Source: http://www.google.com/patents/US7906570?dq=645576
Timestamp: 2017-03-29 04:08:21
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Matched Legal Cases: ['Application No. 10', 'Application No. 10', 'Application No. 2004', 'Application No. 2004', 'Application No. 2004', 'Application No. 200710085053']

Patent US7906570 - Thermoplastic resin composition and production process thereof - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsDisclosed is a thermoplastic resin composition contains including a methacrylic resin having a ring structure in a main chain thereof and a glass transition temperature of 110° C. or higher, and at least one kind of metal compound selected from metal salts, metal complexes, and metal oxides, wherein...http://www.google.com/patents/US7906570?utm_source=gb-gplus-sharePatent US7906570 - Thermoplastic resin composition and production process thereofAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS7906570 B2Publication typeGrantApplication numberUS 11/712,403Publication dateMar 15, 2011Filing dateMar 1, 2007Priority dateMar 1, 2006Fee statusPaidAlso published asCN101029162A, CN101029162B, DE102007009268A1, DE102007009268B4, US20070208119Publication number11712403, 712403, US 7906570 B2, US 7906570B2, US-B2-7906570, US7906570 B2, US7906570B2InventorsKen-ichi Ueda, Shigeo Otome, Shoji Ito, Yow-hei Sohgawa, Hideo AsanoOriginal AssigneeNippon Shokubai Co., Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (38), Non-Patent Citations (12), Classifications (22), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetThermoplastic resin composition and production process thereof
Disclosed is a thermoplastic resin composition contains including a methacrylic resin having a ring structure in a main chain thereof and a glass transition temperature of 110° C. or higher, and at least one kind of metal compound selected from metal salts, metal complexes, and metal oxides, wherein a content of the metal compound in the composition is from 10 to 10,000 ppm in terms of metal atom based on a mass of the methacrylic resin, and a process for producing such a thermoplastic resin composition, the process including carrying out, when preparing a methacrylic resin having a ring structure in a main chain thereof and a glass transition temperature of 110° C. or higher, cyclization condensation reaction using a catalyst to form the ring structure; and then adding a deactivator of the catalyst.
1. A thermoplastic resin composition comprising a methacrylic resin having a ring structure in a main chain thereof and a glass transition temperature of 110° C. or higher, and at least one kind of metal compound selected from metal salts of organophosphorous compounds and metal salts of acidic organosulfur compounds, wherein a content of the metal compound in the composition is from 10 to 10,000 ppm in terms of metal atom based on a mass of the methacrylic resin.
4. The thermoplastic resin composition according to claim 1, wherein a number of bubbles generated when the composition is heated at 260° C. for 20 minutes is 20 pieces/g or smaller.
7. A process for producing a thermoplastic resin composition according to claim 1, the process comprising carrying out, when preparing a methacrylic resin having a ring structure in a main chain thereof and a glass transition temperature of 110° C. or higher, cyclization condensation reaction using a catalyst to form the ring structure; and then adding a deactivator of the catalyst. Description
The present invention relates to a thermoplastic resin composition and a production process thereof, and more specifically, to a thermoplastic resin composition comprising a methacrylic resin having a ring structure in the main chain thereof and a glass transition temperature of 110° C. or higher, and a production process thereof.
Conventionally, as a resin having transparency, there have been known methacrylic resins. Because methacrylic resins are excellent both in transparency and in surface gloss and weather resistance and have a good balance of mechanical strength, forming processability, and surface hardness, they have widely been used in applications relevant to optics in cars, home electric appliances, and the like. However, the glass transition temperatures of methacrylic resins are about 100° C., and therefore, it has been difficult to use methacrylic resins in the fields requiring heat resistance.
Thus, the present invention provides a thermoplastic resin composition comprising a methacrylic resin having a ring structure in a main chain thereof and a glass transition temperature of 110° C. or higher, and at least one kind of metal compound selected from metal salts, metal complexes, and metal oxides, wherein a content of the metal compound in the composition is from 10 to 10,000 ppm in terms of metal atom based on a mass of the methacrylic resin.
In the thermoplastic resin composition of the present invention, a number of bubbles generated when the composition is heated at 260° C. for 20 minutes may preferably be 20 pieces/g or smaller.
The present invention further provides a process for producing a thermoplastic resin composition as described above, the process comprising carrying out, when preparing a methacrylic resin having a ring structure in a main chain thereof and a glass transition temperature of 110° C. or higher, cyclization condensation reaction using a catalyst, to form the ring structure; and then adding a deactivator of the catalyst.
The thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising a methacrylic resin having a ring structure in a main chain thereof and a glass transition temperature of 110° C. or higher, and at least one kind of metal compound selected from metal salts, metal complexes, and metal oxides, wherein a content of the metal compound in the composition is from 10 to 10,000 ppm in terms of metal atom based on a mass of the methacrylic resin. The phrase “at least one kind of metal compound selected from metal salts, metal complexes, and metal oxides” as used herein means a deactivator added after the cyclization condensation reaction for introducing a ring structure into the main chain of a methacrylic resin, or means a product generated by the reaction of a catalyst used in the cyclization condensation reaction for introducing a ring structure into the main chain of a methacrylic resin and a deactivator added after the cyclization condensation reaction, or a denatured product thereof. This product or a denatured product thereof depends on the kinds of catalyst and deactivator or the conditions of cyclization condensation reaction and devolatilization step, and therefore, is not particularly limited. The content of the metal compound can be expressed in terms of metal atom because a metal is contained either in the catalyst or in the deactivator.
To produce the thermoplastic resin composition of the present invention, when preparing a methacrylic resin having a ring structure in a main chain thereof and a glass transition temperature of 110° C. or higher, the ring structure may be formed by cyclization condensation reaction using a catalyst, and then, the catalyst may be deactivated by adding a deactivator. That is, the production process of the thermoplastic resin composition of the present invention comprises carrying out, when preparing a methacrylic resin having a ring structure in a main chain thereof and a glass transition temperature of 110° C. or higher, cyclization condensation reaction using a catalyst to form the ring structure; and then adding a deactivator of the catalyst. As for the production process of the thermoplastic resin composition of the present invention, although the process will be described below in detail when the methacrylic resin is a lactone ring-containing polymer, also in cases where the methacrylic resin is other than the lactone ring-containing polymer, for example, a polymer having a ring structure composed of glutaric anhydride, a 2,5-dioxotetrahydrofuran ring-containing polymer, or a 2,6-dioxotetrahydropyran ring-containing polymer, the production process can similarly be carried out as in case of the lactone ring-containing polymer by appropriately selecting monomer components so as to form one of these ring structures in the main chain by cyclization condensation reaction.
In the thermoplastic resin composition of the present invention, as the methacrylic resin having a ring structure in a main chain thereof and having a glass transition temperature of 110° C. or higher, there can be mentioned, for example, lactone ring-containing polymers, polymers having a ring structure composed of glutaric anhydride shown by the following formula (2):
The glass transition temperature of the methacrylic resin may usually be 110° C. or higher, preferably 115° C. or higher, more preferably 120° C. or higher, and still more preferably 125° C. or higher, and the upper limit thereof is not particularly limited, but may preferably be 170° C., more preferably 160° C., and still more preferably 150° C. The glass transition temperature of the methacrylic resin is a value obtained by a middle point method according to ASTM-D-3418.
Although the polymerization temperature and the polymerization time may vary depending upon the kind and ratio of monomers to be used and the like, for example, the polymerization temperature may preferably be from 0° C. to 150° C. and the polymerization time may preferably be from 0.5 to 20 hours, and the polymerization temperature may more preferably be from 80° C. to 140° C. and the polymerization time may more preferably be from 1 to 10 hours.
In the case of the form of polymerization using a solvent, examples of the polymerization solvent may include, although it is not particularly limited to, aromatic hydrocarbon type solvents such as toluene, xylene, and ethylbenzene; ketone type solvents such as methyl ethyl ketone and methyl isobutyl ketone; and ether type solvents such as tetrahydrofuran. These solvents may be used alone, or two or more kinds of these solvents may also be used in combination. Also, when the boiling point of a solvent is too high, the amount of residual volatile components in the lactone ring-containing polymer finally obtained may become increased, and therefore, solvents having boiling points of from 50° C. to 200° C. may be preferred.
The reaction treatment temperature when the devolatilizer consisting of a heat exchanger and a devolatilization vessel is used may preferably be from 150° C. to 350° C., more preferably from 200° C. to 300° C. When the reaction treatment temperature is lower than 150° C., the cyclization condensation reaction may become insufficient, and therefore, the amounts of residual volatile components may be increased. In contrast, when the reaction treatment temperature is higher than 350° C., the polymer obtained may be colored or decomposed.
The reaction treatment temperature in the case where the extruder with a vent is used may preferably be from 150° C. to 350° C., more preferably from 200° C. to 300° C. When the reaction treatment temperature is lower than 150° C., the cyclization condensation reaction may become insufficient, and the amounts of residual volatile components may be increased. In contrast, when the reaction treatment temperature is higher than 350° C., the polymer obtained may be colored or decomposed.
In the above-described case where the devolatilization step is combined through the whole cyclization condensation reaction, the polymer (a) may partly be decomposed before it undergoes the cyclization condensation reaction due to a difference in thermal hysteresis when the polymer (a) is heat treated at a high temperature around or above 250° C. by using a twin-screw extruder, so that the physical properties of the lactone ring-containing polymer may be deteriorated. For this, when the cyclization condensation reaction is carried out to proceed to some extent in advance before the cyclization condensation reaction combined with the devolatilization step at the same time is carried out, this is preferred because the reaction conditions in the latter half of the reaction can be made milder and a deterioration in the physical properties of the lactone ring-containing polymer obtained can, therefore, be prevented. Particularly preferred cases may include cases where the devolatilization step is started with an interval of certain time after the start of the cyclization condensation reaction, that is, cases where hydroxyl groups and ester groups present in the molecular chain of the polymer (a) obtained in the polymerization step are allowed to undergo cyclization condensation reaction in advance to raise the rate of cyclization condensation reaction to some extent, and subsequently, the cyclization condensation reaction combined with the devolatilization step at the same time is carried out. More specifically, preferred cases may include cases where the cyclization condensation reaction is allowed to proceed to a certain reaction rate in the presence of a solvent in advance in a vessel type reactor and then the cyclization condensation reaction is completed by using a reactor provided with a devolatilizer, for example, a devolatilizer consisting of a heat exchanger and a devolatilization vessel, or an extruder with a vent. Particularly, in these cases, it is more preferred that a catalyst for the cyclization condensation reaction is present.
As described above, the method in which hydroxyl groups and ester groups present in the molecular chain of the polymer (a) obtained in the polymerization step are allowed to undergo cyclization condensation reaction in advance to raise the rate of cyclization condensation reaction to some extent, and subsequently, the cyclization condensation reaction combined with the devolatilization step at the same time is carried out, is a preferred case to obtain a lactone ring-containing polymer in the present invention. This case makes it possible to obtain a lactone ring-containing polymer which has a higher glass transition temperature, which is more improved in the rate of cyclization condensation reaction, and which is excellent in heat resistance. In this case, the standard of the cyclization condensation reaction rate is, for example, as follows: the weight loss rate within a temperature range of from 150° C. to 300° C. in the dynamic TG measurement shown in Examples may preferably be 2% or smaller, more preferably 1.5% or smaller, and still more preferably 1% or smaller.
Examples of the catalyst to be added in the method (i) may include esterification catalysts or ester exchange catalysts such as p-toluenesulfonic acid which are usually used, basic compounds, organic carboxylic acid salts, and carbonates. In the present invention, it is preferred to use the above-described organophosphorus compounds. The time of adding a catalyst is not particularly limited, but the catalyst may be added in the initial stage of the reaction, during the reaction, or at the both times. The amount of catalyst to be added is not particularly limited, but may preferably be from 0.001% to 5% by mass, more preferably from 0.01% to 2.5% by mass, still more preferably from 0.01% to 0.1% by mass, and particularly preferably from 0.05% to 0.5% by mass, relative to the mass of the polymer (a). The heating temperature and heating time in the method (i) are not particularly limited, but the heating temperature may preferably be from room temperature to 300° C., more preferably from 50° C. to 250° C., and the heating time may preferably be from 1 to 20 hours, more preferably from 2 to 10 hours. When the heating temperature is lower than room temperature or the heating time is shorter than 1 hour, the rate of the cyclization condensation reaction may be decreased. When the heating temperature is greater than 300° C. or the heating time is longer than 20 hours, the resin may be colored or decomposed.
The method (ii) may be carried out using a pressure vessel type reactor or the like by heating the polymerization reaction mixture obtained in the polymerization step as it is. The heating temperature and heating time in the method (ii) are not particularly limited, but the heating temperature may preferably be from 100° C. to 350° C., more preferably from 150° C. to 300° C., and the heating time may preferably be from 1 to 20 hours, more preferably from 2 to 10 hours. When the heating temperature is lower than 100° C. or the heating time is shorter than 1 hour, the rate of the cyclization condensation reaction may be decreased. When the heating temperature is higher than 350° C. or the heating time is longer than 20 hours, the resin may be colored or decomposed.
The weight loss rate within a temperature range of from 150° C. to 300° C. in the measurement of dynamic TG may preferably be 2% or lower, more preferably 1.5% or lower, and still more preferably 1% or lower, when the cyclization condensation reaction carried out in advance before the cyclization condensation reaction combined with the devolatilization step at the same time is completed, that is, just before the start of the devolatilization step. When the weight loss rate is higher than 2%, the cyclization condensation reaction rate cannot sufficiently be increased to a high level in some cases, even if the cyclization condensation reaction combined the devolatilization step at the same time is subsequently carried out, and therefore, the physical properties of the lactone ring-containing polymer obtained may be deteriorated. In addition to the polymer (a), any other thermoplastic resin is allowed to exist when the above cyclization condensation reaction is carried out.
The lactone ring-containing polymer may preferably have a weight loss rate of 1% or lower, more preferably 0.5% or lower, and still more preferably 0.3% or lower in a temperature range of from 150° C. to 300° C. in the measurement of dynamic TG.
The 5% weight loss temperature of the lactone ring-containing polymer in the thermogravimetric analysis (TG) may preferably be 330° C. or higher, more preferably 350° C. or higher, and still more preferably 360° C. or higher. The 5% weight loss temperature in the thermogravimetric analysis (TG) is an index of thermal stability, and when it is lower than 330° C., sufficient thermal stability cannot be exhibited in some cases.
The glass transition temperature (Tg) of the lactone ring-containing polymer may preferably be 115° C. or higher, more preferably 125° C. or higher, still more preferably 130° C. or higher. The upper limit of the glass transition temperature (Tg) may particularly be, although it is not particularly limited to, 170° C., more preferably 160° C., and still more preferably 150° C. The glass transition temperature (Tg) of the lactone ring-containing polymer is a value determined by a middle point method according to ASTM-D-3418.
The thermoplastic resin composition of the present invention causes no bubbling phenomenon at the time of thermal processing because even if the catalyst used in the transesterification remains, it is in a very small amount and most of the catalyst has been deactivated. In fact, the amount of bubbles generated when this thermoplastic resin composition is heated at 260° C. for 20 minutes may preferably be 20 pieces/g or smaller, more preferably 15 pieces/g or smaller, still more preferably 10 pieces/g or smaller, and particularly preferably 5 pieces/g or smaller.
The amount of bubbles is measured with a melt indexer defined in JIS-K7210. More specifically, the amount of bubbles is expressed as pieces of bubbles per one gram of the thermoplastic resin composition, which is determined as follows: the dried thermoplastic resin composition is filled in a cylinder of the melt indexer and is kept at 260° C. for 20 minutes, followed by the extrusion of the resin composition in a strand form, and the generation number of bubbles present between the upper marked line and the lower marked line on the strand obtained is counted.
Examples of the melt extrusion method may include T-die methods and inflation methods. At this time, the film formation temperature may appropriately be adjusted according to the glass transition temperature of the film raw materials, and it may preferably be, although it is not particularly limited to, from 150° C. to 350° C., more preferably 200° C. to 300° C.
The stretching temperature may preferably be around the glass transition temperature of the thermoplastic resin composition as a film raw material. The specific stretching temperature may preferably be from (glass transition temperature−30° C.) to (glass transition temperature+100° C.), more preferably from (glass transition temperature−20° C.) to (glass transition temperature+80° C.). When the stretching temperature is lower than (glass transition temperature−30° C.), sufficient stretching ratio cannot be obtained in some cases. In contrast, when the stretching temperature is higher than (glass transition temperature+100° C.), the resin may be fluidized, which makes it impossible to carry out stable stretching.
The polymer (or a polymer solution or polymer pellets) was once dissolved in or diluted with tetrahydrofuran, which was then poured into excess hexane or methanol to cause reprecipitation. The precipitate taken out from the solution was dried under vacuum (1 mmHg (1.33 hPa), 80° C., 3 hours or longer) to remove volatile components. The resulting resin having a white solid form was analyzed by the following method (dynamic TG method).
Temperature rise rate: 10° C./min.
Method: Stepped isothermal control method (weight loss rate within a temperature range of from 60° C. to 500° C. was controlled to 0.005%/s or smaller)
First, the weight loss when all hydroxyl groups were removed as methanol from the resulting polymer composition by dealcoholization was defined as the standard, and then, a dealcoholization reaction rate was determined from the weight loss in the dealcoholization reaction within a temperature range of from 150° C. before the start of weight loss to 300° C. before the start of the decomposition of the polymer in the dynamic TG measurement.
More specifically, a weight loss rate within a temperature range of from 150° C. to 300° C. is measured in the dynamic TG measurement of the polymer having a ring structure in the main chain thereof, and the measured actual value is defined as an actual weight loss rate (X). On the other hand, the weight loss rate is calculated from the composition of the polymer on the premise that all hydroxyl groups contained in the polymer composition are converted into alcohols to participate in the formation of a ring structure and then dealcoholized (specifically, the weight loss rate calculated on the premise that 100% of the alcohols in the composition undergoes dealcoholization reaction) is defined as a theoretical weight loss rate (Y). The theoretical weight loss rate (Y) may be calculated more specifically from the molar ratio of the raw material monomer having a structure (i.e., hydroxyl groups) participating in the dealcoholization reaction in the polymer, that is, from the content of the raw material monomer in the polymer composition. In the following equation of dealcoholization, the above values are substituted to calculate and the obtained value is noted by percentage, thereby obtaining the rate of dealcoholization reaction.
As one example, there will be calculated the proportion of the lactone ring structure in the pellets obtained in Production Example 1 explained later. To determine the theoretical weight loss rate (Y), the content of methyl 2-(hydroxymethyl)acrylate in the polymer is as follows: (32/116)×20.0≅5.52% by mass since the molecular weight of methanol is 32, the molecular weight of methyl 2-(hydroxymethyl)acrylate is 116, and the content (by mass ratio) of methyl 2-(hydroxymethyl)acrylate is 20.0% by mass from the composition. On the other hand, the actual weight loss rate (X) determined by dynamic TG measurement was 0.17% by mass. Substituting these values in the above dealcoholization equation, 1−(0.17/5.52)=0.969, and thus, the dealcoholization reaction rate is 96.9%. Then, on the assumption that lactone cyclization may occur corresponding to this rate of dealcoholization reaction, the proportion of the lactone ring structure in the copolymer can be calculated by multiplying the content (mass ratio), in the copolymer, of a raw material monomer with a structure (i.e., hydroxyl groups) involved in the lactone cyclization by the rate of dealcoholization and then converting the product into the content (mass ratio) of the lactone ring structure. In the case of Production Example 1, the content of methyl 2-(hydroxymethyl)acrylate in the copolymer was 20.0% by mass, the calculated rate of dealcoholization is 96.9% by mass, the formula mass of the lactone ring structure is 170, which structure is formed when methyl 2-(hydroxymethyl)acrylate having a molecular weight of 116 is condensed with methylmethacrylate, and therefore, the proportion of the lactone ring structure in the copolymer becomes 28.4% (=20.0%×0.969×170/116) by mass.
The melt flow rate was measured at a test temperature of 240° C. under a load of 10 kg according to JIS-K6874.
The thermal analysis of the polymer was made using a differential scanning calorimeter (DSC-8230, available from Rigaku Corporation) on the following conditions: sample amount, 10 mg; temperature rise rate, 10° C./min.; and nitrogen flow, 50 mL/min. The glass transition temperature (Tg) was determined by a middle point method according to ASTM-D-3418.
The amount of bubbles was measured for molded articles in a strand form. The dried thermoplastic resin composition was filled in a cylinder of the melt indexer defined in JIS-K7210 and was kept at 260° C. for 20 minutes, followed by the extrusion of the resin composition in a strand form, and the generation number of bubbles present between the upper marked line and the lower marked line on the strand obtained was counted and expressed as pieces of bubbles per one gram of the thermoplastic resin composition.
The mixture was heated to 105° C. under a nitrogen gas stream to cause reflux, at which 5 g of t-butylperoxyisopropyl carbonate (KAYACARBON BIC-75, available from Chemical Akzo Co., Ltd.) was added as a polymerization initiator, and at the same time, solution polymerization was carried out under reflux at from about 105° C. to 120° C., while a solution containing 10 g of t-butylperoxyisopropyl carbonate (KAYACARBON BIC-75, available from Chemical Akzo Co., Ltd.) dissolved in 230 g of methyl isobutyl ketone was added dropwise over 2 hours. The reaction mixture was then aged over further 4 hours.
Then, 30 g of a mixture of stearyl phosphate and distearylphosphate (Phoslex A-18, available from Sakai Chemical Industry Co., Ltd.) was added to the polymer solution obtained, which was allowed to cause cyclization condensation reaction under reflux at from about 90° C. to 120° C. for 5 hours. Then, the polymer solution obtained was introduced at a treatment rate of 2.0 kg/h on the resin basis into a vent type screw twin-screw extruder (φ=29.75 mm, L/D=30) on the following conditions: barrel temperature, 260° C.; revolution number, 100 rpm; degree of vacuum, from 13.3 to 400 hPa (from 10 to 300 mmHg); the number of rear vents, 1; and the number of fore vents, 4. In this extruder, the polymer solution was further allowed to cause cyclization condensation reaction and devolatilization, and then extruded to obtain transparent pellets of lactone ring-containing polymer (A).
When the dynamic TG measurement was carried out for the lactone ring-containing polymer, a weight loss of 0.17% by mass was detected. Moreover, the lactone ring-containing polymer had a weight average molecular weight of 133,000, a melt flow rate of 6.5 g/10 min., and a glass transition temperature of 131° C.
The mixture was heated to 105° C. under a nitrogen gas stream to cause reflux, at which 187 g of t-amyl-peroxyisononanoate (Lupasol 570, available from Arkema Yoshitomi Ltd.) was added as a polymerization initiator, and at the same time, solution polymerization was carried out under reflux at from 105° C. to 110° C., while a solution containing 374 g of t-amylperoxyisononanoate (Lupasol 570, available from Arkema Yoshitomi Ltd.) dissolved in 3.6 kg of toluene was added dropwise over 2 hours. The reaction mixture was then aged over further 4 hours.
Then, 170 g of a mixture of stearyl phosphate and distearyl phosphate (Phoslex A-18, available from Sakai Chemical Industry Co., Ltd.) was added to the polymer solution obtained, which was allowed to cause cyclization condensation reaction under reflux at from about 90° C. to 110° C. for 5 hours. Then, the polymer solution obtained was introduced at a treatment rate of 13 kg/h on the resin basis into a vent type screw twin-screw extruder (φ=42 mm, L/D=42) on the following conditions: barrel temperature, 250° C.; revolution number, 150 rpm; degree of vacuum, from 13.3 to 400 hPa (from 10 to 300 mmHg); the number of rear vents, 1; and the number of fore vents, 4. In this extruder, the polymer solution was further allowed to cause cyclization condensation reaction and devolatilization, and then extruded to obtain transparent pellets of lactone ring-containing polymer (B).
When the dynamic TG measurement was carried out for the lactone ring-containing polymer, a weight loss of 0.15% by mass was detected. Moreover, the lactone ring-containing polymer had a weight average molecular weight of 147,000, a melt flow rate of 11.0 g/10 min., and a glass transition temperature of 130° C.
Using a twin-screw extruder (φ=20 mm, L/D=25) zinc oxide (Nanofine, available from Sakai Chemical Industry Co., Ltd.) in an amount of 500 ppm relative to the amount of the polymer was added to the pellets (A) obtained in Production Example 1, and the mixture was kneaded and extruded at 270° C. to obtain transparent pellets (A1) of a thermoplastic resin composition.
The pellets (A1) obtained were fed to a melt indexer set at 260° C. and then kept for 20 minutes, followed by extrusion in a strand form under a load of 10 kg. At this time, the amount of bubbles was 0 piece/g. In addition, the content of the metal compound was 377 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.
Using a twin-screw extruder (φ=30 mm, L/D=30) having vent ports, zinc acetate in an amount of 1,200 ppm relative to the amount of the polymer was added to the pellets (A) obtained in Production Example 1, and the mixture was kneaded and extruded at 260° C. while sucking from the vent ports to obtain transparent pellets (A4) of a thermoplastic resin composition.
The pellets (A4) obtained were fed to an injection molding machine (model HM7, available from Nissei Plastic Industrial Co., Ltd.) in which the barrel temperature was set at 260° C., and then kept for 20 minutes, followed by injection shot to obtain molded articles in a disk form having a diameter of 40 mm and a thickness of 3 mm. The molded articles obtained were transparent, and no defects such as bubbles and silver streaks were observed. In addition, the content of the metal compound was 435 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.
In the same manner as described in Example 4, except that zinc acetate was not added, the pellets (A) obtained in Production Example 1 were kneaded and extruded at 260° C. using a twin-screw extruder (φ=30 mm, L/D=30) having vent ports while sucking from the vent ports to obtain pellets (A0) of a thermoplastic resin composition.
Using an extruder equipped with a T-die having a lip opening of 0.4 mm and a width of 150 mm, the pellets (A4) obtained in Example 4 were extruded at 260° C. and taken up with a roll having a controlled temperature of 110° C. to obtain a transparent film having a thickness of 100 μm and containing substantially no defects. In addition, the content of the metal compound was 408 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.
Using an extruder equipped with a T-die having a lip opening of 0.4 mm and a width of 150 mm, the pellets (A0) obtained in Comparative Example 2 were extruded at 260° C. and taken up with a roll having a controlled temperature of 110° C. At this time, no fine film was obtained because of the generation of streaks by bubbling.
Using a Dulmadge single-screw extruder (φ=50 mm, L/D=32) having vent ports, the pellets (B) obtained in Production Example 2 and acrylonitrile-styrene (AS) resin (Stylac AS783, available from Asahi Kasei Chemicals Corporation) in a mass ratio of 90/10 were kneaded together with 400 ppm of zinc acetate and extruded at 280° C. while sucking from the vent ports to obtain transparent pellets (B1) of a thermoplastic resin composition.
The pellets (B1) obtained were fed to an injection molding machine (model HM7, available from Nissei Plastic Industrial Co., Ltd.) in which the barrel temperature was set at 260° C., and then kept for 20 minutes, followed by injection shot to obtain molded articles in a disk form having a diameter of 40 mm and a thickness of 3 mm. The molded articles obtained were transparent, and no defects such as bubbles and silver streaks were observed. In addition, the content of the metal compound was 137 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.
In the same manner as described in Example 6, except that zinc acetate was not added, using a Dulmadge single-screw extruder (φ=50 mm, L/D=32) having vent ports, the pellets (B) obtained in Production Example 2 and acrylonitrile-styrene (AS) resin (Stylac AS783, available from Asahi Kasei Chemicals Corporation) in a mass ratio of 90/10 were kneaded and extruded at 280° C. while sucking from the vent ports to obtain pellets (B0) of a thermoplastic resin composition.
The mixture was heated to 105° C. under a nitrogen gas stream to cause reflux, at which 187 g of t-amyl-peroxyisononanoate (Lupasol 570, available from Arkema Yoshitomi Ltd.) was added as a polymerization initiator, and at the same time, solution polymerization was carried out under reflux at from about 105° C. to 110° C., while a solution containing 374 g of t-amylperoxyisononanoate (Lupasol 570, available from Arkema Yoshitomi Ltd.) dissolved in 3.6 kg of toluene was added dropwise over 2 hours. The reaction mixture was then aged over further 4 hours.
Then, 170 g of a mixture of stearyl phosphate and distearyl phosphate (Phoslex A-18, available from Sakai Chemical Industry Co., Ltd.) was added to the polymer solution obtained, which was allowed to cause cyclization condensation reaction under reflux at from about 90° C. to 110° C. for 5 hours. Then, the polymer solution obtained was introduced at a treatment rate of 13 kg/h on the resin basis into a vent type screw twin-screw extruder (φ=42 mm, L/D=42) on the following conditions: barrel temperature, 250° C., revolution number, 150 rpm; degree of vacuum, from 13.3 to 400 hPa (from 10 to 300 mmHg); the number of rear vents, 1; and the number of fore vents, 4. In this extruder, the polymer solution was further allowed to cause cyclization condensation reaction and devolatilization, and then extruded while injecting, between the third fore vent and the fourth vent, zinc acetate in the form of an aqueous solution so as to be 400 ppm relative to the amount of the polymer obtained, to obtain transparent pellets (B3) of a thermoplastic resin composition.
The lactone ring-containing polymer contained in the thermoplastic resin composition obtained was similar to that obtained in Production Example 2, and when the dynamic TG measurement was carried out for the lactone ring-containing polymer, a weight loss of 0.15% by mass was detected. Moreover, the lactone ring-containing polymer had a weight average molecular weight of 147,000, a melt flow rate of 11.0 g/10 min., and a glass transition temperature of 130° C.
The pellets (B3) obtained were fed to an injection molding machine (model HM7, available from Nissei Plastic Industrial Co., Ltd.) in which the barrel temperature was set at 260° C., and then kept for 20 minutes, followed by injection shot to obtain molded articles in a disk form having a diameter of 40 mm and a thickness of 3 mm. The molded articles obtained were transparent, and no defects such as bubbles and silver streaks were observed. In addition, the content of the metal compound was 131 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.
The mixture was heated to 105° C. under a nitrogen gas stream to cause reflux, at which 309 g of t-amyl-peroxyisononanoate (Lupasol 570, available from Arkema Yoshitomi Ltd.) was added as a polymerization initiator, and at the same time, solution polymerization was carried out under reflux at from about 105° C. to 110° C., while a solution containing 621 g of t-amylperoxyisononanoate (Lupasol 570, available from Arkema Yoshitomi Ltd.) dissolved in 3.7 kg of toluene was added dropwise over 2 hours. The reaction mixture was then aged over further 6 hours.
Then, 300 g of octyl phosphate (Phoslex A-8, available form Sakai Chemical Industry Co., Ltd.) was added to the polymer solution obtained, which was allowed to cause cyclization condensation reaction under reflux at from about 90° C. to 110° C. for 5 hours. Then, the polymer solution obtained was introduced at a treatment rate of 16 kg/h on the resin basis into a vent type screw twin-screw extruder (φ=42 mm, L/D=42) on the following conditions: barrel temperature, 250° C.; revolution number, 240 rpm; degree of vacuum, from 13.3 to 400 hPa (from 10 to 300 mmHg); the number of rear vents, 1; and the number of fore vents, 4. In this extruder, the polymer solution was further allowed to cause cyclization condensation reaction and devolatilization, and then extruded while injecting, between the third fore vent and the fourth vent, zinc octoate (Nikka Octix Zinc 18%, available from Nihon Kagaku Sangyo Co., Ltd.) in the form of a toluene solution so as to be 1,470 ppm relative to the amount of the polymer obtained, to obtain transparent pellets (B4) of a thermoplastic resin composition.
The lactone ring-containing polymer contained in the thermoplastic resin composition obtained had a weight average molecular weight of 148,000, a melt flow rate of 10.9 g/10 min., and a glass transition temperature was 131° C.
The pellets (B4) obtained were fed to an injection molding machine (model HM7, available from Nissei Plastic Industrial Co., Ltd.) in which the barrel temperature was set at 260° C., and then kept for 20 minutes, followed by injection shot to obtain molded articles in a disk form having a diameter of 40 mm and a thickness of 3 mm. The molded articles obtained were transparent, and no defects such as bubbles and silver streaks were observed. In addition, the content of the metal compound was 250 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.
The mixture was heated to 105° C. under a nitrogen gas stream to cause reflux, at which 12 g of t-amylperoxyisononanoate (Lupasol 570, available from Arkema Yoshitomi Ltd.) was added as a polymerization initiator, and at the same time, solution polymerization was carried out under reflux at from about 105° C. to 120° C., while a solution containing 24 g of t-amylperoxy-isononanoate (Lupasol 570, available from Arkema Yoshitomi Ltd.) dissolved in 136 g of toluene was added dropwise over 2 hours. The reaction mixture was then aged over further 4 hours.
Then, 20 g of magnesium ethoxide was added to the polymer solution obtained, which was allowed to cause cyclization condensation reaction under reflux at from about 90° C. to 120° C. for 5 hours. Then, the polymer solution obtained was introduced at a treatment rate of 2.0 kg/h on the resin basis into a vent type screw twin-screw extruder (φ=29.75 mm, L/D=30) on the following conditions: barrel temperature, 260° C.; revolution number, 100 rpm; degree of vacuum, from 13.3 to 400 hPa (from 10 to 300 mmHg); the number of rear vents, 1; and the number of fore vents, 4. In this extruder, the polymer solution was further allowed to cause cyclization condensation reaction and devolatilization, and then extruded while injecting, between the third fore vent and the fourth vent, a mixture of stearyl phosphate and distearyl phosphate (Phoslex A-18, available from Sakai Chemical Industry Co., Ltd.) in the form of a toluene solution so as to be 5,000 ppm relative to the amount of the polymer obtained, to obtain transparent pellets (C1) of a thermoplastic resin composition.
The polymer having a ring structure composed of glutaric anhydride, contained in the thermoplastic resin composition obtained, had a weight average molecular weight of 140,000, a melt flow rate of 13.0 g/10 min., and a glass transition temperature of 127° C.
The pellets (C1) obtained were fed to a melt indexer set at 260° C. and then kept for 20 minutes, followed by extrusion in a strand form under a load of 10 kg. At this time, the amount of bubbles was 0 piece/g. In addition, the content of the metal compound was 430 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.
Thus, it is found that thermoplastic resin compositions obtained by causing cyclization condensation reaction using a catalyst, in the production of a methacrylic resin having a ring structure in the main chain thereof and a glass transition temperature of 110° C. or higher, to form the ring structure and then adding a deactivator for the catalyst to the methacrylic resin obtained can provide molded articles, which are excellent both in transparency and in heat resistance and have desired characteristics such as mechanical strength and forming processability, and particularly, which cause neither bubbling phenomenon nor entering of bubbles or silver streaks at the time of thermal processing.
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