JPH0649336A - Copolyester composition - Google Patents

Abstract

PURPOSE:To obtain a copolyester composition having excellent mechanical characteristics, moldability and abrasion resistance and good transparency by mixing a copolyester consisting of two kinds of specified structural units with a specified amount of fine organic particles having a specified diameter. CONSTITUTION:A copolyester consisting of units of formulas I and II is mixed with fine organic particles having a mean particle diameter of 0.01-5.0mum in an amount of 0.01-5.0wt.% based on the polyester. In the formulas, Ar1, Ar2, Ar3 and Ar4 are each independently a divalent aromatic residue; R1 and R2 are each independently a 1-12C linear, branched or cyclic divalent aliphatic group; and x+y=1, provided that 0.02<=x<=0.70. Fibers, films, molding, etc., made from this composition are excellent in handleability even if they are fine or thin. Even when used in contact with metal, this composition scarcely suffers scraping.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to mechanical properties, wear resistance,
The present invention also relates to a polyester composition having excellent transparency.

[0002]

2. Description of the Related Art In recent years, miniaturization in the field of electric and electronic equipment,
With the progress of weight reduction, not only downsizing of materials to be used but also simplification, shortening of process, speeding up, heat resistance, high strength, and abrasion resistance are required. Aromatic polyesters typified by polyethylene terephthalate have been used in these fields, but they have limited mechanical properties and heat resistance, and in the case of direct contact with metal, wear resistance is low. Weakly scraped or scratched,
It has become difficult to satisfy the required characteristics. Therefore, for higher heat resistance and higher rigidity, copolymerization of liquid crystal polyester and liquid crystal components (for example, "High-performance aromatic polymer materials" edited by The Polymer Society of Japan (Maruzen)) is also used to improve wear resistance. A particle addition system (for example, Japanese Patent Laid-Open No. 61-60722) is under study.

[0003]

However, although the liquid crystal polymer has relatively high heat resistance and high rigidity among the molten polymers, it has a problem that it is strongly oriented in the flow direction and the strength in the direction perpendicular thereto is lowered. However, the moldability into a film that needs to be biaxially stretched in the machine direction and the width direction was poor. On the other hand, there was a problem that even if an attempt was made to copolymerize a rigid component that contributes to the expression of liquid crystallinity with an aromatic polyester to such an extent that the liquid crystallinity is not expressed, the degree of polymerization does not increase and a polymer having sufficient strength cannot be obtained. . Furthermore, although the wear resistance has been improved by the effect of adding fine particles, it is not yet sufficient.

It is an object of the present invention to provide a copolymerized polyester composition which solves the above problems, is excellent in mechanical properties, moldability and abrasion resistance and has good transparency.

[0005]

The present invention provides units I and II represented by the following formula.

[Chemical 2] (In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ independently represent a divalent aromatic residue, and R ₁ and R ₂ are independently linear or branched having 1 to 12 carbon atoms. Represents a cyclic or cyclic divalent aliphatic, and x and y satisfy the following formulas (1) and (2)) x + y = 1 (1) 0.02 ≦ x ≦ 0.70 ( 2) a copolymerized polyester consisting of
The present invention relates to a copolyester composition characterized by containing organic fine particles of 5.0 μm in an amount of 0.01 to 5.0% by weight based on the copolyester.

Ar ₁ , Ar ₂ , Ar ₃ , Ar of the above units I and II constituting the copolyester of the present invention
Each ₄ independently represents a divalent aromatic residue, preferably an aromatic ring having 6 to 24 carbon atoms. This aromatic ring may be formed not only by one but also by two or more, and hydrogen on the aromatic ring may be substituted with halogen, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a cyano group, a nitro group or the like. May be. When there is one aromatic ring, para or meta structure is preferable,
In the case of two or more, divalent aromatic residues corresponding to these are preferable, for example, the following structures are more preferable.

[0007]

[Chemical 3] (However, the above aromatic ring includes those substituted with halogen, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a cyano group, a nitro group, etc.) More preferably, a para type

[Chemical 4] And so on.

On the other hand, R ₁ and R ₂ independently have 1 to 1 carbon atoms.
It is a linear, branched, or cyclic divalent aliphatic residue having 2 carbon atoms, preferably a linear or branched alkylene group having 2 to 8 carbon atoms, or cycloalkylene having 4 to 10 carbon atoms. Group, a cycloalkylenedialkylene group having 6 to 12 carbon atoms, and more preferably

[Chemical 5] And the like, in _{particular, - (CH 2) 2 -} , - (C
H _{2) 4} - are preferred.

When the proportion of the above unit I constituting the copolyester of the present invention is x, the proportion of II is y, and x + y = 1, x is in the range of 0.02≤x≤0.70. It is necessary to be. When x <0.02, the effect of the present invention is not remarkable, and the mechanical properties and abrasion resistance are not sufficiently improved, and when x> 0.70, liquid crystal properties start to develop and strongly oriented in one direction to a film or the like. May have poor moldability. Preferably, 0.04 ≦ x ≦ 0.60, and more preferably 0.05 ≦ x ≦ 0.50.

Next, a method for producing the copolyester of the present invention will be described.

First, dicarboxylic acid (III) which is one of the polyester monomers of unit I

[Chemical 6] (Wherein Ar ₁ , Ar ₂ and Ar ₃ are the same as defined above), or the ester derivative thereof is

[Chemical 7] (Wherein Ar ₁ and Ar ₃ are the same as defined above), for example, methyl of hydroxycarboxylic acid such as p-hydroxybenzoic acid, m-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid. One or more of ester or ethyl ester derivatives,

[Chemical 8] (Wherein Ar ₂ is the same as defined above), for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4 , 4'-biphenylenedicarboxylic acid, 3,4'-biphenylenedicarboxylic acid, 3,3'-biphenylenedicarboxylic acid, or one or more of these aromatic ring hydrogens substituted with halogen, alkyl group, etc. It can be obtained by carrying out a deacetic acid reaction using acetic acid. It can also be obtained by reacting the dichloride of the above-mentioned dicarboxylic acid with the above-mentioned hydroxycarboxylic acid or its ester derivative in a solvent in the presence of a dehydrochlorination agent such as triethylamine.

Also, the dicarboxylic acid monomer (IV) of unit II

[Chemical 9] (Wherein Ar ₄ is as defined above), terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid,
1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4′-biphenylenedicarboxylic acid,
Preference is given to 3,4′-biphenylenedicarboxylic acid, 3,3′-biphenylenedicarboxylic acid, those obtained by substituting the hydrogen of the aromatic ring with halogen, an alkyl group and the like, and alkyl esters thereof.

These dicarboxylic acid monomers (III),
(IV) and a diol, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5
By polymerizing with one or more alkylene glycols such as pentanediol, 1,6-hexanediol and cyclohexanedimethanol by known methods such as solution polycondensation method, melt polycondensation method and solid phase polymerization method. A copolyester having the units I and II of the present invention can be obtained. The total diol and the total dicarboxylic acid monomer (III + IV) are preferably equimolar, but in practice, the number of moles of the diol may be 90 to 110 mol% with respect to the total number of dicarboxylic acid monomers, More preferably, it is 95 to 105 mol%. Further, the dicarboxylic acid monomer III needs to be 2 to 70 mol% with respect to the total dicarboxylic acid monomer.

As a particularly preferred method, a predetermined ratio of dicarboxylic acid which is a source of the above units I and II and /
Or an alkyl ester of a dicarboxylic acid and an alkylene glycol, preferably in an inert atmosphere in the presence of a suitable catalyst such as lithium acetate, calcium acetate, magnesium acetate, manganese acetate, cobalt acetate, tetraalkyl titanate, etc. An esterification reaction or transesterification reaction is carried out at 270 ° C. while removing water or alcohol produced to obtain an oligomer,
Further subsequently, in the presence of a suitable polymerization catalyst such as antimony compound, germanium compound, titanium compound, silicon compound, more specifically antimony trioxide, germanium dioxide, tetraalkyl titanate,
A method of polymerizing at 200 to 320 ° C. under reduced pressure can be mentioned.
Further, the dicarboxylic acid and / or the alkyl ester of the dicarboxylic acid which is the source of the units I and II are separately esterified or transesterified to synthesize an oligomer, which is then mixed at a predetermined ratio before polymerization. You may take the method of doing.

The copolyester thus obtained preferably has an intrinsic viscosity (o-chlorophenol, measured at 25 ° C.) of 0.4 dl / g or more. If it is less than this, the mechanical strength may not be sufficient and molding into a film or the like may be difficult. Solid phase polymerization or the like may be performed to adjust the intrinsic viscosity to this range. More preferably, the intrinsic viscosity is 0.5 to 5.0 dl / g.

The particles contained in the particle-containing copolyester composition of the present invention have an average particle diameter of 0.01 to 5.0.
It is necessary that the organic fine particles have a size of μm. 0.01μ
When it is less than m, it is not possible to sufficiently exhibit the background reinforcing effect of the present invention for improving wear resistance, and 5.0 μ
If it exceeds m, the transparency deteriorates. Preferably 0.02
To 4.0 μm, more preferably 0.02 to 3.0 μm
Is. The addition amount was 0.
It is necessary to be 01 to 5.0% by weight. 0.01
If it is less than 5% by weight, the background reinforcing effect is not sufficient, and if it exceeds 5.0% by weight, the surface becomes rough and wear resistance is deteriorated. It is preferably 0.05 to 4.0% by weight, more preferably 0.08 to 3.5% by weight.

Further, as the organic fine particles, cross-linked polymer particles are preferable, considering that the composition is molded at a high temperature. As the crosslinked polymer particles, generally, a monovinyl compound (A) having only one aliphatic unsaturated bond in the molecule, and a compound having two or more aliphatic unsaturated bonds in the molecule as a crosslinking agent ( Examples thereof include, but are not limited to, copolymers with B) and any insoluble or infusible crosslinked polymer particles may be used. Examples of the compound (A) include aromatic monovinyl compounds such as styrene, α-methylstyrene, fluorostyrene and vinylpyrine, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, butyl acrylate, 2-ethylhexyl acrylate and methyl acrylate. -Acrylic acid ester monomers such as hydroxyethyl acrylate, glycidyl acrylate, N, N'-dimethylaminoethyl acrylate, butyl methacrylate,
Methacrylic acid ester monomers such as 2-ethylhexyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, N, N'-dimethylaminomethacrylate, acrylic acid, methacrylic acid maleic acid, itaconic acid mono or Dicarboxylic acids and acid anhydrides of dicarboxylic acids, and amide monomers such as acrylamide and methacrylamide can be used. Among them, styrene, α-
Methylstyrene and p-methylstyrene are preferred. Examples of the compound (B) include divinylbenzene compound, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, and 1,3. -Polyvalent acrylates and methacrylates such as butylene glycol dimethacrylate. Preferred are divinylbenzene, ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate. These compounds (A),
Each of (B) can be used as a mixture of two or more kinds.

Preferred examples of the composition of the crosslinked polymer particles of the present invention include styrene-divinylbenzene copolymer, styrene-acrylonitrile-divinylbenzene copolymer, styrene-methylmethacrylate-divinylbenzene copolymer and the like. To be Among them, a styrene-divinylbenzene copolymer is particularly preferable in terms of heat resistance.

The organic fine particles used in the present invention preferably have a spherical particle shape and a uniform particle size distribution in terms of transparency and surface uniformity. That is, it is preferable that the volume shape factor is 0.35 to 0.52, and further 0.45.
The above is preferable. (However, the volume shape factor f is expressed by the following equation: f = V / D ³ , where V is the particle volume (μm ³ ), and D is the maximum diameter (μ of the particle on the projection plane).
m). ) As the crosslinked polymer particles of the present invention, those obtained by a known method can be used. As a known production method, there is a method such as the following by emulsion polymerization. (1) Soap-free polymerization method, that is, a method of using no emulsifier or using an extremely small amount of emulsifier. (2) A method in which polymer particles are added to the polymerization system prior to emulsion polymerization and then emulsion polymerization is performed. (3) A core-shell polymerization method in which a part of the monomer components is emulsion polymerized and the remaining monomers are polymerized in the polymerization system. (4) JP-A-54-97582, or JP-A-5-
The method according to Eugelstat et al., Which is disclosed in Japanese Patent Publication No. 4-126288. (5) A polymerization method which does not use a swelling aid in the method of (4). Among the above methods, the methods (3) and (4) are particularly preferable because spherical crosslinked polymer particles having a uniform particle size distribution can be obtained.

Next, a method of incorporating organic fine particles into the copolyester of the present invention, a method of polymerizing the polymer in the presence of particles, a method of using a twin-screw extruder, and a small amount There is a method of using a mixing roll. For example, ethylene glycol, which is a type of monomer, is dispersed in the form of a slurry and mixed with other diol components and then polymerized with a predetermined dicarboxylic acid component, or ethylene glycol or water slurry is mixed with a copolyester, and a vent method is used. There is a method of kneading using a twin screw extruder. As a method for adjusting the content of particles, a high-concentration master is prepared by the above method, and the content of particles is adjusted by diluting it with a thermoplastic polymer that does not substantially contain particles during film formation. The method of doing is effective.

When a film is produced using the copolyester composition of the present invention, a conventionally known film production method can be applied. For example, after drying the pelletized copolyester composition as needed, it is supplied to a known melt extruder and extruded into a sheet form from a slit die at a melting point of the polymer or more and a decomposition point or less, and a casting roll. Cool on top to make an unstretched film. Next, this unstretched film is biaxially stretched and biaxially oriented. As a stretching method, a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used. The stretching area ratio (the ratio of the stretching ratio in the machine direction and the stretching ratio in the transverse direction) is preferably 2.0 to 30.0 times, and the stretching temperature varies depending on the type of polymer and cannot be generally stated, but it is 50 to 200. C is preferred. Further, this stretched film may be heat treated, and the heat treatment temperature is preferably 150 to 250 ° C. and the heat treatment time is preferably 0.5 to 120 seconds.

The film haze of the film obtained as described above is preferably 1.0% or less, more preferably 0.7% or less. The edge tear resistance in at least one direction is preferably 0.01 kg / μm, and 0.1 kg / μm
Is more preferable, and still more preferably 0.3 kg / μm or more.

[0023]

EXAMPLES Next, the embodiments of the present invention will be explained based on examples, but the invention is not limited thereto. In addition, the measuring method of the characteristic in an Example is as follows.

(1) Young's Modulus A Young's modulus was measured with a TRS type tensile tester under conditions of a width of 10 mm, a length of 50 mm and a pulling speed of 300 mm / min.

(2) Abrasion resistance and dynamic friction coefficient Abrasion resistance is obtained by molding the obtained copolyester into a film and fixing a tape-shaped roll slit in a narrow width to a stainless steel (SUS-304) guide roll. Rubbing was carried out at a high speed with tension (traveling speed of 1000 m / min) for 1 hour, and ranked according to the amount of white powder generated on the surface of the guide roll. Class A: No white powder is generated B Class: White powder is generated C Class: White powder is often generated Also, the coefficient of dynamic friction is measured from the tension on both sides sandwiching the metal guide when the film is running, and 0.25 or less is judged to be good slipperiness. did.

(3) Film haze Measured according to ASTM-D1003-52.

(4) Edge Tear Resistance The resistance was measured according to JIS-C-2318 and converted per 1 μm of thickness.

(5) Average particle size of particles A particle slurry was prepared and measured using a centrifugal sedimentation particle size analyzer (CAPA500 manufactured by Horiba, Ltd.).

(6) Intrinsic viscosity O-chlorophenol was used as a solvent and measured at 25 ° C.

Reference Example 1 Production of bis (p-methoxycarbonylphenyl) terephthalate (BMT) 2.2 mol of methyl p-hydroxybenzoate (p-MHB) and acetic anhydride 2. 1 mol of terephthalic acid (TPA). 5 mol was charged into a reaction tank equipped with a nitrogen introduction tube, a thermometer, and a stirrer, and gradually heated under nitrogen while stirring,
The temperature was raised to 250 ° C. in 5 hours. Acetic acid started to flow out at around 150 ° C, and when it reached 250 ° C, the system became transparent. After further holding at 250 ° C. for 30 minutes, the reaction was completed and the mixture was filtered through a 400-mesh wire net. The obtained reaction product was cooled, pulverized into powder, washed twice with acetone, and dried under reduced pressure. When analyzed by NMR, it was confirmed that the structure was as shown in Table 1, and it was found that the reaction occurred almost quantitatively and BMT was obtained.

[0031]

[Table 1] Reference Examples 2 to 6 In Reference Example 1, TPA and p-MHB were replaced with the raw materials shown in Table 1, respectively, and the same conditions were used.
It was confirmed by NMR that the obtained product had the structure shown in Table 1.

Example 1 First, 90 mol% of dimethyl terephthalate (DMT) as a compound represented by the raw material formula (IV) of the unit (II), and the formula (III) which is the raw material of the unit (I) produced in Reference Example 1
10% by mole of BMT, which is a compound represented by the formula (1), 0.02% by weight of magnesium acetate as a catalyst in ethylene glycol (EG) in a double amount (that is, 200% by mole) with respect to these carboxylic acid components (based on the obtained polymer). hand)
Was added and heated under a nitrogen stream (up to 230 ° C.) and stirred to carry out a transesterification reaction. After the reaction was completed, 0.03% by weight of antimony trioxide (based on the obtained polymer) and 0.03% by weight of trimethyl phosphate (based on the obtained polymer) were added, and the temperature was raised to 290 ° C in 2 hours. While
After reducing the pressure to 0.5 mmHg in 1.5 hours, and further polymerizing at 290 ° C. and 0.5 mmHg for 1 hour,
I took out the polymer. The intrinsic viscosity was 0.63 g / dl. Using a bent type twin-screw extruder, a water slurry (particle concentration 2% by weight) of styrene-divinylbenzene copolymer particles (volume shape factor 0.50) having an average particle diameter of 0.3 μm was added to the obtained polymer. It was added and mixed so as to be 0.6% by weight (based on the polymer fraction).

Next, at 290 ° C., an extruder was used to extrude from a T die onto a casting drum having a surface temperature of 50 ° C.,
An unstretched film was produced. This unstretched film is
It was stretched 3.5 times in the machine direction at 0 ° C. This stretching was carried out in three stages with the difference in peripheral speed between each pair of rolls. This uniaxially stretched film was stretched 4.0 times in the transverse direction at 95 ° C. using a stenter and then wound into a roll. The properties of the obtained film were excellent as shown in Table 2.

[0034]

[Table 2]

[Table 3] In the table, TPA: terephthalic acid, NDA: 2,6-naphthalenedicarboxylic acid, BBA: biphenyldicarboxylic acid, EG: ethylene glycol, BD: butanediol, St: styrene, DB: divinylbenzene, AN:
It represents acrylonitrile and MM: methyl methacrylate, and was calculated as a value of * 1: (MD + TD) / 2.

Examples 2 to 10 Films obtained in the same manner as in Example 1 except that the raw material of the copolyester, the kind and the amount of the particles were changed as shown in Table 2, all had excellent properties. .

Comparative Examples 1 to 3 The characteristics of the film obtained in the same manner as in Example 1 except that the raw material for the copolyester, the kind and the amount of the particles, etc. are changed as shown in Table 2 are abrasion resistance, It was inadequate such as poor transparency and mechanical properties.

[0037]

The copolymerized polyester composition of the present invention is
Since organic particles are used, generation of voids is suppressed, and not only transparency is good, but also mechanical properties, wear resistance, and moldability are excellent. For example, when it is made into a fiber, a film, a molded product or the like, it is excellent in handleability even when it is thin or thin, and when it comes into contact with metal or the like, abrasion or the like is unlikely to occur. In particular, it is suitable for magnetic recording media, base films such as printer ribbons, capacitors, electric insulating materials such as FPCs, and packaging materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 101: 00) 7242-4J B29K 67:00 B29L 7:00 4F

Claims (1)

[Claims] 1. Units I and II represented by the following formula: (In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ independently represent a divalent aromatic residue, and R ₁ and R ₂ are independently linear or branched having 1 to 12 carbon atoms. Represents a cyclic or cyclic divalent aliphatic, and x and y satisfy the following formulas (1) and (2)) x + y = 1 (1) 0.02 ≦ x ≦ 0.70 ( 2) a copolymerized polyester consisting of
A copolymerized polyester composition comprising organic fine particles of 5.0 μm in an amount of 0.01 to 5.0% by weight based on the copolymerized polyester.