JP2000136294A - Amorphous polyethylene terephthalate resin composition and its calendering processing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an amorphous polyethylene terephthalate resin composition, capable of giving by a calendering method the sheet-like products whose peeling properties from metal rolls are good and which have excellent surface smoothness, by adding a specific acrylic resin, etc., to an amorphous polyethylene terephthalate resin in a specific rate. SOLUTION: This amorphous polyethylene terephthalate resin composition comprises (A) 100 pts.wt. of an amorphous polyethylene terephthalate resin composition and one or both of (B) 0.1-15 pts.wt. of an acrylic acid-based resin having a weight-average mol.wt. of 50,000 to 6,000,000 and (C) 0.05-2 pts.wt. of a tetrafluoroethylene-modified acrylic acid-based resin. At least one of titanium dioxide, talc and calcium carbonate is preferably further added in an amount of 1-20 pts.wt. The component C preferably comprises 100 mol.% of terephthalic acid, 65-80 mol.% of ethylene glycol and 20-35 mol.% of 1,4- cyclohexanedimethanol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-crystalline polyethylene terephthalate resin composition having excellent calenderability and a method for processing the same.

[0002]

2. Description of the Related Art In general, polyethylene terephthalate is
It is used as a packaging material for food and industrial materials, and as a sheet for lamination of buildings, home appliances, automobiles, and the like. The polyethylene terephthalate sheet used for these applications has been conventionally produced by an extrusion molding method and an injection molding method. Extrusion molding and injection molding are methods of adjusting the dice to a specific thickness, then discharging the molten resin and rapidly cooling it from the softening temperature of the resin and pulling it out. It is easy to peel off the sheet from the die, but the uniform discharge of the molten resin is hindered due to defective die adjustment and the effects of resin and additives attached to the die. Different parts often occurred. Sheets with locally different thicknesses are unsuitable for printing, laminating, coating, etc., and may cause holes in the sheets when secondary forming into blister packs, trays, carrier tapes, etc. Had become.

[0003] In contrast to these molding methods, the calendering method is a method of rolling a molten resin with a heated metal roll into a sheet having a specific thickness. It is excellent in that there is no local thickness unevenness due to troubles such as dies due to rolling process, but when using amorphous polyethylene terephthalate resin as the material, the peelability of the sheet from the metal roll is poor. Implementation was difficult.

[0004]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a non-crystalline polyethylene which can obtain a sheet-like material having good releasability of a sheet from a metal roll and excellent surface smoothness by a calendering method. An object of the present invention is to provide a terephthalate sheet resin composition and a processing method thereof.

[0005]

The non-crystalline polyethylene terephthalate resin composition of the present invention has an acrylic resin having a weight-average molecular weight of 50,000 to 6,000,000 per 100 parts by weight of the non-crystalline polyethylene terephthalate resin. It is made by mixing one or both of 15 parts by weight and 0.05 to 2 parts by weight of a 4-fluoroethylene-modified acrylic acid resin, and can easily perform sheet processing by a calendering method that solves the above-mentioned problem.

Further, by adding 1 to 20 parts by weight of at least one of titanium oxide, talc and calcium carbonate to the amorphous polyethylene terephthalate resin composition, calendering processability and surface smoothness of the sheet are obtained. Can be improved. Further, the acrylic acid resin has a weight average molecular weight of 50,000 or more to less than 700,000 and an acrylic acid resin having a weight average molecular weight of 700 to 6,000,000 or less and 0.2 to 10 parts by weight. Part 2
It is preferable to use a combination of these types, whereby the releasability and surface smoothness of the sheet from the metal roll of the calender can be improved.

The calendering of the non-crystalline polyethylene terephthalate resin composition is performed using a calendering machine equipped with four or more metal rolls, and the surface temperature of the final metal roll is adjusted to the glass of the non-crystalline polyethylene terephthalate resin composition. This is achieved by performing in a temperature range of 80 to 160 ° C. higher than the transition temperature. According to this processing method,
The amorphous polyethylene terephthalate resin composition can be processed into a sheet having an arbitrary thickness, and a sheet having a uniform thickness and excellent surface smoothness can be extremely economically produced. The obtained sheet can be used without problems in printing, laminating, and coating, and a molded article without holes due to secondary molding can be obtained.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As the non-crystalline polyethylene terephthalate resin used in the non-crystalline polyethylene terephthalate resin composition of the present invention, terephthalic acid: 100 mol%, ethylene glycol: 30 to 90 mol%, and 1,4-cyclohexane Dimethanol: 10 to 70 mol%, especially terephthalic acid: 100 mol%, ethylene glycol: 65 to 80 mol% and 1,4-cyclohexanedimethanol: 20 to 35
Molar% is preferred. If the ethylene glycol component is less than 30 mol% or the 1,4-cyclohexane dimethanol component is more than 90 mol%, recrystallization of the polyethylene terephthalate resin proceeds and calendering cannot be performed. Conversely, when the ethylene glycol component exceeds 90 mol% or the 1,4-cyclohexanedimethanol component is less than 10 mol%, calendering cannot be performed due to recrystallization.

The acrylic resin used in the non-crystalline polyethylene terephthalate resin composition includes acrylic acid and methacrylic acid polymers described in "Self-regulation Standards for Food Containers and Packaging Made of Vinyl Chloride Resin". Used. This includes, for example, polyacrylic acid ester, polymethacrylic acid ester, acrylic acid / methacrylic acid copolymer, copolymer of acrylic acid ester and methacrylic acid ester, one or both of acrylic acid ester and methacrylic acid ester and one of the following monomers:
And copolymers with species or more. Examples of the monomer include acrylic acid, glycidyl methacrylate, acrylonitrile, vinyl chloride, butadiene, vinyl acetate, vinylidene chloride, itaconic acid, dibutyl itaconate, styrene, methacrylic acid, α-methylstyrene, cyclohexylmaleimide, and the like. .

The acrylic resin has a weight average molecular weight in the range of 50,000 to 6,000,000, and is blended in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the amorphous polyethylene terephthalate resin. The acrylic resin also has a weight average molecular weight in the range of 50,000 or more to less than 700,000.
10 parts by weight, especially 0.5 to 5 parts by weight, having a weight average molecular weight of
Acrylic resin within the range of 700,000 to 6,000,000
Those composed of two kinds of combinations of 0.1 to 5 parts by weight, particularly 0.2 to 3 parts by weight are preferable.

If the weight-average molecular weight of the acrylic resin is less than 50,000, the rubber elasticity of the melted or softened sheet is reduced, and the sheet peeled from the metal roll of the calender becomes difficult to take off, and the weight-average molecular weight becomes 600. If it exceeds 10,000, the sheet will not peel off from the metal roll of the calendar. If the amount is less than 0.1 part by weight, the effect of peeling the calender from the metal roll is not obtained, and calendering becomes difficult. If the amount exceeds 15 parts by weight, the metal roll peeling property is large, the penetration of the rolled resin into the metal roll is poor, and stable processing becomes difficult, and the rotation of the molten resin bank to be rolled becomes uneven, so that the surface of the obtained sheet Poor smoothness.

On the other hand, as the 4-fluoroethylene-modified acrylic resin, a resin obtained by copolymerizing an acrylic acid or methacrylic acid polymer with 4-fluoroethylene is used. The amount added is 0.05 to 2 parts by weight, preferably 0.3 to 1 part by weight, based on 100 parts by weight of the amorphous polyethylene terephthalate resin. If the added amount is less than 0.05 parts by weight, the elasticity of the melted or softened sheet rubber decreases, and the sheet peeled off from the metal roll of the calender elongates and becomes difficult to be taken off. If the amount is more than 2 parts by weight, the rubber surface of the sheet is too strong, so that the sheet surface is roughened and the smoothness is deteriorated.

The above-mentioned amorphous polyethylene terephthalate resin composition may further contain one or more of titanium oxide, talc and calcium widely used as pigments or fillers in an amount of 100% by weight of the amorphous polyethylene terephthalate resin. By blending 1 to 20 parts by weight, preferably 2 to 10 parts by weight with respect to parts, there is an effect that the rotation of the calendar bank is smooth and that air is prevented from being mixed into the resin sheet. This facilitates the adjustment for preventing the air from being mixed in the sheet, which is usually performed by changing the temperature and the speed ratio of each roll of the calender. And the obtained sheet becomes a sheet excellent in surface smoothness without air marks. If the addition amount is less than 1 part by weight, the effect of preventing air from being mixed into the resin sheet is small, and if it exceeds 20 parts by weight, calendering becomes difficult.

The non-crystalline polyethylene terephthalate resin composition may contain, in addition to the above-mentioned materials, a stabilizer, a surfactant, an antioxidant, an antistatic agent, a filler, an ultraviolet ray inhibitor, a pigment, if necessary. And the like can be added by selecting the kind or amount so as not to impair the suitability for calendering.

The method for calendering the non-crystalline polyethylene terephthalate resin composition of the present invention uses a calendering machine equipped with four or more metal rolls, and the surface temperature of the final metal roll is adjusted to the non-crystalline polyethylene terephthalate resin. By processing at a temperature 80 to 160 ° C. higher than the glass transition temperature of the composition, particularly 100 to 140 ° C., an amorphous polyethylene terephthalate sheet excellent in surface smoothness can be obtained. When the surface temperature of the final metal roll is lower than the glass transition temperature of the amorphous polyethylene terephthalate resin composition + 80 ° C, the sheet surface becomes rough and poor in smoothness, and conversely, the glass transition temperature of the amorphous polyethylene terephthalate resin composition Than 160 ℃
If the temperature exceeds the high temperature, the releasability of the sheet from the metal roll deteriorates.

[0016]

EXAMPLES Specific embodiments of the present invention will be described below with reference to examples and comparative examples. Examples 1 to 8 and Comparative Examples 1 to 12 A composition obtained by mixing the following materials in the proportions shown in Tables 1 and 2 with 100 parts by weight of non-crystalline polyethylene terephthalate resin and uniformly mixing them with a Henschel mixer. Use a reverse L-shaped four-roll calendering machine for the thickness of 0.3m
m, processed into a 1000 mm wide sheet. The surface temperature of the metal roll of the calender is 200 ° C for the first roll and 2 for the second roll from the rolls into which the molten resin composition is charged.
00 ° C, third roll at 195 ° C, final roll at 140 ° C,
The temperature was changed to 190 ° C and 250 ° C, and the releasability from the metal roll, the surface smoothness of the obtained sheet, and the take-off property of the sheet from the final metal roll of the calender were evaluated based on the following criteria. Also shown in Table 2.

(Materials used) Amorphous polyethylene terephthalate resin PETG 6763
(Eastman Chemical Company, trade name, terephthalic acid 1
00 mol%, 65-70 mol% ethylene glycol and 1,4
-Amorphous polyethylene terephthalate resin consisting of 30 to 35 mol% of cyclohexane dimethanol, glass transition temperature: 80 ° C)-Acrylic resin L-1000 (manufactured by Mitsubishi Rayon Co., trade name, weight average molecular weight 200,000)-Acrylic Acid-based resin P-550A (previous, weight average molecular weight 100
10,000) Acrylic resin having a weight-average molecular weight of 10,000 or 8 million used a material polymerized by a conventionally known method.・ 4-Fluoroethylene-modified acrylic acid-based resin A-3000

(Evaluation method) Removability of calender from metal roll (in the table, metal roll releasability): Very good release of melt-softened sheet from metal roll. Good peeling of the melt-softened sheet is good ... Poor peeling of the melt-softened sheet from the metal roll is bad.
…………… ×

Sheet surface smoothness (referred to as sheet surface smoothness in the table): The surface of the sheet is very smooth. ◎ The surface of the sheet is smooth .... The surface of the sheet is rough. Not smooth ... ×

Sheet take-off property (referred to as sheet take-off property in the table): The sheet peeled off from the final metal roll of the calender does not extremely stretch and is very easy to take off. The stretched sheet does not stretch extremely and is easy to pick up .... The sheet peeled from the last metal roll of the calendar is extremely stretched and is difficult to pick up.

[0021] The weight average molecular weight is measured using a measuring device SHODEX GPC.
Column SYODEX G was added to SYSTEM11 (manufactured by Showa Denko KK).
Using PC KF-800P (same as above, protection), SYODEX GPC KF-806F (same as above, analysis), standard polystyrene (manufactured by Water Associates) as a calibration curve, and using tetrahydrofuran as a solvent, GPC Measured at 40 ° C.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

The non-crystalline polyethylene terephthalate resin composition of the present invention has a good separation from the metal roll during calendering, has a small elongation of the peeled sheet, and can be easily taken off from the final metal roll of the calender. The obtained sheet is a high-quality sheet having excellent surface smoothness and no local thickness variation, and is excellent in productivity. By using this sheet-like material, there is no hole due to local thickness fluctuation of the sheet during vacuum forming and pressure forming, and it is possible to eliminate wrinkles during lamination and application omission during coating.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/34 C08K 3/34 // (C08L 67/02 33:06) B29K 67:00 B29L 7:00 (72) Inventor Yasuki Kodama 1-406-1, Yoshino-cho, Omiya-shi, Saitama F-term in Shin-Etsu Polymer Co., Ltd. Tokyo Plant (reference) 4F204 AA24 AB15 AB16 AG01 AR06 FA06 FB02 FF01 FF21 FQ31 FQ32 4J002 BB203 BC022 BD052 BD102 BD153 BF022 BG012 BG042 BG043 BG052 BG102 BL012 CD192 CF061 DE136 DE236 DJ046 GG00 GL00

Claims (4)

[Claims] An amorphous polyethylene terephthalate resin
One or both of 0.1 to 15 parts by weight of an acrylic acid resin having a weight average molecular weight of 50,000 to 6,000,000 and 0.05 to 2 parts by weight of a 4-fluoroethylene-modified acrylic acid resin are mixed with 100 parts by weight. A non-crystalline polyethylene terephthalate resin composition, comprising: 2. The amorphous polyethylene terephthalate resin composition according to claim 1, wherein at least one of titanium oxide, talc and calcium carbonate is blended in an amount of 1 to 20 parts by weight. 3. An acrylic resin having a weight-average molecular weight of 50,000 to 6,000,000 is 0.2 to 10 parts by weight of an acrylic resin having a weight-average molecular weight of 50,000 to less than 700,000 and a weight-average molecular weight of 700,000 or more. 2. The non-crystalline polyethylene terephthalate resin composition according to claim 1, comprising a combination of two kinds of 0.1 to 5 parts by weight of an acrylic acid resin of up to 6,000,000 or less. 4. A process using a calendering machine equipped with four or more metal rolls, wherein the surface temperature of the final metal roll is 80 to 160 ° C. higher than the glass transition temperature of the amorphous polyethylene terephthalate resin composition. A method for calendering a non-crystalline polyethylene terephthalate resin composition.