Polyethylene terephthalate resin compositions

The present invention relates to polyethylene terephthalate resins useful in molding applications. More particularly, it relates to polyethylene terephthalate resins containing an inorganic filler or reinforcing material.

.11 is advantageous to increase the mechanical strength of molded articles formed of a polyethylene terephthalate resin by using a reinforcing material, such as glass fibers, asbestos fibers or other fibrous mineral materials with an agent coupling, in the resin.

In addition, it is sometimes sufficient to simply increase the modulus by using a filler, such as beads or a mineral material of low aspect ratio, in the resin. However, until now, it has been necessary to use very high mold temperatures, of the order of 150 ° C., in order to obtain articles molded from such reinforced or filled resins having a shiny surface and no not having a rough texture. If these high mold temperatures were not used, the molded articles had a rough surface with poor gloss. It is believed that the rate of crystallization of polyethylene terephthalate is too small below about 130 ° C to give a molded article having good surface characteristics.

Although good surface characteristics can be obtained at molding temperatures of 130 ° C or higher, the use of such temperatures is not convenient in the molding field, since most molds are heated with l and reach temperatures of only around 85-110 ° C.

OJ A small number of molding devices use * heating means such as oil to reach temperatures higher than 85-110 ° C, but these devices are generally inconvenient to use and furthermore they do not they generally do not reach such temperatures or they reach them irregularly due to insufficient coring. Because of these heating problems, it has been found industrially unattractive to use these. high temperature molding devices with reinforced or filled polyethylene terephthalate resins.

It is desirable to obtain a reinforced or charged polyethylene terephthalate resin which can be molded to "

mold temperatures below about 110 ° C to give a molded article having a smooth and shiny surface * The polyethylene terephthalate resins reinforced or loaded according to the present invention make it possible to achieve this result by incorporating 1) a sodium or potassium salt of a selected hydrocarbon acid or a sodium or potassium salt of a selected organic polymer containing pendant carboxyl groups and 2) an organic compound of molecular mass^re P^had high chosen from esters, ketones, sulfones, sulfoxides, nitriles and amides.

More particularly if the resins according to the present invention are compositions essentially comprising:

At M. polyethylene terephthalate having an inherent viscosity of at least about 0.4;

B) between approximately 10% and approximately 60% by weight of a filler or reinforcing material; characterized in that they further comprise:

C) a material chosen from a sodium or potassium salt of a hydrocarbon acid containing between approximately 7 25 carbon atoms, and a sodium or potassium salt of an organic polymer which contains pendant carboxyl groups, this material being present in an amount sufficient to give an AHg / 4Ή ratio of less than 0.25 to a mixture of the constituents A, B and C;

D) a compound present in an amount sufficient to give a temperature Tpk at least 4 ° C lower than the temperature Tpk of a mixture of the constituents A, B and C, this compound being chosen from

a) organic esters chosen from the product of an aromatic carboxylic acid of 7 to 11 carbon atoms containing at least 1 carboxyl group per aromatic ring and of an alcohol chosen from those of the formula (HOCE ^^ R * where x is 1, 2 or 3 and E 'is a hydrocarbon radical from 2 to. 15 carbon atoms (preferably 2 to 10 carbon atoms) and those of the formula EO- ^ R'O ^ yR 'where y is a cardinal number, between 1 and 15 and preferably between 2 and 8, R is a hydrocarbon radical of 2 to 15 carbon atoms (preferably 2 to 8 carbon atoms) and R′ -H or a hydrocarbon radical of 2 to 20 carbon atoms (preferably 2 to 12 carbon atoms carbon);

b) organic ketones of the formula

CPR;

c) organic sulfones of the formula RSOOR;

d) organic sulfoxides of the formula RgSO;

e) organic nitriles of the formula ROT; and

f) organic amides of the formula RCNR'R or

RSO & R'R where, in formulas b) to f), each R may be identical to the others or different from any other R and is * a hydrocarbon radical of 1 to 25 carbon atoms, while in formulas from f), R 'is hydrogen or a hydrocarbon radical of 1 to 25 carbon atoms.

The polyethylene terephthalate used herein is a polyethylene terephthalate which has an inherent viscosity of at least 0.4. Polyethylene terephthalate preferably has an upper limit on the inherent density of., J, 2, approximately, a solution of 0.5 g of polyethylene terepntate in the liquid. The inherent viscosity is measured on / a mixture in a volume ratio of 3: 1 cMethylene chloride and trifluoroacetic acid at 50 ° C. Polyethylene terephthalate may contain minor amounts of other comonomers such as diethylene glycol or glutaric acid.

The filler or reinforcing material used here includes glass fibers, glass beads, aluminum silicate, asbestos, mica, etc., or combinations of these materials, such as for example a mixture of mica and fiberglass.

The materials present in sufficient quantity so that the compositions according to the invention have a ratio of less than 0.25 (component 0 defined above) include the sodium or potassium salts of carbo55 xylic hydrocarbon acids containing between 7 and 25 carbon atoms, preferably more than 12 carbon atoms. Representative examples of these acids (which are fatty acids) are stearic, pelargonic and behenic acids.

These materials also include the sodium or potassium salts of organic polymers containing carboxyl groups, such as copolymers of olefins and acrylic or methacrylic acid, or copolymers of aromatic olefins and maleic anhydride. Preferably, these materials are the sodium or potassium salt of stearic acid;

the sodium or potassium salt of ethylene / methacrylic acid copolymers (including both fully and partially neutralized salts, for example at least about 50% neutralized), the sodium salt of styrene / maleic anhydride copolymers (including salts both completely and partially neutralized, e.g. at least about 50% neutralized) and sodium versatate. In the copolymers listed above, the olefin or aromatic olefin portion usually constitutes from 50 to 98% of the weight of the copolymer

- and preferably from 80 to 98%. A particularly preferred material is the sodium salt of an ethylene / methacrylic acid copolymer. The copolymers can be prepared by conventional high pressure polymerization techniques.

Preferred organic esters of the constituent D specified above are those in which the aromatic carboxylic acids are hydrocarbon acids containing from 1 to 5 carboxyl groups and the alcohols are aliphatic.

In other words, the R groups in the alcohols are alkyl or alkylene groups depending on the particular R group. Preferably also when the carboxylic acids contain two or more carboxyl groups, the carboxyl groups have all reacted to form ester bonds (COO), that is to say that there are no more free carboxyl groups present in ester. Preferably, all the hydroxyl groups of the alcohols will also have reacted to form ester bonds (COO), that is to say that there are no more free hydroxyl groups. present in the ester.

A preferred class of esters consists of those in which the acid is benzoic acid and the alcohol is (HOCB ^^ - R 'where R' is an alkylene group of 4 to 6 carbon atoms (preferably the neopentyl glycol) or H0 (R09_thereH where R is an ethylene or propylene group and is 2 or 5 there.

Preferred compounds from ketones, sulfones, sulfoxides, nitriles and amides are those in

which R groups in the formulas given above for these organic compounds are aryl groups of 6 to 10 carbon atoms or alkyl groups of 1 to 10 carbon atoms.

Specific compounds meeting these definitions are listed below [the number in parentheses after each compound is the number of ° C whose temperature Tph is lowered by 1% by weight of the compound present (relative to polyethylene terephthalate) in the reinforced or filled polyethylene terephatalate]: neopentyl glycol dibenzoate (2.0), triethylene glycol dibenzoate (3.0), diethylene glycol dibenzoate (3.2), dipropylene glycol dibenzoate (3.0), tris-2-ethyl trimellitate hexyl (2.5), phenyl benzoate (3.0), trimethylolethane tribenzoate (1.53), dioctyl phthalate (1.3), diisodecyl phthalate (0.8), benzophenone (2.5), 4-fluorobenzophenone (1.9), diphenyl sulfone (2.8), N-ethyl-o, p-toluene sulfonamide (2.3), tolyl sulfoxide (2.6), lauryl nitrile (2.9), and erucyl nitrile (2,3).

Components (C) and (D) in the compositions according to the present invention help to obtain molded articles with a large surface luster at molding temperatures below 110 ° C by increasing the rate of crystallization of polyethylene terephthalate. Component (O) is believed to assist primarily in increasing the rate of crystallization while component (D) is believed to primarily increase the mobility of polyethylene terephthalate in its supercooled state by reducing the viscosity in this state. Both are necessary to achieve the high sheen observed on articles molded from the composition.

The amount of component (c) present in the compositions according to the present invention is an amount which will give a ratio ÄH-g / ΔH_vs of the composition less than 0.25. To determine the AHjj / ÛH ratio, the polyethylene terephthalate is molded at 70 ° C. into bars 1.6 mm thick. The bars are heated and between 95 ° W and 120 ° G a heat release (called ÙHg ·) is recorded on a differential scanning calorimeter cell (DSO) mounted on a Du Pont 900 differential thermal analysis device (ATD) . The bar is heated to 290 ° C (which is above its melting point) and the molten sample is cooled to 10 ° C / minute. Another heat release between about 200 and 220 ° C (called HA) is the heat release recorded when the sample is frozen. We found that the ZiH report_w/.OiH is a convenient method to measure the xi c degree of crystallization.

The temperature Tpk of the composition according to the present invention is the temperature at which heat is released very quickly during the heating cycle specified in the preceding paragraph. As specified above, the amount of component (D) present in the composition according to the present invention is an amount which lowers the temperature Tpk of the composition by at least 4 ° C. compared to that of an identical composition which does not contains no constituent (D).

_AT The upper limits of the quantities of the constituents

C and D are not critical. However, physical properties can be adversely affected as the amounts increase. In general, the upper limit of the amount used for any component will usually be about 12% by. weight relative to the weight of polyethylene tere20 phthalate, while the lower limit will be approximately 1%. For the preferred constituent (C), namely salts of ethylene / methacrylic acid copolymer, the upper limit concerning the amount present will be approximately 12% by weight relative to the weight of polyethylene terephthalate while the lower limit will be about 0.5%, but preferably use an amount between 1 and 5% ·

In addition to the constituents specified above, the compositions according to the present invention may contain additives commonly used with polyester resins, such as dyes, release agents, antioxidants, ultraviolet stabilizers , flame retardants, etc. Additives which improve physical properties, such as tensile strength and elongation, can also be used; such additives are, for example, epoxy compounds (for example an epoxy compound formed from bisphenol-A and epichlorohydrin) present in proportions of 0.1 to 1.5% θη weight relative to the weight of the composition.

The compositions according to the present invention are prepared by mixing the constituents together by any convenient means, either temperature or pressure is of critical importance. For example, the polyethylene terephthalate can be dry blended in any suitable mixer or barrel with the components B, C and D and the mixture is extruded in the molten state. The extruded product can be cut and mixed with a reinforcing agent and then this mixture is extruded in the molten state. More conveniently, all of the components can be dry blended in any suitable mixer or barrel and the mixture is then extruded in the molten state.

The following nonlimiting examples describe the best mode of implementing the invention. The ratio and the temperature Tpk are determined as described above, while the brightness of a molded sample is measured with a Gardner apparatus (model GG-9095) set at a chosen angle in degrees specified in the examples.

EXAMPLE 1:

A dry mixture of 92.57% by weight of dry polyethylene terephthalate having an inherent viscosity of 0.5 to approximately, 1% by weight of sodium stearate, 5% θη weight of benzophenone and 1.43% by Weight of H-stearyl erucamide (a mold release additive) is extruded through a 28 mm twin screw extruder at a melt temperature of approximately 264 ° C. The cut strands from the extruded melt are dried at about 110 ° 0 for 16 hours in a vacuum oven. The dried cut strands are dry mixed with enough OCE 419AA glass fiber (cut to 4.8 mm) to make 30% by weight of glass fiber and the mixture is extruded through a single extruder screw and two-stage at a melt temperature of about 264 ° C. The ratio is 0.06 and the temperature Tpk is 12 ° C lower than that of the same composition but without the benzophenone present. The extruded strands are cooled and cut and then dried at about 110 ° G for 16 hours in a vacuum oven. The dried cut strands are molded in an injection molding machine of 177 cm ^ at about 290 ° C, with a fast piston, a duration of the injection stroke of 20 seconds, a closing of the mold of 20 seconds and a temperature 95 ° G cavity. The shine of the molded article is very good. By carrying out the determination with a Gardner apparatus (model GG-9095) adjusted at an angle of 20 degrees, there is a brightness of 23. At a cavity temperature of 70 ° C., the brightness measured in the same way is 5 "Examples 2 to 15 and comparisons A to E

5 'In the examples and the comparisons which follow, the procedure generally used for preparing the compositions according to the present invention is as follows:

A dry polyethylene terephthalate having an inherent viscosity of about 0.5-0.85 is mixed manually with glass free as specified in the tables below and with an ethylene / methacrylic acid copolymer (85/15 by weight) which has been neutralized to 60% with sodium (which is component G defined here) in an amount specified in the tables, and with component D specified in the tables. Other additives may be present to increase the mechanical strength of the molded articles or to improve the mold release properties. These additives, if present, are specified in the tables.

The resulting mixture is then extruded through a two-stage 5.08 cm single screw extruder at a melt temperature of 285 ° C and under a vacuum of 71.1 cm. The extruded strand is cut and the resulting resin pellets are dried at 110 ° C in a vacuum oven for about 16 hours. The resin pellets are then molded into cups having 9.2 cm in height, 7.5 cm in diameter at the top, 5.5 cm in diameter at the bottom and having a wall thickness of 0.19 cm. The temperature of the melt in the molding machine is 295 ° C, while the surface temperature of the mold is 85 ° C. The cycle times jq and the ejection pressures are specified in the tables.

The brightness is measured at an angle of 60 ° by the Gardner instrument (model GG-9095) several times for each sample. The sheen is measured around the circumference of the goblet at a third of the height from the top. The pressure required to remove the cup is also measured by noting the air pressure required to operate the ejector. The tables show the strongest and weakest results obtained in all the brightness measurements made on the sample. The tables also indicate the surface visual appearance of the molded cups.

In the tables, the. percentages of components C and D are based on the weight of polyethylene terephthalate used. The percentages of filler or reinforcing agent and of the other additives are based on the weight of the mixture to be extruded.

In the tables, constituent D is identified by a single letter. The letters represent the particular constituent D as follows:

A - neopentyl glycol dibenzoate

B - Lauryl nitrile

G - Dipropylene glycol dibenzoate

D - Erucyl nitrile

E -Benzophenone

P - Trioctyl trimellitate

G - Diphenyl sulfone

H - N-ethyl-o, p-toluene sulfonamide

I - Diethylene glycol dibenzeate

The reinforcing filler or material used is identified in the tables by two letters. The letters represent particular subjects as follows:

AA - Fiberglass OOP 277B

BB - Glitter of mica (Suzorite A60)

CC - Fiberglass OOF 4-19AA

The other additives are identified by a letter as follows ï

X - Epoxy resin formed from bisphenol-A and epichlorohydrin

Y - tetrakis [methylene (3, 5 “é.i ~ tert-bu.tyl-4 + -hydroxy30 hydrocinnamate)] methane —i _Λ _ï _ï

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<td>Η</td><td>Φ '1—1</td><td>Φ 'Η</td><td>Φ '</td><td>φ "</td><td>Φ '</td><td>Φ</td><td>Φ</td><td>Φ '</td><td>Φ '</td><td>Φ '</td><td>Φ '</td><td> 0)'</td>

<td>and</td><td>CQ Η ·</td><td>03 Η</td><td> 03</td><td> 03</td><td> 03</td><td></td><td></td><td> 03</td><td> 03</td><td> 03</td><td> 03</td><td>τα</td>

<td>Ο</td><td> 03</td><td> 03</td><td></td><td></td><td></td><td>"Ö</td><td>σ</td><td></td><td></td><td></td><td></td><td></td>

<td>Ρ</td><td>Η 03</td><td>Η 03</td><td>Ρ</td><td>Η</td><td>Η</td><td> 03</td><td> 03</td><td>Ρ</td><td>Ρ</td><td>Ρ</td><td>Ρ</td><td>Ρ</td>

<td>and</td><td>Η · Φ</td><td>Η · Φ</td><td>Η ·</td><td>Η ·</td><td>Η ·</td><td> 4</td><td> 4</td><td>Ρ</td><td>Ρ</td><td>ρ</td><td>Ρ</td><td>Ρ</td>

<td></td><td> 03</td><td> 03</td><td> 03</td><td> 03</td><td> 03</td><td>and</td><td>and</td><td> 03</td><td> 03</td><td> 03</td><td>εο</td><td> 03</td>

<td></td><td> 03</td><td> 03</td><td> 03</td><td> 03</td><td> 03</td><td>Ο</td><td>Ο</td><td> 03</td><td>at</td><td>you</td><td> 03</td><td> 03</td>

<td></td><td>Φ</td><td>Φ</td><td>Φ</td><td>Φ</td><td>Φ</td><td>Ρ</td><td>Ρ</td><td>Φ</td><td>φ</td><td>φ</td><td>φ</td><td>Φ</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td>and</td><td>and</td><td></td><td></td><td></td><td></td><td></td>

$ (D £

t&gt; £&gt;

.W Jh o W en \

ο e

Η3 »Ö

ΡΤ ο ϋ

313

Ρ (0% φ φ

Ρ h) -4 φο Φ ο. ω φ τα

Ο ρ · ΓΌ and Ο

Ρ 'ϊ = 5 Ο Ρ &lt;i &lt;Ρ · Μ

0) Φ ο ΗΗ Η φ φ g ta ib ο and 4 RP

Ό 0)

CFP? I-¹ë Φ ω Φ '' Ct HjO 03 O Pet 4 g and CO σ '4 H&gt; p! 03 and H · σ '

H Φ {c * geo "H&gt; Φ 03 OO and Φ

P g Φ

O

P

H ·

H

H

Φ "

Φ

Ο&gt;

bd §

ΓΌ

In the following comparisons, the same general procedure is used as in the previous examples and the tables which follow contain the same column headings as the tables above. The component killing K is varied in the comparisons and the component C used is indicated

Example

AT

<td colspan="4">for each comparison.</td>

<td rowspan="3">Quantity of constituent c ")</td><td colspan="3">TABLE 3</td>

<td rowspan="2">Constituent D and quantity (%)</td><td colspan="2">Filler and Other Additives</td>

<td>amount (%)</td><td>present (%)</td>

<td>nothingness</td><td>Α (5Λ)</td><td>AA (25)</td><td>X (0.6)</td>

B c

Of

E

Y (0.3) Talc (0.7)

<td>material used in examples 2-15 (5 * 5)</td><td>nothingness</td><td> 00(25)</td><td>N-stearyl erucamide (Release agent) (0.9)</td>

<td>nothingness</td><td>E (10)</td><td> 00(25)</td><td>nothingness</td>

<td>sodium stearate (0.5)</td><td>nothingness</td><td>CC (25)</td><td>Methyl stearate (0.53)</td>

<td>Material used in Examples 2-15 (5.5)</td><td>A (1</td><td>CC (25)</td><td>nothingness</td>

<td>Material used in Examples 2-15 (0.35) *</td><td>E (5.0)</td><td>CC (25)</td><td>nothingness</td>

^xThe quantity is too small

F

Ex.

/ SHjj / ^ΔΗο

TABLE $ (continued)

Duration Pressure Brightness in Aspect state

Tpk of gross molding ejection of the cycle (kg / cm2) (lower surface value / more molded high value)

<td>AT</td><td>About. 0.4</td><td>Not measured</td><td> 10/15</td><td> 2150</td><td> 29/38</td><td>very rough</td>

<td>B</td><td>Not measured</td><td> 0</td><td> 10/30</td><td> 1440</td><td> 13/23</td><td>surface mo dérément rough</td>

<td>G</td><td>about 0.5</td><td>Not measured</td><td> 10/30</td><td>You need a spray</td><td> 36/4?</td><td>area rough</td>

on the mold

<td>D</td><td>Not measured</td><td>Not measured</td><td> 10/25</td><td> 1590</td><td> 15/23</td><td>area very rough</td>

<td>E</td><td> 0,16</td><td> -3</td><td> 10/30</td><td> 1790</td><td> 9/18</td><td>smooth to moderately rough surface</td>

<td>E</td><td>about 0.45</td><td>Not measured</td><td colspan="3">Adhesion / spraying 5/8 No established molding cycle</td><td>area very rough</td>

<td></td><td></td><td>Although</td><td colspan="2">the shards for</td><td colspan="2">some of the experiences</td>

<td>u</td><td>Board</td><td>3 be</td><td>of the same</td><td colspan="2">order that the shards</td><td>found</td>

for some of the examples in Table 2, the surface roughness is not acceptable in the comparison experiments.