JPH0491137A - Polyester elastomer sheet - Google Patents

Abstract

PURPOSE:To obtain a polyester elastomer sheet having improved tensile strength and elongation at break by melting and molding a reaction product of a specific aromatic polyester and a lactone into a sheetlike state, rolling or drawing and heat-treating. CONSTITUTION:(A) An aromatic polyester obtained from A1: a diol component mainly comprising ethylene glycol and/or butylene glycol and containing 0.1-30mol% dihydroxy compound shown by the formula (R<1> and R<2> are H or CH2CH2OH) and A2: a dicarboxylic acid component consisting essentially of terephthalic acid is reacted with (B) a lactone (preferably 5-membered ring to 8-membered ring) in the weight ratio of the component A/B of 30/70-80/20, preferably 30/70-70/30 at 180-300 deg.C to give a polyester copolymer, which is melted and molded into a sheetlike state, rolled or drawn and heat-treated to give a polyester elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polyester elastomer sheet (including a film and a plate-like body) formed of a polyester copolymer having rubber-like elasticity.

(Prior Art) As a method for manufacturing a polyester elastomer sheet, for example, Japanese Patent Publication No. 1-49741 describes
A method has been proposed in which a crystalline polyester elastomer having a melting point of C or higher is melt-molded into a sheet, rolled in the width direction and simultaneously rolled in the length direction, and then heat treated. According to such a method, a sheet having higher tensile strength and tear strength than an unstretched sheet can be obtained.

(Problems to be Solved by the Invention) In the sheet obtained in the above publication, a polyester having a relatively high melting point and crystallinity is used. However, because aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate are used as the hard segment of the elastomer,
Physical properties such as tensile strength at break and elongation of the sheet were insufficient.

The present invention has been made to solve the above-mentioned drawbacks, and its purpose is to provide a polyester elastomer sheet that has further improved physical properties such as tensile strength at break and elongation compared to conventional sheets. be.

(Means for Solving the Problems) The polyester elastomer sheet of the present invention has (A) ethylene glycol and/or butylene glycol as a main diol component, terephthalic acid as a main dicarboxylic acid component, and has a general formula of the following formula (I). A polyester copolymer obtained by reacting an aromatic polyester containing 0.1 mol % to 30 mol % of the dihydroxy compound represented by the diol component with (B) lactones is melted in a sheet form. After shaping, the sheet is obtained by rolling or stretching and then heat treatment, whereby the above object is achieved.

CI) (wherein R1 and R2 are independently -H or -C)+2C
Indicates H20H. ) The aromatic polyester used in the present invention mainly contains ethylene glycol and/or butylene glycol, a diol component containing the dihydroxy compound represented by the above formula [I), and a dicarboxylic acid component mainly containing terephthalic acid. Constituent components.

Butylene glyfur is 1,4-butanediol, 13-
Any butanediol can be used. The dihydroxy compound [■] is a low-molecular compound exhibiting liquid crystallinity, for example, 4,4°゛°-Nhidokogyu/
-p-quarterphenyl, 4,4''-di(2-hydroxyethoxy)-p-quarterphenyl, and the like are preferably used.

The second transition from the crystalline state to the liquid crystalline state of the above 4,4°°°-dihydroxy-p-quarterphenyl is at 336°C.
1 and 4.4”-(2-hydroxyethquine)
-p-quarterphenyl has a temperature of 403°C.

In addition, 4.4-perdihydroxy-p-quarterphenyl is described, for example, in the Journal of Chemical
5ociety, 1379-115 (1940). Further, the liquid crystal state refers to a state in which the compound is in a molten state and the molecules maintain an oriented state.

The above dihydroxy compounds CI) may be used alone or in combination.

Liquid crystal molecules generally have high crystallinity, and as mentioned above, 4
．． 4''-dihydroxy-p-quaterphenyl and 4.4''-di(2-hydroxyethoxy)-p-quaterphenyl have a high transition point from crystal to liquid crystal state, so these dihydroxy compounds [I ] is incorporated into the polymer chain, the polymer exhibits unique properties.In other words, dihydroxy compound [1] exhibits crystallinity and has a high transition point, so the amount of dihydroxy compound [I] incorporated is Even in small amounts, it forms strong and highly heat-resistant physical crosslinks.As a result, it is presumed that a thermoplastic elastomer with high heat resistance can be obtained without impairing the flexibility derived from the soft segment.

An aromatic polyester consisting of at least one of ethylene glycol and butylene glycol, a dihydroxy compound [■], and terephthalic acid, a glycol other than the above, a polyalkylene ochind, a borinlicone having two hydroxyl groups, the formula Aromatic diol components other than [I], aromatic dicarboxylic acids other than terephthalic acid, aromatic hydrocarbon dicarboxylic acids, and aliphatic dicarboxylic acids may be contained as constituent components, but these are the diol components and dicarboxylic acid components. It is preferably 10 mol% or less of the total amount. .

The above glycols include propylene glycol, trimethylene glycol, 1.5-bentanediol, 16-bentanediol,
-hebutanediol, 17-hebutanediol, 1.8
-octanediol, 1,9-nonanediol, 1.1
0-decanediol, cyclopenkune-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimetatool, etc. These may be used alone or in combination of two or more.

Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene oxide, etc.
These may be used alone or in combination of two or more. The number average molecular weight of polyalkylene oxide is
If it becomes too small, the ability to impart flexibility to the resulting aromatic polyester will decrease, and if it becomes too large, the physical properties such as thermal stability of the resulting aromatic polyester will decrease.
00 to 20.000 is preferable, more preferably 500
~5.000.

Examples of the polysilicone include dimethylpolysiloxane, diethylpolysiloxane, diphenylpolysiloxane, and the like. The number average molecular weight of the polysilicone is preferably 100 to 20,000, more preferably 500,000 because if it becomes small, the ability to impart flexibility to the polyester produced will decrease, and if it becomes large, the production of polyester will be difficult. ~5000.

Examples of the aromatic diol include hydrogynone, resorcinol, chlorohydroquinone, flomohydroquinone, methylhydroquinone, phenylhydroquinone, metquinhydroquinone, phenoxyhydroquinone, 44'-dihydroxybiphenyl, 4,4-dihydroxydiphenyl ether, 4,4'' -dihydroxydiphenyl sulfide,
44゛-dihydroxydiphenylsulfone, 4,4°-
Dihydro-bovine dibenzophenone, 4,4-dihydroxydiphenylmethane, bisphenol A, 1,1-di
(4-hydroxyphenyl)cyclohegyusan, 1.2-
Bis(4-hydroxyphenoxy)ethane, 1,4-
Examples include dihydroxynaphthalene and 26-dihydroxynaphthalene.

The aromatic dicarboxylic acids include isophthalic acid, 5-
Metal salt of sulfoisophthalic acid, 4,4-dicarboxybiphenyl, 4,4'-dicarboxy7diphenyl ether, 4,4-dicarboxydiphenyl sulfide, 44
゛-Dicarboxydiphenyl sulfone, 33°-dicarboxybenzophenone, 44゛-dicarboxybenzophenone, 1,2-bis (4-carboxybenzophenone 7)
Ethane, 1,4-dicarboxynaphthalene, or 26
- Examples include dicarboxynaphthalene.

The above-mentioned aromatic hydroquine carboxylic acids impart rigidity and liquid crystallinity to polyester, and include salicylic acid, metahydroquine benzoic acid, barahydrobinbenzoic acid, 3-chloro-4-hydroxybenzoic acid, 3-bromo-4- Hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid #2-hydroxy-6-naphthoic acid, 4-hydroxy-4- Examples include carboxybiphenyl, preferably parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-hydroxy-
4-carboxybiphenyl.

The aliphatic dicarboxylic acid is preferably a dicarboxylic acid having 10 or less carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, speric acid, and cepatic acid.

The aromatic polyester consisting of the above dihydroxy compound CI), at least one of ethylene glycol and butylene glycol, and a dicarboxylic acid component mainly containing terephthalic acid has a dihydroxy compound (the lower the content of N, the lower the heat resistance decreases, and if increases, the elastic modulus increases and flexibility decreases, making it unsuitable as a thermoplastic elastomer.
) content is 0.1 to 30 mol% of the diol component constituting the polyester, more preferably 0.5 to 2 mol%.
0 mol%, more preferably 1.0 to 10 mol%
It is. In addition, when polyalkylene oxide or polysilicone is used as a diol component other than aromatic, the structural unit thereof is counted as one monomer. That is, the degree of polymerization is 10
of polyethylene oxide counts as 10 monomers.

The aromatic polyester used in the present invention may be a mixture of a plurality of aromatic polyesters, such as a combination of two or more aromatic polyesters having different soft segments.

Furthermore, it may be made by copolymerizing a small amount of a branched component such as trimellitic acid or glycerin, or it may be an aromatic polyester obtained by blocking the terminal carboxyne group with epoxy or the like to stabilize the aromatic polyester. .

Aromatic polyester consisting of the above components is
It can be produced using any generally known polycondensation method. For example, ■ a method in which a dicarboxylic acid component and a diol component are reacted directly, ■ a method in which a lower ester of a dicarboxylic acid component and a diol component are reacted using transesterification, and ■ a method in which a halide of a dicarboxylic acid component and a diol component are reacted with pyridine. (2) A method in which a metal alcoholade as a diol component is reacted with a halide as a dicarboxylic acid component; (2) A method in which an acetylated diol component and a dicarboxylic acid component are reacted using transesterification. , etc.

When performing polycondensation, catalysts that are generally used in producing polyester may be used.

This catalyst includes lithium, sodium, potassium,
Cenium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt,
germanium, tin, lead, antimony, arsenic, cerium,
Examples include metals such as boron, cadmium, and manganese, their organometallic compounds, organic acid salts, metal alkoxides, and metal oxides.

Particularly preferred catalysts include calcium acetate, diacyl stannous, tetraacyl stannous, dibutyltin dilaurate, dimethyltin maleate, tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyltitanate, germanium dioxide,
and antimony trioxide. Two or more of these catalysts may be used in combination. In addition, water produced as a by-product during polymerization,
In order to efficiently distill off alcohols, glycols, etc. and obtain high molecular weight polymers, the reaction system must be kept at lm in the late stage of polymerization.
It is preferable to reduce the pressure to mHg or less. The reaction temperature is generally 150-350°C.

The lactones used in the present invention ring-open, react with acids and hydroxyl groups, and add aliphatic chains, giving flexibility to the polyester copolymer, and adding aliphatic chains to the polyester copolymer. Those having 4 or more carbon atoms are preferred, and 5- to 8-membered rings are more preferred. Examples include ε-caprolactone, δ-valerolactone, γ-butyrolactone, enantolactone, cabryrolactone, and the like. Two or more types of lactones may be used in combination.

The composition ratio of the above-mentioned aromatic polyester and lactones is such that the weight ratio of aromatic polyester/lactones is 30/70 to 8 from the viewpoint of elastic properties of the resulting polyester copolymer.
0/20 is preferable, and a particularly preferable range is 30/70 to
It is 70/30.

For the reaction between aromatic polyester and lactones, the above-mentioned catalyst used for producing aromatic polyester may be used. When the reaction is carried out in a solvent-free system, the reaction temperature is usually a temperature at which the mixture of aromatic polyester and lactones is uniformly melted, and is higher than the melting point of the produced block copolymer.

When the aromatic polyester and lactone are reacted in a solvent system, an appropriate reaction temperature can be adopted. Generally, a temperature in the range of 180'C to 300C is preferred. 180°C
If the temperature is less than 300°C, it is difficult for the aromatic bossester to dissolve easily and uniformly with the lactones, and if it exceeds 300°C, decomposition and other undesirable side reactions occur. Further, when the above reaction is carried out in a solvent system, the solvent needs to be a common solvent with the aromatic polyester and lactones. For example, α-methylnaphthalene can be used.

The aromatic polyester-polylactone polyester copolymer thus obtained is usually formed into a sheet by melt extrusion, and the obtained sheet is stretched by rolling or stretching. Rolling or stretching may be uniaxial or biaxial. When rolling the sheet, it can be carried out mainly using a rolling roll and, if necessary, using a take-up roll, and the rolling ratio is preferably about 2 to 7 times in the longitudinal direction and 1 to 2 times in the transverse direction. The temperature of the sheet during rolling is
Usually, the temperature range is above the glass transition point of the polyester copolymer and at least 30°C lower than the melting point, preferably at room temperature to at least 50°C below the melting point.
C It is a low temperature.

Stretching of the sheet can usually be carried out using a take-up roll, and the stretching ratio is preferably 2 to 10 times, and the temperature during stretching can be set in the same manner as in the above-mentioned rolling.

It is necessary to heat-treat rolled or stretched sheets so that the sheet does not undergo dimensional changes or performance deterioration when used in a high-temperature atmosphere. The heat treatment temperature is preferably higher than the use temperature considering the use environment of the sheet, but if heat treatment is performed at a temperature too close to the melting point of the polyester copolymer, the rolling or stretching effect will be relaxed, so the melting point It is preferable to limit the temperature to about 20°C or more lower than the temperature range.

(Example) The present invention will be explained below by giving comparative examples and examples.

Comparison fertilizer (A) Synthesis of aromatic polyester In a glass flask with an internal volume of 11 equipped with a stirrer, a thermometer, a gas inlet, and a distillation port, 194 g (1.0 mol) of dimethyl terephthalate and 138 g of ethylene glycol were added.
g (2.24 mol>, a small amount of carunium acetate and acid or antimony were added as catalysts. After purging the inside of the flask with nitrogen, the temperature inside the flask was raised and the reaction was carried out at 180°C for 3 hours. Along with the reaction, the inside of the flask Methanol began to be distilled out, and bis(2-hydroxyethyl) terephthalate was obtained.

50.7 g (0.15 mol) of 4,4"°-dihydroxy-p-quarterphenyl was added to this flask, and the temperature of the flask was raised to 280°C, and the reaction was carried out at this temperature for about 2 hours. Next, distillation The mouth of the flask was connected to a vacuum vessel, and the flask was reacted for 1 hour while the pressure inside the flask was reduced to 1 mm and 1 g.

During the reaction, ethylene glycol was distilled out, and an extremely viscous liquid was formed in the flask. After cooling the flask,
The glass flask was broken and the product was taken out.

(B) Synthesis of polyester copolymer Internal volume 1 equipped with stirring blade, gas inlet and distillation port
In a glass flask of λ, 250 g of the aromatic polyester obtained in section (A) above and 250 g of ε-caprolactone.
, 1.0 g of tetrabutyl titanate as a catalyst.

and I,3,5-trimethyl-2, as a heat stabilizer.
After charging 1.0 g of 4,6-tris(3,5-di[-butyl-4-hydro/benzene) and purging the inside of the flask with nitrogen, it was heated in an oil bath with stirring for 2 hours.
Heated to 50°C. The reaction system became a homogeneous viscous liquid.

Subsequently, after reacting for 1 hour under a nitrogen stream, the gas inlet was connected to a vacuum pump, and the inside of the flask was heated to i torr.
The reaction was further continued for 1 hour under the following reduced pressure.

Next, the obtained polyester copolymer was melt-extruded through a T-die at a temperature of 240°C to obtain a film-like product, and the film-like product was passed through a cooling roll kept at 20"C to reduce the thickness. A 3 mm unstretched sheet was obtained.

The obtained sheet was punched and formed into a Tsuki S K6301 No. 3 dumbbell, and a tensile test was conducted using Autograph AGB-5000 manufactured by Shimabara in accordance with ASTM D638 to determine tensile strength at break, tear strength, and elongation during tensile war. The results are shown in Table 1.

Note that the tensile strength at break and the elongation during tensile war are the values when the sheet is pulled in the longitudinal direction, and the bow tear strength is the value when the sheet is pulled in the direction orthogonal to these.

An unrolled sheet (thickness 3
mm) was rolled under the following conditions and then heat treated to obtain a polyester elastomer sheet.

The unstretched sheet was heated through a preheating chamber set at 80°C, and then stretched 182 times in the width direction and rolled 2.5 times in the machine direction between a pair of rolls heated to 100°C. .

Note that the magnification in the longitudinal direction (feeding direction) was adjusted by changing the circumferential speed ratio of the rolling roll and the take-up roll, and the magnification in the width direction was adjusted by the press pressure of the rolling roll.

Next, the rolled sheet is taken up and placed next to the roll at 160°.
Heat fixation was carried out by passing through a heating chamber of C at a constant speed.

At this time, the sheet feeding speed was 15 m/min, and the heat setting time was 2 minutes.

The physical properties of the obtained rolled and heat-treated sheet (polyester elastomer sheet) were measured in the same manner as in the comparative example. The results are shown in Table 1.

In Example 1, an unrolled sheet (thickness: 3 mm) was uniaxially stretched 5 times at 100°C, and then a heat-treated sheet was obtained in the same manner as in Example 1.

The physical properties of the obtained sheet were measured in the same manner as in the comparative example. The results are shown in Table 1.

Table 1 It is obtained by rolling or stretching a polyester copolymer into which a node segment based on a quarter phenyl compound, which has higher crystallinity and a higher melting point than conventional polyesters, is then heat-treated. Alternatively, during stretching and then heat treatment, the hard segments are oriented to form strong physical crosslinks. Furthermore, since polylactones are introduced into the polyester copolymer as a soft segment, it also has rubber elasticity.

Therefore, for example, it has heat resistance that does not cause creep phenomenon even when used in areas subject to heavy loads or at high temperatures.
An elastomer sheet with excellent mechanical properties etc. can be provided.

Claims (1)

[Claims] 1. (A) Ethylene glycol and/or butylene glycol is the main diol component, terephthalic acid is the main dicarboxylic acid component, and a dihydroxy compound whose general formula is represented by the following formula [I] is the diol component. A polyester copolymer obtained by reacting an aromatic polyester containing 0.1 mol% to 30 mol% with (B) lactones is melt-molded into a sheet shape, and then the sheet is rolled or Polyester elastomer sheet obtained by stretching and then heat treatment: ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R^1 and R^2 are independently -H or -CH_
Indicates 2CH_2OH. ).