JPH01256521A - Copolymerized polyester having excellent toughness and crystallinity - Google Patents

Abstract

PURPOSE:To obtain a copolymerized polyester having excellent toughness and crystallinity, by incorporating a specified polyfunctional component, a polyalkylene glycol component and an aliph. dicarboxylic acid component besides two main constitutional components. CONSTITUTION:0.01-8mol% polyfunctional component (C) having at least two functional groups selected from among carboxylic acids and alcohols and also an alkali metal salt group of a carboxylic acid as a substituent (e.g., an alkali metal salt of dimethylolpropionic acid) based on the component A, 1-20wt.% polyalkylene glycol component (D) having a number-average MW of 400-4,000 (e.g., polyethylene glycol) based on a polyester consisting of both components A and B and 0.2-5mol% 9C or higher aliph. dicarboxylic acid component (E) (e.g., dimer acid or sebacic acid) based on the component A are incorporated in a polyester consisting of an arom. dicarboxylic acid component (A) wherein the main component is terephthalic acid and a glycol component (B) wherein the main component is ethylene glycol. A copolymerized polyester having improved brittleness which has been a defect of polyethylene terephthalate and improved moldability in injection molding at a low mold temp. which is 100 deg.C or lower can be obtd. without spoiling excellent properties such as high m.p. and high rigidity which polyethylene terephthalate has.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field] The present invention relates to copolyesters having improved physical properties, in particular good toughness and good crystallinity.

[Conventional technology]

Polyethylene terephthalate (hereinafter abbreviated as pE'r) has been used for various purposes, but it has the advantage of having a higher glass transition point and melting point than polybutylene terephthalate, which is the same thermoplastic polyester. On the other hand, PET injection molded or extrusion molded products that have undergone 1M crystallization without reinforcement with glass fiber or other reinforcing materials exhibit brittleness if the molecular chains are fully crystallized without orientation. The reality is that it cannot be put to practical use.

On the other hand, PET is known to have major drawbacks in terms of moldability and physical properties due to its crystallization behavior. That is, since PET has a low crystallization rate at low temperatures, it is difficult to obtain a molded product with good crystallization when injection molding is performed at a mold temperature of, for example, 130° C. or less, and only a molded product with poor surface hardness is obtained. Moreover, if the obtained molded product is used at a temperature above the glass transition, crystallization will proceed, resulting in poor shape stability. In addition, surface roughness occurs due to uneven crystallization within the mold.

Furthermore, molding is carried out at a mold temperature of around 50°C, and PE
In some cases, a method is used in which T is heat-treated after obtaining a molded product with almost no crystallization, but this method is not only inefficient, but also causes the molded product to crystallize due to heat treatment. It has disadvantages such as volumetric shrinkage and deformation.

Therefore, PET molding is usually carried out using a special molding machine that can achieve a mold temperature of 130°C or higher.
Since such molding machines are not common, there has been a desire for a PET resin that can be molded favorably using a commonly used molding machine with a mold temperature of 80 to 100°C or lower.

As a method for imparting ductility to PET, for example, a method of adding a copolymer of a metal ion neutralized product of α-olefin and α, β ethylenically unsaturated carboxylic acid is disclosed in JP-A-52-84.
No. 244 discloses a method of copolymerizing polyalkylene glycol and aliphatic dicarboxylic acid to PET in JP-A No. 62-2.
It is disclosed in Japanese Patent No. 80221.

In addition, as a means for improving the crystallinity of PET, for example, a method of adding a metal salt compound of an organic carboxylic acid is disclosed in Japanese Patent Publication No. 46-29977 and Japanese Patent Publication No. 47-14502.
It is disclosed in the publication No. Additionally, 4.548,978
No. 2, proposes a method in which PET contains a polyalkylene glycol component as a crystallization aid, and further includes a known nucleating agent.

[Problems to be solved by the present invention]

However, in the method disclosed in JP-A-52-84244, the melt viscosity of the composition increased significantly, which caused problems in injection molding, and the resulting composition had the problem of discoloration and deterioration during heating. . The method disclosed in JP-A No. 62-280221 has been found to be effective in imparting ductility, but it is difficult to see a sufficient effect in improving low crystallinity at low temperatures, which is another drawback of PET. .

Also, Japanese Patent Publication No. 46-29977 and Special Publication No. 47-
The method disclosed in Japanese Patent No. 14502 has a problem in that when the compound is added, the molecular weight of PET significantly decreases during molding. Furthermore, in the method disclosed in JP-A-56-92918, metal salts such as carboxylic acids are introduced only at the ends of the molecules, and therefore in ordinary polyesters, only two at most are introduced per molecule, which is significant. It is difficult to obtain a significant crystallization promoting effect. In addition, in order to obtain the polyester having a sufficiently high molecular weight, it is usually necessary to carry out a polycondensation reaction for a long time, which has the disadvantage of coloring the polymer, making it difficult to obtain the desired high molecular weight polyester. There is.

At temperatures below 100°C, it is not possible to obtain a good molded product.

Therefore, the purpose of the present invention is to improve the brittleness, which is a drawback of PET, without impairing the excellent properties of PET such as high melting point and high rigidity, and to improve injection molding at a low mold temperature of 100°C or less. The object of the present invention is to provide a new PET-based copolyester with improved moldability.

[Means to solve the problem]

As a result of intensive research to achieve the above object, the present inventors have discovered that a polyalkylene glycol component and an aliphatic dicarboxylic acid component having 9 or more carbon atoms are combined with the main aim of improving the ductility of PET. In addition to using it as a polymerization component, when a polyfunctional component having an alkali metal base of carboxylic acid is copolymerized as a constituent component of the polyester, the tensile elongation of PET increases significantly, and The present inventors have discovered that a good molded product with sufficiently advanced 5M crystallization can be obtained even when injection molding is carried out at a low mold temperature of .degree. C. or lower, and the present invention has been achieved.

In other words, the present invention provides a polyester comprising an aromatic dicarboxylic acid component (a) mainly consisting of terephthalic acid and a glycol component (mainly ethylene glycol) containing at least two functional groups selected from carboxylic acids or alcohols. and a polyfunctional component C having an alkali metal base of a carboxylic acid in a ratio of 0.0% to component a.
A polyalkylene glycol component d having a molar ratio of 01 to 8 and a number average molecular weight of 400 to 4000 is 1 to 20% by weight based on the polyester consisting of both components a and b, and an aliphatic dicarboxylic acid component having 9 or more carbon atoms e. 0 for component a
．． The present invention provides a copolymerized polyester containing 2 to 5 moles and having excellent toughness and crystallinity.

The aromatic dicarboxylic acid component a in the present invention is primarily a terephthalic acid component, but a portion of it, ie, less than 10 moles, may be replaced by another dicarboxylic acid component other than the terephthalic acid component. Examples of the dicarboxylic acid component other than dicarboxylic acids other than cacarterephthalic acid include aromatic dicarboxylic acids such as inphthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenoxyethane dicarboxylic acid, and diphenyl dicarboxylic acid.

The glycol component in the present invention mainly refers to the ethylene glycol component, but a portion thereof, ie, less than 10 moles, may be replaced with a glycol component other than the ethylene glycol component. Such glycol components include trimethylene glycol, tetramethylene glycol,
hexamethylene glycol, neopentyl glycol,
Examples include aliphatic or alicyclic glycols such as cyclohexane-1,4-dimetatool, and hydroquinone,
Aromatic glycols such as resol 7 and bisphenols can also be exemplified. Furthermore, oxycarboxylic acids such as oxybenzoic acid may be copolymerized.

A major feature of the present invention is that the above a is used as a constituent component of the polymer.
, b, a polyfunctional component c1 having an alkali metal base of carboxylic acid, a polyalkylene glycol component d, and an aliphatic dicarboxylic acid component θ having 9 or more carbon atoms in the polyester. Although the reason for the effect has not been clearly understood at present, the coexistence of these three components is essential for simultaneously improving both the ductility and crystallinity of the copolyester.

In the present invention, the polyfunctional component C having an alkali metal base of carboxylic acid has 3 or more carbon atoms, preferably 3 to 3 carbon atoms.
22 aliphatic, cycloaliphatic or aromatic polyokinecarboxylic acids and mono- or dialkali metal salts of polycarboxylic acids. Among them, dioxydicarboxylic acids and dioxymonocarboxylic acids are preferred and most preferred are dioxinemonocarboxylic acids, such as dimethylolpropionic acid, such as tartronic acid, and alkali metal salts of malic acid, monooxypolycarboxylic acids, , for example, quench > acid, etc. (
D Alkali metal salt has a dioxidation force of 7°.

Alkali metal salts of dicarboxylic acids, such as glyceric acid, 4,4-bis(4-hydroxychlorohexyl)valeric acid, 9,10-dioquine octadecanoic acid, and dioquine dicarboxylic acids, such as tartaric acid, Oxyglutaric acid, α,
Alkali metal salts of δ-dioxyadipic acid, 6,7-dioxydodecanedioic acid, 7,8-dioxyhexadecanedioic acid, furionic acid, dioxyfumaric acid, etc. , alkali metal salts such as citric acid, and polycarboxylic acids, such as oxycarboxylic acids, may be substituted with non-functional If substituents such as alkyl groups.

The present invention is not limited to these exemplary components.

Examples of alkali metal salts include lithium salts, sodium salts, potassium salts, cesium salts, etc., and sodium salts or potassium salts are particularly preferably used.

Multifunctional component C in the copolymerized polyester of the present invention
The amount of O-functional filtrate is 0.01 to 8 mol, preferably 0.1 to 5 mol, based on the aromatic dicarboxylic acid component a. If the amount is less than 0.01 mol, there will be no substantial effect on promoting crystallization, which is one of the objects of the present invention, while if it is added in excess of 8 mol, mechanical properties will deteriorate, which is not preferable.

In the copolymerized polyester of the present invention, using the polyalkylene glycol component d as a copolymerization component means that P
It is necessary to improve the brittleness of the substantially unoriented crystallized product of ET, and is also necessary to lower the glass transition temperature of PELT and improve its crystallinity at low temperatures.

Such realkylene glycols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxy) (!: glycol of a copolymer with brobylene oxide, or a glycol having one end thereof as an alkyl group, aryl group, or aryl group). Examples include derivatives bonded to groups through ester bonds, ether bonds, etc. The polyalkylene glycols may be used alone or in a mixture of 21i1 or more. In the present invention, polyethylene glycols and/or polyalkylene glycols are preferably Tetramethylene glycol.

Further, it is important that the polyalkylene glycol component dO number average molecular weight of the present invention is in the range of 400 to 4,000. Use of a polyalkylene glycol having a molecular weight outside the above range is not preferred because ductility decreases. A more preferred molecular weight range is about 600 to 2,000.
It is.

(6) The proportion of the polyalkylene glycol component d in the copolymerized polyester of the present invention is as specified in a above.

b 1 to 20% by weight of the polyester consisting of both components
, preferably 3 to 1 sit%. If the proportion is less than 1% by weight, it will not improve the PET (D brittleness or crystallinity at low temperatures), and if it exceeds 20% by weight, the rigidity of the crystallized product will decrease and the melting point will also decrease significantly. It would be contrary to the purpose of the invention.

In the aliphatic dicarboxylic acid component e having 9 or more carbon atoms in the copolymerized polyester of the present invention, the number of carbon atoms in the aliphatic dicarboxylic acid is determined by the number of carbon atoms in the main chain between the carboxyl groups of the dicarboxylic acid (carbon ) is preferably 7 or more, and the main chain may optionally have a branch chain or may partially form a ring. Among aliphatic dicarboxylic acids that form a ring, the number of carbon atoms between carboxyl groups is the minimum. Examples of such aliphatic dicarboxylic acids having 9 or more carbon atoms include linear dicarboxylic acids such as azelaic acid, sepacic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, and eicosanedicarboxylic acid, dimer acids, and hydrogenated dimer acids. Examples include compounds or ester-forming derivatives thereof. The aliphatic dicarboxylic acids or their ester-forming derivatives may be used alone or in combination of two or more. Particularly preferred dicarboxylic acids in the present invention are dimer acids and dimer acid hydrogenated products.

Dimer acids in the present invention are unsaturated fats containing 18 carbon atoms, such as linoleic acid and lylunic acid! It is produced from R or its monovalent alcohol ester, and its main component is a dimer acid having 36 carbon atoms, but it also contains some -basic acids and trimer acids. In order to achieve the object of the present invention, it is preferable to use a dimer acid with a low content of basic acid and trimer acid. It is preferably contained in a proportion of 0.2 molti or more and 5 molti or less based on the aromatic dicarboxylic acid component a. Within this range, the crystallized product of the copolymerized polyester exhibits excellent ductility while maintaining high rigidity, and as a result, toughness is imparted. 0.
At a ratio of less than 2 molt, the toughness cannot be sufficiently improved as in the case where polyalkylene glycol is used alone as a copolymer component. In addition, at a ratio exceeding 5 molt,
The melting point of the crystallized product decreases greatly and the rigidity is also impaired, which is not suitable for the purpose of the present invention.

Furthermore, in the present invention, when P-modified with component e in the above-described proportion, the brittleness of the PET crystallized product, which is slightly improved by modification with only polyalkylene glycol, is dramatically improved. This effect is not achieved with aliphatic dicarboxylic acids having less than 9 carbon atoms. There is no particular upper limit to the number of carbon atoms in the aliphatic dicarboxylic acid.

In the present invention, the reason why the effect of the coexistence of the aliphatic dicarboxylic acid component having 9 or more carbon atoms is not clearly understood at present, but for example, when polyalkylene glycol is copolymerized alone with PKT, Whereas a polymerization reaction product with a phase-separated structure is obtained, when an aliphatic dicarboxylic acid having 9 or more carbon atoms is used together, the polymerization reaction product changes to a polymerization reaction product with a fine particle-like dispersed structure. It was observed in transmission electron microscopy using acid staining. The inventors presume that this change in phase separation form is related to improvement in ductility, that is, toughening.

When obtaining the copolymerized polyester of the present invention, for example, a small amount of glycerin, trimethylolpropane, pentaerythritol, hexanetriol 11216% to the extent that the effects of the present invention are not impaired. J Triol or tetraol represented by methylolethane, benzenetricarboxylic acid represented by trimellitic acid, trimesic acid, pyromellitic acid, benzenetetracarboxylic acid, or 3 to 4 hydroxyl groups and carboxyl Polyfunctional monomers such as polyvalent hydroxycarboxylic acids, stearic acid, olefinic acids, etc. to which groups are bonded
Monofunctional aromatic monocarboxylic acids such as -1=nocarboxylic acid, benzoic acid, phenylacetic acid, diphenylacetic acid, and β-naphthoic acid can also be used in combination.

The copolymerized polyester in the present invention is produced by a known method used in producing ordinary polyesters. Polyesters are generally copolymerized by mixing a mixture of reacting components in the presence or absence of a catalyst.

It is produced by raising the temperature in an inert gas atmosphere at atmospheric pressure or under increased pressure. In that case, each raw material component is used in the form of an acid or alcohol or an ester-forming derivative thereof. The temperatures employed to carry out these reactions range from 200°C to 270°C, preferably from 230°C to 260°C. After completion of this reaction, the resulting oligomer product is subjected to polycondensation. The electrocondensation reaction can be performed using known antimony, titanium, iron, zinc,
copal), i, manganese, -17'c is reduced to about 70° C. to about 300° C. in the presence of a polycondensation catalyst such as a germanium catalyst at a pressure of 15 mHy or less, preferably 1 mHy or less.
It is carried out at a temperature in the range of ”C.

In the production of the copolymerized polyester of the present invention, the above-mentioned component C5, component d, and component e can be added at any stage during the production of the polyester, for example, at the stage of esterification or transesterification, or at the stage of polycondensation. Alternatively, it may be added after polycondensation and the polycondensation may be continued to complete the reaction.

The intrinsic viscosity of the copolyester of the present invention is in the range of 0.4 to 1.5, preferably 0.5 to 1.0 when measured in a mixed solvent system of equal weights of phenol and tetrachloroethane at 30°C. It is in.

As mentioned above, the copolymerized polyester of the present invention has a carboxylic acid alkali metal base-containing component C that can act as a crystal nucleating agent and a polyalkylene glycol component d that can act as a crystallization aid, both as constituent components of the polyester. Since it has already been incorporated into the polymer molecule, it is characterized by a sufficiently high crystallization rate even when used alone, and a low glass transition point. Therefore, when used as a molding material, it is virtually unnecessary to separately incorporate a crystal nucleating agent, which is required with conventional PET, and problems associated with the addition of such a nucleating agent are inevitable. This problem has been solved, and it has become possible to obtain excellent moldability even at low molding temperatures of 100°C or less, which was difficult with conventional PET.

introduced inside. For example, in the copolymerized polyester of the present invention obtained from terentalic acid, ethylene glycol, sodium dimethylolpropionate, polytetramethylene glycol, and sepanoic acid, the polyester (
Solvent ditrifluoroacetic acid) 0500 MHz L(-NMR
In the spectrum, the blown absorption of the methyl group is 1
．． It is observed as a singlet at the position of 3 ppm, and even in a sample in which core copolymerized polyester is dissolved in a solvent (isobaric evacuation mixture of phenol and tetrachloroethane, tIX) and reprecipitated with methanol, absorption of protons of methyl groups is observed. is observed in the same way (position and intensity), and in addition to this information, in the same spectrum of sodium dimethylolpropionate (solvent: trifluoroacetic acid), the absorption of 10 tons of methyl group is 1. ippmhl, 21)
pm and 1.3 pprn, and each peak appears at the position of l-13 HL)-CI-12-C-Qlz-(J-1(-C)
Considering that it can be assigned to the structure of (a (D bouton: 1.1 III')")I0ONaUUJNasuH3, sodium dimethylolpropionate in the polyester is not simply heated or introduced at the polymer terminal. It is clear that the polyfunctional component C is introduced into the polymerized molecule as a copolymer component rather than as a copolymer component.However, in the copolymerized polyester of the present invention, if It is not something to be excluded.

In the copolymerized polyester obtained according to the present invention, a plasticizer may be added, if necessary, in order to further enhance the crystallinity of polynisder molecules at low temperatures. As such a substance, any known substance can be used as long as it functions as described above.

Such examples include, for example, aliphatic esters of polyhydric alcohols, aromatic esters of polyhydric alcohols, esters of polycarboxylic acids, polyalkylene glycols, and mono- or dialkyl ethers of polyalkylene glycols. , polyester diols consisting of aliphatic glycol and aliphatic dicarboxylic acid, cyclic polyester (
polyester diols obtained by ring-opening polymerization of lactones), mono- or di-aliphatic and/or aromatic carboxylic acid esters of various polyester diols.

Examples include aromatic sulfonic acid amides, sodium aromatic sulfonates, and fluorinated polyolefins.

Among these substances, polyalkylene glycols and mono- or dialkyl ethers of polyalkylene glycols are preferably used.

Among them, the general formula % formula % (1) (Rz, R't represents f-j or an alkyl group having 1 to 10 carbon atoms, or aroyl, and R2 represents an alkylene group having 2 to 4 carbon atoms. n is a number of 5 or more.) Polyalkylene glycols coated with these are preferred. Particularly preferred are substances in which 16 and R1 are lower alkyl groups. For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and their mono- or dialkyl ethers (such as monomethyl or dimethyl ether, monoethyl or diethyl ether, monopropyl or dipropyl ether, monomethyl or dibutyl ether, etc.), mono- or sialkyl ethers and mono- Alternatively, sialylates (eg, monoacetylate, diacetylate, mono-2-ethylhexanoate, di-2-ethylhexanoate, monobenzoate, dibenzoate, etc.) can be used. In the present invention, it is preferable that the polyalkylene glycol has alkyl ether at both ends, since the inherent viscosity of the polyester resin during molding is less likely to decrease. When using a monoalkyl ether in which only one end is etherified or a polyalkylene glycol in which one and both ends are hydroxyl groups, the intrinsic viscosity of the polyester resin decreases significantly during molding. It is necessary to use a polyester resin of The degree of polymerization n of the polyalkylene glycol (1) must be 5 or more; however, if it is less than 5, the polyalkylene glycol (1) tends to stand out on the surface of the molded product, which is not preferred. The amount of polyalkylene glycol (1) used is 10 parts by weight or less, preferably 5 parts by weight, based on 100 parts by weight of the copolymerized polyester.
Parts by weight or less are appropriate. If the amount is more than 10 parts by 1 part, the rigidity of the molded product will decrease, which is inappropriate.

Further, in the copolymerized polyester of the present invention, it is also possible to add a crystal nucleating agent in anticipation of an effect of improving the crystallization rate and the υ-layer. Furthermore, if necessary, organic...
It is possible to use known flame release agents such as those based on fluorine and phosphorus. Particularly preferred flame retardants include poly(halogenated styrene), halogenated epoxy compounds, and the like. Various flame release aids can be used in combination with flame retardants. Specifically used flame retardant aids include antimony trioxide, antimony compounds such as sodium antimonate, salts of salt, aluminum hydroxide, and silconium oxide 9.
Examples include molybdenum oxide, molybdenum oxide, and the like.

In the copolymerized polyester of the present invention, various additives other than the above-mentioned components for the purpose of improving properties, such as coloring agents, mold release agents, antioxidants, and ultraviolet rays, may be added to the extent that the effects of the present invention are not impaired. Fillers other than glass fibers can be added to the stabilizer, and other polymers such as polyester resins, polyolefin resins, acrylic resins, polycarbonate resins, polyamide resins, rubber-like elastic bodies, etc. can also be added. It is.

The copolyester of the present invention can be processed into fibers, films, '/I's bottles, containers, laminates, etc. using molding machines such as injection molding machines, extrusion molding machines, blow molding machines, and compression molding machines.
It can be molded into a desired shape.

The present invention will be explained in further detail below by giving examples.

In the present invention, all parts in the examples are based on weight.

Examples 1-8, Comparative Examples 1-4 Terephthalic acid (TA) 83 HAs Ethylenezo! J
: A slurry consisting of 36.5 g of l-3, 0.005 part of phosphorous acid, and 0.034 part of antimony trioxide was mixed with a stirrer,
While gradually and continuously charging a reactor equipped with a rectification column and a cooling pipe for water distillation, under a pressure of 2.6 kt/-・G, 250
The esterification reaction was carried out at a temperature of ~255°C. Next, after bringing the reaction system to normal pressure, 0.2 of Irganox 1010 (Ciba Geigy) as an antioxidant was added to the reactant.
part, sodium dimethylolpropionate (DMP-Na) as a modifier, polytetramethylene glycol (PTM3) with a number average molecular weight of about 860, and a number average molecular weight of about 1
000 polyethylene glycol (PEG), dimer acid (Versadime 288 manufactured by Henkel Japan), and sepanoic acid were added in the proportions shown in Table 1, and the mixture was stirred for 10 minutes.

The resulting reaction mixture was transferred to a reactor equipped with a stirrer and an ethylene glycol distillation condenser, and heated from 250°C to 275°C.
The condensation reaction proceeded while gradually increasing the temperature and gradually lowering the pressure of the system from normal pressure to a high vacuum of lse*Hf or less, and the polycondensation reaction was terminated when a predetermined melt viscosity was reached. The obtained polymer was evaluated as follows, and the results are shown in Table 1.

The intrinsic viscosity [η] of the polymer was measured at 30° C. using a mixed system of equal amounts of phenol and tetrachloroethane. In addition, the molecular weight of polyalkylene glycol is JIS K155.
It is calculated from the terminal aqueous group value quantified based on 7.

Crystallinity was evaluated from ΔT and TchO values determined by the following method: ΔT = Tcc - Tch where Tea and Tch are measured using a differential scanning calorimeter (Metra).
Tch shows the exothermic peak temperature when the dried sample is melted in an air stream and then cooled at a cooling rate of 10°C/min. Shows the crystallization exothermic peak temperature when the temperature is raised at a temperature increase rate of 10°C/min for an amorphous film sample formed into a film of about 50μ by a heat press heated to 285°C and quenched with liquid nitrogen. . Regarding the relationship between crystallinity and these peak temperatures determined by DSC, the larger ΔT (i.e.,
The higher the Tcc and the lower the Tch), the faster the crystallization rate.
This shows that good injection moldability can be achieved with low-temperature gold.

The melting point (Tm), which is an index of heat resistance, was expressed by the crystalline melting peak obtained when the amorphous film was subjected to 1) SC measurement at a heating rate of 10''07 minutes.

In addition, the obtained copolymerized polyester was heated at 120°C for 12 hours.
After vacuum drying, it was sandwiched between Teflon-coated iron plates and heat press molded at 280°C using a 1% thick spacer, then immediately transferred to another heat press set at 150°C and held for 5 minutes. After cooling, a 1% thick sheet was formed which was substantially unoriented and fully crystallized. Tensile test specimens were made from this sheet using a preheated No. 2 rubber dumbbell punching die.

This test piece was tested at 23°C using a universal testing machine.
Takumi conducted a tensile test at a tensile speed of 0.5 cm/m.
The average value was determined for n-5, and the tensile property values are shown in Table 1.

It is clear that the copolymerized polyesters of the present invention (Examples 1 to 8) have excellent crystallinity since they all have high Tea, low Tch and large ΔT. It also has an extremely high tensile elongation at break and is rich in toughness.

On the other hand, PET (Comparative Example 1) or copolymerized polyester (Comparative Example 2), which does not contain component ., has a low Tec. PET (Comparative Example 1) or copolyester (Comparative Example 3) that does not contain component d has a high Tch. In all of these comparative examples, ΔT is small and crystallinity is poor.

Also, copolymerized polyester not containing component e (Comparative Example 4)
Although the crystallinity was excellent, the tensile elongation rate was low and it was weak.

Regarding the polyester obtained in Example 7, it was dissolved in trifluoroacetic acid and analyzed by 500 MHz 'H-NMR.
As a result of analysis, an absorption singlet of the proton of the methyl group b\ was observed at the position of 1.3 pl)m. In addition, similar NMR analysis was performed on a sample in which the polyester was dissolved in a mixed solvent of equal weights of phenol and tetrachloroethane and then reprecipitated with methanol, and the absorption of the proton of the methyl group was found to be approximately the same intensity at 1.3 ppm. It was observed in

Example 9 100 parts by weight of the copolymerized polyester obtained in Example 3 and 3 parts by weight of polyethylene glycol dimethyl ether (average molecular weight of the polyethylene glycol portion: 1000) were dried and mixed in advance, and then mixed with Plastograph (manufactured by Brabender, Inc., PL-3000 model) was used to melt and cross-wire (conditions = 275°C).

Rotor speed 3 Q rpm). The obtained composition was evaluated in the same manner as in Example 3, and the results are shown in Table 1.

Example 10 68 parts by weight of the copolymerized polyester obtained in Example 3, 2 parts by weight of polyethylene glycol dimethyl ether (average molecular weight of the polyethylene glycol portion: 1.000), and 30 parts by weight of phlogopite (Graf Sugilite Mica 200HK)
After drying the weight parts in advance, they were mixed and placed in a 40 φ extruder (
Pour into the hopper of a UT-40-T (manufactured by Japan Plastics Institute), and keep the cylinder temperature at 250-275-27.
Strand pellets were obtained by melt-kneading and extrusion molding at a temperature of 5-275°C (from the hopper side) and a goo temperature of 265°C. After drying the pellets at 120°C for 15 hours.

Injection molding machine with cylinder temperature maintained at 250-275-275-275°C (manufactured by Nissei Jushi Kogyo ■, F8aoS 1
2ASE) by changing the temperature of the whole mold extensively, and
.

A flat test piece with a width of 3 mm and a thickness of 3 mm was molded.

The surface gloss of the obtained test piece was measured using a gloss needle (manufactured by Suga Test Instruments,
Measurement was performed using a digital variable angle gloss meter (model UGV-50). The results are shown in Table 2.

Example 11 Evaluation was carried out in the same manner as in Example 10, except that talc (Micron Why 5008, manufactured by Hayashi Kasei) was used instead of phlogopite. The results are shown in Table 2.90 Comparative Example 5 Evaluation was carried out in the same manner as in Example 10 except that PET obtained in Comparative Example 1 was used as the copolymerized polyester p in Example 10. The results are shown in Table 2.

Comparative Example 6 Evaluation was carried out in the same manner as in Example 11 except that the PET obtained in Comparative Example 1 was used instead of the copolymerized polyester. The results are shown in Table 2.

As is clear from Table 2, when the copolymerized polyester of the present invention was used, crystallization proceeded sufficiently even at low mold temperatures, giving molded products with extremely high gloss.

On the other hand, when PET is used, a glossy molded product cannot be obtained at a mold temperature of 120° C. or lower.

The gloss level showed only a low value.

〔Effect of the invention〕

According to the present invention, the copolymerized polyester has improved brittleness, which is a drawback of conventional PET, without impairing its characteristics of high melting point and high rigidity, has toughness, and has improved crystallinity at low temperatures. is obtained.

Patent applicant: RiRashi Co., Ltd.

Claims (1)

[Scope of Claims] 1. A polyester consisting of an aromatic dicarboxylic acid component (a) mainly consisting of terephthalic acid and a glycol component (b) mainly consisting of ethylene glycol, containing at least two functional groups selected from carboxylic acids or alcohols.
0.01 to 8 mol% of polyfunctional component c having an alkali metal base of carboxylic acid to component a. A copolymerized polyester having excellent toughness and crystallinity, which contains 1 to 20% by weight of the polyester consisting of the components and 0.2 to 5 mol% of the aliphatic dicarboxylic acid component e having 9 or more carbon atoms based on the component a. 2. At least 90 of the aromatic dicarboxylic acid component a
The copolymerized polyester according to claim 1, wherein mol% of the glycol component b is a terephthalic acid component, and at least 90 mol% of the glycol component b is an ethylene glycol component. 3. The copolymerized polyester according to claim 1 or 2, wherein the polyfunctional component c having an alkali metal base of a carboxylic acid is an alkali metal salt of a dioxymonocarboxylic acid. 4. The copolymerized polyester according to claim 1 or 2, wherein the polyfunctional component c having an alkali metal base of carboxylic acid is an alkali metal salt of dimethylolpropionic acid. 5. The copolymerized polyester according to any one of claims 1 to 4, wherein the proportion of the polyfunctional component c having an alkali metal base of carboxylic acid to the component a is 0.1 to 4 mol%. 6. The copolymerized polyester according to any one of claims 1 to 5, wherein the proportion of the polyalkylene glycol component d to the polyester consisting of both components a and b is 3 to 15% by weight. 7. The copolymerized polyester according to any one of claims 1 to 6, which has an intrinsic viscosity of 0.4 to 1.5. 8. The copolymerized polyester according to any one of claims 1 to 7, wherein the polyalkylene glycol component d is polytetramethylene glycol and/or polyethylene glycol.