydroxide content.
[0039]
(Comparative Examples 6, 7, 8)
Reaction comprising 2 parts of layered double hydroxide described in Table 2, 254 parts of bis (β-hydroxyethyl) terephthalate, 0.068 part of tetrabutyl titanate as a reaction catalyst, equipped with thermometer, stirrer, and condenser for distillation The container was charged and the temperature in the system was raised to 230 ° C. Thereafter, the pressure inside the system was gradually reduced and finally reached 0.5 mmHg. The temperature at that time was kept at 270 ° C. Thus, a highly viscous polyethylene terephthalate (PET) composition containing 1% of layered double hydroxide was obtained. However, the layered double hydroxide was poorly dispersed and formed a lump that could be observed with the naked eye. Evaluation was performed in the same manner as in Example 4. The results are shown in Table 2. In addition, Example 5 and Comparative Example 6, Example 6 and Comparative Example 7, Example 7 and Comparative Example 8 each used the same layered double hydroxide.
[0040]
[Table 2]

[0041]
As is clear from Tables 1 and 2, Examples 1 to 3 in which the layered double hydroxide was added during the polycondensation of the polyester were simply performed after the completion of the comparative example 1 and the polycondensation not including the layered double hydroxide. Compared with Comparative Example 2 in which the content of the layered double hydroxide was outside the scope of claims, Comparative Examples 3, 4 and Comparative Examples 5, 6, 7, and 8 not using ethylene glycol, the appearance, strength, It can be seen that the elastic modulus and gas barrier properties are dramatically improved.
[0042]
【The invention's effect】
According to the present invention, a polyester resin composition having improved mechanical strength, hardness, rigidity, gas barrier properties and the like can be obtained. This composition has improved gas barrier properties and can be used as a packaging material. Moreover, the adhesive agent excellent in adhesiveness can be obtained by mix | blending with a hardening | curing agent and increasing rigidity. Moreover, if it mix | blends with a hardening | curing agent and is apply | coated to a steel plate, the coated steel plate excellent in abrasion resistance etc. can be obtained by hardness increasing.

Claims (2)

In the method for producing a composition comprising 0.1 to 10 parts by weight of layered double hydroxide with respect to 100 parts by weight of polyester resin and polyester resin, layered double water swollen with ethylene glycol by heating in ethylene glycol in advance A method for producing a polyester resin composition, comprising blending an oxide at an arbitrary stage until polycondensation is completed in a polyester resin polymerization step, and then completing polycondensation of the polyester resin. A polyester resin composition produced by the method according to claim 1.