WO1998033637A1

WO1998033637A1 - Process for producing polycarbonate sheet

Info

Publication number: WO1998033637A1
Application number: PCT/JP1998/000087
Authority: WO
Inventors: Hiroshi Akamine; Masaya Okamoto
Original assignee: Idemitsu Petrochemical Co., Ltd.
Priority date: 1997-01-31
Filing date: 1998-01-13
Publication date: 1998-08-06
Also published as: JPH10211642A

Abstract

A process for producing a polycarbonate sheet which comprises melt-extruding into a sheet form a polycarbonate resin composition obtained by compounding 100 parts by weight of a polycarbonate resin with a phenolic antioxidant and a phosphorus compound antioxidant in amounts of 100 to 1,000 ppm and 100 to 2,000 ppm, respectively. Thus, a sheet having a satisfactory surface state and improved resistance to thermal deterioration can be produced, without causing smoking or vent clogging.

Description

Akira Itoda Shoichi Polycarbonate sheet manufacturing method

Technical field

The present invention relates to a method for producing a sheet using a polycarbonate resin composition, and more specifically, to obtain a sheet that can be formed stably, has a good surface condition, and has improved heat aging resistance. It relates to a method of producing a polycarbonate sheet.

Background art

Conventionally, polycarbonate sheets have been used for windows of buildings, automobiles, and vehicles because of their excellent transparency, heat resistance, and mechanical strength. Polycarbonate sheets are generally prepared by melting the polycarbonate resin, extruding it from a die with an extruder, pressing and pressing it with a plurality of mirror-surface cooling rolls, and taking it up with a take-off roller. Manufactured. In this case, the obtained polycarbonate sheet may have poor releasability from the mirror cooling roll, or may have a poor surface condition due to foreign matter adhering to the mirror cooling roll. In addition, it may result in a polycarbonate sheet having poor thermal stability.

Conventionally, as a method of solving the poor surface condition of a polycarbonate sheet, a method of adjusting the temperature of a mirror surface cooling port at the time of manufacturing a polycarbonate sheet is disclosed in Japanese Patent Publication No. — Japanese Patent Application Publication No. 62-48525 discloses a method of providing a temperature difference between the holding rolls of a polycarbonate sheet in Japanese Patent Application Laid-Open No. 254550/1990, but it is not sufficient. Absent. Further, as another improvement method, a method of adding a release agent or a lubricant to a polycarbonate resin is disclosed in Japanese Patent Application Laid-Open No. 2-255588. There are problems such as smoke and vent clogging during the molding of the bone sheet and a decrease in the molecular weight of the obtained polycarbonate sheet. It is also known that a phosphorus-based antioxidant is blended in order to impart heat stability during molding of a poly-carbonate sheet, but the resulting poly- There is a problem that the heat aging resistance of the carbon sheet is inferior. The present invention relates to a polycarbonate sheet capable of obtaining a sheet having a good surface condition and an improved heat aging resistance without generating smoke or clogging of a polycarbonate sheet during molding. The purpose is to provide a method for manufacturing one-bonnet sheets.

Disclosure of the invention

The present inventors have conducted intensive studies to achieve the above object, and as a result, the object can be solved by forming a polycarbonate resin composition containing a specific additive into a sheet shape. The inventors have found this and completed the present invention based on the finding.

That is, the present invention relates to 100 parts by weight of a polycarbonate resin, 100 to 100 ppm of a phenol-based antioxidant, and 100 to 200 ppm of a phosphorus-based antioxidant. An object of the present invention is to provide a method for producing a polycarbonate sheet, which comprises melting and extruding a polycarbonate resin composition containing 0 ppm into a sheet.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows an example of a manufacturing apparatus for a polycarbonate sheet which is suitable for carrying out the present invention. ·

[Explanation of symbols]

1 dice

2 First mouth

3 Second roll

4 Third roll

5 Poly force bone sheet 6 Collection Roll 1-Best Mode for Carrying Out the Invention

The polycarbonate resin used in the present invention is typically one which can be easily produced by reacting a divalent phenol with phosgene or a carbonate compound, and is not particularly limited. . Typical examples of divalent phenols include hydridoquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, and bis (4-hydroxyphenyl). ) Cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfon, bis (4-hydroxyphenyl) keto And 9,9-bis (4-hydroxyphenyl) fluorene and the like, and their halogen derivatives. Among them, 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A is preferably used. Representative examples of carbonate compounds include dialkyl carbonates such as diphenyl carbonate and dialkyl carbonates such as diethyl carbonate. No.

The terminal terminator may have any structure as long as it is a monovalent phenol, and is not particularly limited. Typical examples of the terminating agent are p-tert-butynolef-enol, p-tert-octynolef-eno-nore, p-kminolef-enol, phenol, p- tert-aminophenol, p-nonylphenol, p-cresol, tribromophenol, ρ-bromophenol, 4-hydroxybenzophenol and the like. These may be used alone or in combination of two or more.o

Further, a branching agent may be used in combination as long as the effects of the present invention are not impaired. The branching agents used are 1, 1, and 1 tris (4—hydroxy phenol). Nil) ethane, hi, a ', a', tris (4—hydroxyenino) -1,3,5—triisopropylbenzene, 1— [α-methyl α-1 (4, Hydroxyphenyl) ethyl] — 4 — [a ', a' Bis (4 '' —hydroxyphenyl) ethyl] benzenefluoroglucin, trimellitic acid, isatin bis (0-k A compound having three or more functional groups is preferably used.

The viscosity average molecular weight (MV) of the polycarbonate resin used in the present invention is usually from 100,000 to 100,000, preferably from 1,200 to 7,000, more preferably It is in the range of 15,000 to 50,000. If the viscosity average molecular weight is less than 1000, the impact resistance may be poor. If it exceeds 100000, molding of the polycarbonate sheet may be difficult.

The phenol-based antioxidant used in the present invention is not particularly limited, but a hindered phenol-based antioxidant is preferably used. Typical examples are octadecyl-3- (3,5-di-tert-butyl-4-hydroxyxylphenyl) propionate and triethylene glycol [3- (3-tert-butyl) —Butynole-5—methinole-4—hydroxyphenyl) propionate], 1,6—Hexanediol-bis [3— (3,5—G-tert-butyl-14—hydroxyphenyl) propionate ], Pentaerythryl citrate trakis [3— (3,5—di-tert-butyl-1-4-hydroxyphenyl) propionate], N, N′—hexamethylethylene bis [(3,5 —Di-tert-butyl-1 4 —Hydroxynamic) -Hydrocinnamamide], 2,2—Thiodiethylenebis [3— (3,5—G-tert-Butinole-4-Hydroxyfenyl) ) 2, 4 - bis (n- cycle Chiruchio) one 6 - (4-arsenide Dorokishi one 3, 5 - di one tert - Puchiruani Li Roh) one 1, 3, 5 Track Liazine, 1,3,5—trimethyl 2,4,6—tris (3,5—-di-tert-butyl-1 4—hydroxybenzyl) benzene, tris-1 (3 , 5-di-tert-butyl-4-hydroxybenzyl)-sodium cyanide, bis (3,5-di-tert-butyl-1-hydroxyethyl benzylphosphonate) calcium, etc. Among them, octadecyl 3- (3,5-di-tert-butyl-14-hydroxyphenyl) propionate is preferably used.

The phosphorus antioxidant used in the present invention is not particularly limited. Typical examples are tris (nonylphenyl) phosphite, 2-ethylhexyldienephosphoreite, trimethylinolevite, Triethyl phosphite, tributyl phosphite, trioctinole phosphite, trinonyl phosphite, tri-desinole phosphite, tri Octadecyl phosphite, distearyl penta-erythyl diphosphite, tris (2-chloroethyl) phosphite, tris (2, 3—dicyclo mouth pro) Pill) Trialkyl phosphates such as phosphorites, tricycloalkyl phosphates such as tricyclohexyl phosphates, and triphenyl phosphates , Tri-recyl phosphite, tris (ethyl phenyl) phosphite, tris (butyl phenyl) phosphite, tris (nonylphenyl) phosphite Triaryl phosphite, tris (hydroxy phenyl) phosphite, tris (2,4-di-tert-butyl phenyl) triphenyl, etc. Sphere, Trimethyl phosphite, Triethyl phosphite, Tributyl phosphite, Trioctyl phosphite, Tridecyl phosphite , Trioctadecylphosphite, distant lipstick, erythrityl phosphate, tris (2-chloroethyl) phosphate, tris (2, 3 — jig Trialkylphosphites, tricyclohexyl phosphates, etc. Tricycloalkyl phosphates, triphenylhexyl phosphates, etc. Tricycloalkyl phosphates, triphenylhexyl phosphates, etc. Tri-folio, such as tri-phosphate, tri-phosphorite, tris (nonylphenyl) phosphate, 2-ethylethyl diphenyl phosphate, etc. Trialkyl phosphates and triaryl phosphates are preferably used because of their ability to give a weight.

The polycarbonate resin composition used for molding in the present invention has the following composition. That is, 100 to 100 parts by weight of a polycarbonate resin and 100 to 100 ppm of a phenolic antioxidant, preferably 150 to 500 ppm, and phosphorus The antioxidant contains 100 to 2000 ppm, preferably 500 to 1500 ppm.

If the blending amount of the phenolic antioxidant in the polycarbonate resin composition is too high, and the amount exceeds 100 ppm, the heat aging resistance of the resulting polycarbonate sheet is poor, and l When the content is less than OO ppm, deposits are generated on the surface of the mirror cooling port, and the appearance of the obtained polycarbonate sheet is deteriorated, and the effect of improving the surface is not recognized. In addition, when the amount of the phosphorus-based antioxidant exceeds 2000 ppm or is less than 100 ppm, the heat aging resistance of the obtained polycarbonate sheet is inferior.

In addition, various additives may be added as needed as long as the effects of the present invention are not impaired. Representative examples include benzotriazole-based and benzophenone-based ultraviolet absorbers, hindered amine-based light stabilizers, aliphatic carboxylic acid ester-based, paraffin-based And internal lubricants such as silicone oil, silicone oil, and polyethylene wax, ordinary flame retardants, flame retardant aids, mold release agents, antistatic agents, coloring agents, and the like. In particular, Poli Carbo Nate sheets are often used outdoors and are directly affected by environmental changes, so it is desirable to add an ultraviolet absorber.

The kneading of the polycarbonate resin composition having the composition of the present invention may be performed by a general method, and a predetermined amount is added to a flake-like polycarbonate resin or a pellet-like polycarbonate resin. The phenol-based antioxidant and the phosphorus-based antioxidant may be further mixed and kneaded with various additives as necessary. Then, the mixture is uniformly mixed by any mixing means such as a ribbon blender, a hensyl mixer, a banbari mixer, a drum tumbler, etc., and a single screw extruder, a twin screw extruder, a coneder. It may be extruded and pelletized by a multi-screw screw extruder or the like. At this time, the melt-kneading temperature of the polycarbonate resin composition is from 280 to

320 ° C. is a suitable range.

No special conditions are required for forming the polycarbonate sheet using the pellets obtained in this manner, and the polycarbonate sheet is formed under the conditions generally used. You.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Examples 1 and 2 and Comparative Example 3] Teflon FN270 (trade name, manufactured by Idemitsu Petrochemical Co., Ltd.) (MV: 270) was used as the polycarbonate resin.

0 0) was used. Examples of phenolic antioxidants include (A) octadecyl-3- (3,5-di-tert-butyl-1-4-hydroxyphenyl) propionate (manufactured by Ciba-Geigy Corporation, trade name) Ilganox 1 0 7

6), and (a) tris (2,4-di-tert-butylphenyl) phosphite (trade name: ilgafoss, manufactured by Ciba-Geigy Corporation) Using 168), they were blended in the proportions shown in Table 1, melt-kneaded at 300 ° C, and extruded into pellets. In addition to the above additives, as an ultraviolet absorber, 2— (2′—hydroxy 5′—tert-octylphenyl) benzotriazole (manufactured by SITE INDUSTRY CO., LTD.) 35,000 ppm of name sodium UV5 411) was added.

The obtained polycarbonate pellet was extruded by an extruder (diameter: 115 mm) provided in the apparatus shown in Fig. 1, and then a polycarbonate sheet was manufactured under the following conditions. did. The manufacturing conditions are: cylinder set temperature of 265 to 280 ° C, gear pump set temperature of 260 to 290 ° C, die set temperature of 250 to 280 ° C, screw The pump rotation speed is 50 to 60 rpm, the gear pump rotation speed is 14 rpm, the degree of vacuum is 720 mm Hg.The lip interval is 6.O mm, and the first roll temperature is 120 to 1 33 ° C, second outlet temperature is 120 to 130 ° C, third roll temperature is 144 to 148 ° C, and polycarbonate sheet pick-up speed is 0.6 The thickness was 6 to 1.52 m / min, and the thickness of the obtained polycarbonate sheet was 3.0 to 4.5 mm. After the operation of the polycarbonate sheet manufactured under the above manufacturing conditions was in a steady state, continuous operation was performed for 24 hours to evaluate roll adhesion and heat aging resistance. Table 2 shows the evaluation results of the roll adhesion and the heat aging resistance. The presence or absence of roll adhesion was evaluated by visually determining the presence or absence of contamination on the roll surface 24 hours after the start of the poly-carbonate sheet molding. The heat aging resistance was evaluated by measuring the yellowing degree after leaving a 3.0 mm thick polycarbonate sheet at 100 ° C. for 100 hours. The measurement of the degree of yellowing was in accordance with JIS K—7103—19777.

The viscosity average molecular weight (MV) of the polycarbonate resin was determined by measuring the intrinsic viscosity [] of the methylene chloride solution at 20 ° C with a Ube-Machine-type viscometer, and using the following relational expression. Calculated. . [77] = 1 2 3 X 1 0 "5 M v ° - 8 3 one above port Li Kabone preparative sheet produced in production conditions, the surface condition is good, clogging smoke or venting during molding However, in Comparative Example 3, the heat aging resistance of the sheet was insufficient.

[Example 3] As a phenolic antioxidant, (B) pentaerythryl citrate trakis [3- (3,5-di-tert-butyl-41-hydroxyphenyl) probionet] ] A table of polycarbonate sheets manufactured under the same manufacturing conditions as in Example 1 except that (manufactured by Ciba Geigy Co., Ltd., trade name: Irganox 100) was used. The surface condition was good, and there was no smoke or vent clogging during molding. Also, no roll adhesion occurred.

Example 4 The same procedure as in Example 1 was carried out except that (b) tris (nonylphenyl) phosphite was used as the phosphorus antioxidant. The surface condition of the polycarbonate sheet manufactured under the same manufacturing conditions as in Example 1 was good, and no smoke or clogging of the vent occurred during molding. Also, no roll adhesion occurred.

[Comparative Example 1] As a phenolic antioxidant, (A) octadecyl —3— (3,5—di-tert-butyl-14-hydroxy-phenyl) propionate (manufactured by Ciba-Geigy Corporation) , Trade name: IRGANOX 1076), UV-absorbing agent, 2- (2'-hydroxy-5, -tert-butyl benzoyl) benzotriazole (CYTEC INDUSTRIES) The same procedure as in Example 1 was carried out, except that sir soap UV 5411) manufactured by the Company was used and no phosphorus-based antioxidant was used.

Table of polycarbonate sheets manufactured under the same manufacturing conditions as in Example 1. The surface condition was good, and there was no fume or clogging during molding and no roll adhesion, but the heat aging resistance of the sheet was insufficient.

[Comparative Example 2] As a phosphorus-based antioxidant, (a) tris (2,4-di-tert-butyl-phenyl) phosphite (a product of Ciba-Geigy Corporation, trade name: Irgafoss 1) 6 8), 2-(2'-hydroxy-1,5-tert-octylphenyl) benzotriazole (trade name: CYSOL INDUSTRY CO., LTD., Trade name: UV-5) Example 4 was carried out in the same manner as in Example 1 except that 411) was used and no phenolic antioxidant was used.

In the polycarbonate sheet manufactured under the same manufacturing conditions as in Example 1, mouth adhesion occurred during molding, and the surface of the obtained polycarbonate sheet was reduced.

The condition was also poor.

頹

table 1

Phenyl antioxidants Lin antioxidants

Blending amount Blending amount

(Type I (PPm) ppm)

Example 1 A 3 7 5 a 1 1 2 5

2 A 2 5 0 a 7 5 0 3 B 3 7 5 a 1 1 2 5 4 A 3 7 5 b 1 1 5 Comparative example 1 A 3 7 5

2 a 1 1 2 5 3 A 7 0 0 a 2 1 0 0 Table 2

Industrial applicability

ADVANTAGE OF THE INVENTION According to this invention, it does not generate | occur | produce smoke and clogging of a vent at the time of sheet | seat shaping | molding, It can improve the heat aging resistance and can obtain the polycarbonate sheet with favorable surface condition.

Claims

The scope of the claims -

1. 100 parts by weight of polycarbonate resin mixed with 100 to 100 ppm of phenol-based antioxidant and 100 to 200 ppm of phosphorus-based antioxidant A method for producing a polycarbonate sheet, comprising melting and extruding the resulting polycarbonate resin composition into a sheet.

2. 100 parts by weight of polycarbonate resin is blended with 100 to 100 ppm of phenol-based antioxidant and 100 to 200 ppm of phosphorus-based antioxidant. Polycarbonate resin composition for melt extrusion sheet molding.

3. 100 parts by weight of polycarbonate resin is mixed with 100 to 100 ppm of phenol-based antioxidant and 100 to 200 ppm of phosphorus-based antioxidant. A polycarbonate sheet obtained by extruding a polycarbonate resin composition obtained by melting and extruding in a sheet form.