JP4645809B2 - Thermoplastic resin composition - Google Patents

Description

The present invention relates to a thermoplastic resin composition having a main component of a condensation polymer such as a polyester resin and having excellent moldability. The present invention also relates to a molded product obtained by molding the resin composition.

Condensation polymers represented by polyester resins are used in various fields such as bottles, sheets, and films because of their excellent mechanical strength. In particular, polyester resins are widely used as food packaging materials such as bottles and blister packs because they are excellent in transparency and hygiene. In recent years, there has been an active movement to collect and recycle discarded plastics in order to reduce environmental impact. In particular, the amount of collected and reused polyethylene terephthalate (hereinafter also referred to as PET) resin bottles has been increasing year by year. is doing. The main demand for recycled PET bottles is for egg pack sheets and clothing / carpet fibers, while the amount of recycled PET resin recovered has increased, while demand for recycled products such as sheets and fibers has increased. Is leveling off.
Therefore, the development of new products and molded products is now required to expand the demand for recycled PET resin products. Originally, PET resin has a low melt viscosity and melt tension, so it is suitable for molded products with small diameters and small cross-sectional areas such as fibers and films. However, in order to obtain a molded product having a large diameter and a large cross-sectional area, particularly an extrusion molded product, the melt tension is too low and a drawdown phenomenon occurs, and a molded product having a desired size cannot be obtained. Also in vacuum forming, uneven thickness unevenness due to the drawdown phenomenon is likely to occur. The inherent low viscosity and low melt tension of PET resin are barriers to the development of new products and molded products. Furthermore, in the recycled PET resin, since the thermal history is large and the hydrolysis proceeds, the melt viscosity and melt tension are lower than that of the virgin PET resin, so that it is extremely difficult to develop a new molded product application.
Therefore, conventionally, as a method for improving (increasing) the melt viscosity and melt tension of the PET resin and the recycled PET resin, a method of blending a polymer having an epoxy group (see, for example, Patent Document 1 and Patent Document 2) and epoxy. A method of blending a group-containing compound and an organic alkali metal salt (see, for example, Patent Document 3 and Patent Document 4) has been proposed.

Japanese Patent No. 2675718 International publication pamphlet WO03 / 066704 Republished WO01 / 094433 JP 2004-155968 A

According to the method described in Patent Document 1 or Patent Document 2, it is possible to improve (increase) the melt viscosity and melt tension of the polyester resin and improve drawdown during molding. However, in the above method, the reaction between the epoxy group-containing compound and the polyester resin may be insufficient depending on the conditions. Therefore, it is necessary to add a large amount of the epoxy group-containing compound in the resin composition. In this case, for example, there is a problem that a cross-linked product of the polyester resin and the epoxy group-containing compound is generated at the time of melt kneading in an extruder, and appearance defects of a molded product such as fish eye are likely to occur.
According to the method described in Patent Document 3 or Patent Document 4, the reactivity with the polyester resin is enhanced by using an epoxy group-containing compound and an organic alkali metal salt in combination. However, depending on the conditions, there arises a problem that the viscosity of the thermoplastic resin composition is lowered.
An object of the present invention is to provide a thermoplastic resin composition having a high melt viscosity and a high melt tension, which gives a molded article having excellent dimensional stability. Moreover, it aims at providing the molded article excellent in dimensional stability.

In order to solve the above-mentioned problems, the thermoplastic resin composition of the present invention comprises a thermoplastic resin (A) having a functional group having reactivity with an epoxy group, a polymer (B) having an epoxy group, and an epoxy group. The ratio of the polymer (B) and the catalyst (C) based on the thermoplastic resin (A) containing the catalyst (C) that promotes the reaction between the functional group having the reactivity and the epoxy group is 0. 1 to 5% by mass and 1.0 to 50 ppm.
The molded article of the present invention is obtained by molding the thermoplastic resin composition according to any one of claims 1 to 11.

A thermoplastic resin composition having a large melt viscosity and melt tension and giving a molded article having excellent dimensional stability was obtained. In addition, a molded article having excellent dimensional stability was obtained.

  Hereinafter, embodiments of the present invention will be described in detail. In the present invention, acrylic and methacryl are also referred to as (meth) acryl.

  The thermoplastic resin (A) having a functional group reactive with an epoxy group (also simply referred to as a thermoplastic resin (A)) is a main component of the thermoplastic resin composition, and is obtained by molding the composition. It is responsible for the basic performance of molded products. Specific examples of the functional group having reactivity with the epoxy group include a carboxyl group, a hydroxyl group, an amide group, and an amino group. Examples of the thermoplastic resin (A) include polyester resin, polyamide resin, polycarbonate resin, polylactic acid resin, polycaprolactone resin, polybutylene succinate resin, poly (butylene succinate / adipate) resin, polyphenylene sulfide resin, polyether Examples include ketone resins, polyetherimide resins, cellulose resins, carboxylic acid-modified polyolefin resins, carboxylic acid-modified SBS resins, and carboxylic acid-modified SEBS resins. Moreover, it may be what is called recycled resin from which the waste of these thermoplastic resins is collect | recovered and reused. Preferably, a polyester resin, a polyamide resin, a polycarbonate resin, a polylactic acid resin, and a recycled resin thereof can be used. More preferable thermoplastic resins (A) include polyester resins (including recycled polyester resins).

Examples of the polyester resin include condensation-type polymers or copolymers having a dicarboxylic acid unit and a diol unit as constituent units.
Examples of raw materials used to form dicarboxylic acid units include aromatic dicarboxylic acids or dialkyl ester or diallyl ester thereof, and specific examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid. Acid, naphthalene 1,4-dicarboxylic acid, naphthalene 2,6-dicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, etc. Can be mentioned. An aliphatic dicarboxylic acid or a dialkyl ester or diallyl ester thereof can be used in combination. Specific examples of the aliphatic dicarboxylic acid include glutaric acid, adipic acid, sebacic acid, oxalic acid, and succinic acid.
Specific examples of raw materials used to form diol units include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene Examples include glycol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol.

  Of the polyester resins, crystalline homopolyethylene terephthalate resins and crystalline copolyester resins containing terephthalic acid units and / or isophthalic acid units as dicarboxylic acid units and ethylene glycol units as diol units are preferred. In addition, an amorphous copolyester resin containing a terephthalic acid unit as a dicarboxylic acid unit and an ethylene glycol unit and a 1,4-cyclohexanedimethanol unit as a diol unit is preferable. Examples of other polyester resins include aromatic polyester resins such as polybutylene terephthalate and polyethylene-2,6-naphthalate, aliphatic polyester resins such as polylactic acid resin, and biodegradable polyester resins. Two or more kinds can be mixed and used.

The polymer (B) having an epoxy group (also simply referred to as polymer (B)) is a component responsible for increasing the melt viscosity and melt tension of the thermoplastic resin composition. The polymer (B) is obtained by polymerizing a vinyl monomer having an epoxy group and another vinyl monomer. Examples of the vinyl monomer having an epoxy group include glycidyl (meth) acrylate, (meth) acrylic acid ester having a cyclohexene oxide structure, and (meth) allyl glycidyl ether. A preferred vinyl monomer having an epoxy group is glycidyl (meth) acrylate.
Other vinyl monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms (alkyl group may be linear or branched) such as cyclohexyl acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, etc. Ester, (meth) acrylic acid polyalkylene glycol ester, (meth) acrylic acid alkoxyalkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid dialkylaminoalkyl ester, (meth) acrylic acid benzyl ester, (meta ) Phenoxyalkyl ester of acrylic acid (Meth) acrylic acid isobornyl ester, (meth) acrylic acid alkoxysilyl alkyl esters. (Meth) acrylamide, (meth) acrylic dialkylamide, vinyl esters such as vinyl acetate, vinyl ethers, (meth) allyl ethers, aromatic vinyl monomers such as styrene and α-methylstyrene, ethylene, propylene, etc. Alpha olefin monomers can also be used. These can use 1 type, or 2 or more types.

  In designing the vinyl monomer composition used in the polymer (B), a vinyl monomer can be selected in accordance with the purpose of the present invention and the purpose of imparting other functions. For example, when transparency is required as the performance of the obtained molded product, it is preferable to select a vinyl monomer having a refractive index close to that of the thermoplastic resin (A). When the thermoplastic resin (A) is polyethylene terephthalate (refractive index: about 1.565), other vinyl monomers include aromatic vinyl monomers such as styrene and α-methylstyrene having a high refractive index. preferable. In addition, when the molded article to be obtained is required to have flexibility, the vinyl monomer having a low glass transition temperature such as butyl (meth) acrylate or ethyl (meth) acrylate is used as another vinyl monomer. Is preferred. Further, when the polymer (B) also has a function as a compatibilizer, for example, when targeting a polyethylene terephthalate / polyolefin blend composition or a polycarbonate / polyolefin composition, as other vinyl monomers, It is preferable to use olefinic vinyl monomers such as ethylene, propylene and butadiene.

  The polymer (B) preferably contains a vinyl monomer unit having an epoxy group and other vinyl monomer units in a proportion of 1 to 70% by mass and 30 to 99% by mass, respectively, and 5 to 60% by mass, respectively. % And 40 to 95% by mass are more preferable, and 10 to 50% by mass and 50 to 90% by mass are more preferable. When the proportion of the vinyl monomer unit having an epoxy group is less than 1% by mass, the effect of increasing the melt tension of the thermoplastic resin composition is small, and the desired molded product without suppressing the drawdown phenomenon It may not be possible to obtain the shape. Moreover, when the ratio of the vinyl monomer unit which has an epoxy group exceeds 70 mass%, a thermoplastic resin composition is shape | molded by the excessive crosslinking reaction of a thermoplastic resin (A) and a polymer (B). There are cases where a cross-linked product is formed in the machine and a molded product having a desired shape cannot be obtained.

The number of average epoxy groups per molecule of the polymer (B) is preferably 1.2 or more. More preferably, it is 1.5-100, More preferably, it is 2.0-50.
The number of average epoxy groups per molecule of the polymer (B) can be determined from the following formula (1).
Average number of epoxy groups = a × b / 100c (1)
In the formula (1), a, b and c are as follows.
a: Ratio (% by mass) of a vinyl monomer unit having an epoxy group contained in the polymer (B)
b: Number average molecular weight of polymer (B) c: Molecular weight of vinyl monomer having epoxy group Polymer (B) If the number of average epoxy groups per molecule is less than 1.2, The effect of increasing the melt viscosity and melt tension of the plastic resin composition is small, and the drawdown phenomenon may not be improved.

  The number average molecular weight of the polymer (B) is preferably 300 to 30000, more preferably 350 to 25000, and still more preferably 400 to 20000. When the number average molecular weight is less than 300, the number of average epoxy groups per molecule of the polymer (B) decreases, and therefore the effect of increasing the melt viscosity and melt tension of the thermoplastic resin composition becomes insufficient. There is. On the other hand, if the number average molecular weight exceeds 30000, the number of average epoxy groups per molecule of the polymer (B) increases, and the thermoplastic resin composition causes an excessive crosslinking reaction in the molding machine to deteriorate the moldability. There is a case.

  The polymer (B) can be produced by any method such as a bulk polymerization method, a solution polymerization method, and an emulsion polymerization method. A preferred method is a continuous bulk polymerization method, and a more preferred method is a high temperature continuous bulk polymerization method. The polymerization temperature is preferably 130 to 350 ° C, more preferably 150 to 330 ° C, and even more preferably 170 to 270 ° C. At the above polymerization temperature, a polymer having a desired molecular weight can be efficiently obtained by using no radical polymerization initiator or chain transfer agent or using a very small amount. When the polymerization temperature is lower than 130 ° C., a large amount of radical polymerization initiator or chain transfer agent is required to obtain the target molecular weight, and thus the resulting polymer is likely to contain many impurities. Therefore, problems such as coloring and off-flavor may occur in the thermoplastic resin composition or molded product. When the polymerization temperature exceeds 350 ° C., thermal decomposition of the polymer occurs, and the target polymer may not be obtained efficiently.

  Such high-temperature continuous polymerization may be carried out in accordance with known methods disclosed in JP-T-57-502171, JP-A-59-6207, JP-A-60-21.5007, and the like. For example, after setting a reactor capable of pressurization to a predetermined temperature under pressure, a vinyl monomer mixture comprising each vinyl monomer and, if necessary, a polymerization solvent is supplied to the reactor at a constant supply rate. And a method of extracting a polymerization reaction solution in an amount commensurate with the supply amount of the vinyl monomer mixture. Moreover, a polymerization initiator can also be mix | blended with a vinyl monomer mixture as needed. In this case, the blending amount is preferably 0.001 to 2% by mass with respect to 100% by mass of the vinyl monomer mixture. The pressure depends on the reaction temperature, the vinyl monomer mixture to be used and the boiling point of the solvent, and does not affect the reaction. Any pressure can be used as long as the reaction temperature can be maintained. The residence time of the monomer mixture in the reactor is preferably 1 to 60 minutes. If the residence time is less than 1 minute, the monomer may not sufficiently react, and if it exceeds 60 minutes, the productivity may deteriorate. The preferred residence time is 2 to 40 minutes.

  The ratio of the polymer (B) contained in the thermoplastic resin composition is 0.1 to 5% by mass, preferably 0.3 to 3% by mass, based on 100% by mass of the thermoplastic resin (A). More preferably, it is 0.5-2 mass%. When the proportion of the component (B) is less than 0.1%, the effect of improving the melt tension of the thermoplastic resin composition is poor, and the dimensional stability of the molded product becomes insufficient. Moreover, when the ratio of (B) component exceeds 5 mass%, the crosslinked material will produce | generate at the time of shaping | molding, and the problem which becomes a low gloss and opaque molded article will generate | occur | produce.

  The catalyst (C) is a component for promoting the reaction between the functional group having reactivity with the epoxy group and the epoxy group. Any compound having a function of promoting the reaction between the functional group having reactivity with the epoxy group and the epoxy group can be used, and a metal salt compound is preferably used. Specific examples include sodium stearate, calcium stearate, aluminum stearate, magnesium stearate, zinc stearate, lead stearate, cadmium stearate, lithium stearate, barium stearate, zinc laurate, zinc ricinoleate, 2- Organic fatty acid metal salts such as zinc ethylhexoate, aluminum 12-hydroxystearate, zinc 12-hydroxystearate. Aromatic carboxylic acid metal salts such as sodium benzoate, calcium benzoate, magnesium benzoate, and aluminum benzoate. Acid pyrophosphates such as sodium pyrophosphate, potassium pyrophosphate, aluminum pyrophosphate and sodium dihydrogen pyrophosphate. Metal phosphates such as sodium phosphate, aluminum phosphate, calcium phosphate. Metal salts of acidic phosphates such as sodium stearyl phosphite, calcium stearyl phosphite, aluminum stearyl phosphite, zinc stearyl phosphite. Examples include chlorides such as sodium chloride, calcium chloride, magnesium chloride, and zinc chloride. Since the compatibility with the thermoplastic resin (A) is good, organic acid metal salts, organic carboxylic acid metal salts, and metal salts of acidic phosphoric acid esters are preferred as the catalyst (C). Zinc stearate, aluminum stearate, barium stearate and sodium benzoate are particularly preferred.

  The ratio of the catalyst (C) contained in a thermoplastic resin composition is 1.0-50 mass ppm on the basis of a thermoplastic resin (A), Preferably it is 2.0-35 mass ppm. When the proportion of the component (C) is less than 1.0 ppm by mass, the effect of improving the melt tension of the thermoplastic resin composition is poor, and the dimensional stability of the molded product becomes insufficient. On the other hand, when the proportion of the component (C) exceeds 50 mass ppm, the melt tension and the melt viscosity are lowered, and the dimensional stability of the molded product becomes insufficient. Therefore, the use ratio of the catalyst (C) is a very important condition for the present invention.

The thermoplastic resin composition preferably contains a compound (D) (also referred to as a carboxyl compound (D)) other than the thermoplastic resin (A) having one carboxyl group.
The carboxyl compound (D) adjusts the melt viscosity and melt tension of the thermoplastic resin composition, and prevents molding defects caused by gelation before or during the molding of the thermoplastic resin composition. It is a component. “Other than the component (A)” means a compound having only one carboxyl group among those defined as “thermoplastic resin (A) having a functional group reactive with an epoxy group” ( For example, a polyester resin having one carboxyl group and one hydroxyl group at two terminals) is also included, but such (A) component is clearly expressed as being excluded from the carboxyl compound (D).
All or part of the carboxyl groups of the carboxyl compound (D) must not form a salt with a metal such as sodium, potassium, magnesium or calcium. The reason is that those forming a salt with these metals do not sufficiently exhibit the effect of preventing the molding defects of the thermoplastic resin composition.
Specific examples of the carboxyl compound (D) include lower aliphatic carboxylic acid compounds such as acetic acid, butyric acid, isobutyric acid, pentanoic acid and isopentanoic acid, and decanoic acid, undecanoic acid, lauric acid, palmitic acid, oleic acid, and stearic acid. Higher aliphatic carboxylic acid compounds such as benzoic acid, methylbenzoic acid, 4-ethylbenzoic acid, 2,4-dimethylbenzoic acid, o-tolylacetic acid, m-tolylacetic acid, p-tolylacetic acid, 2-phenylbutyric acid And aromatic carboxylic acid compounds such as 4-phenylbutyric acid, 1-naphthoic acid and 2-naphthoic acid. Preference is given to benzoic acid and stearic acid. Monofunctional carboxylic acid anhydrides such as benzoic anhydride, butyric anhydride, hexanoic anhydride, propionic anhydride and the like are converted into compounds having one carboxyl group by hydrolysis and are therefore included in the carboxyl compound (D). Dihydric carboxylic acid anhydrides such as phthalic anhydride and maleic anhydride are not included in the carboxyl compound (D) because they are converted into compounds having two carboxyl groups by hydrolysis.

  As the carboxyl compound (D), a carboxylic acid compound having 5 or more carbon atoms is preferable, and an aromatic carboxylic acid compound is more preferable. When the carboxyl compound (D) is an aromatic carboxylic acid compound, there is an effect of improving the compatibility of the thermoplastic resin (A) and the polymer (B) which are components of the thermoplastic resin composition. Molded products are preferred because they tend to be more homogeneous.

  The carboxyl compound (D) preferably has a boiling point of 100 ° C. or higher. 150 degreeC or more is more preferable, and 200 degreeC or more is further more preferable. When the boiling point is less than 100 ° C., the carboxyl compound (D) is easily diffused during the heating and melting process in the production of the composition. Therefore, it is difficult to control the concentration in the composition, and the working environment is unsanitary or unsafe. There is also a case.

  The ratio of the carboxyl compound (D) contained in the thermoplastic resin composition is preferably from 0.3 to 10 mass ppm, more preferably from 0.5 to 5 mass ppm, based on the thermoplastic resin (A). When the ratio of the component (D) is less than 0.3 ppm by mass, a cross-linked product may be generated at the time of molding, which may cause a problem of forming a molded product with low gloss and opaqueness. Moreover, when the ratio of (D) component exceeds 10 mass ppm, the fall of melt tension and melt viscosity will be caused, and the dimensional stability of a molded article may become inadequate.

The thermoplastic resin composition is obtained by mixing the thermoplastic resin (A), the polymer (B), the catalyst (C) and, if necessary, the carboxyl compound (D) by an arbitrary method. For example, single-screw extruder, meshing same-direction parallel-shaft twin-screw extruder, mesh-type different-direction parallel-shaft twin-screw extruder, mesh-type different-direction oblique-shaft twin-screw extruder, non-meshing-type twin-screw extrusion Each raw material is mixed by an extruder, a kneader, etc. such as an incompletely meshing twin screw extruder, a kneader extruder, a planetary gear extruder, a transfer mix extruder, a ram extruder, a roller extruder, etc. Is obtained. Prior to the mixing, the raw materials can be premixed using a Henschel mixer, a tumbler, or the like.
As raw material components of the thermoplastic resin composition, those having an arbitrary shape or property such as a pellet shape, a powder shape, and a liquid can be used.

The polymer (B), the catalyst (C), and, if necessary, the carboxyl compound (D) are prepared in advance as a masterbatch mixed with a certain amount of thermoplastic resin, and the masterbatch and the thermoplastic resin (A) Can be mixed to produce a thermoplastic resin composition (hereinafter also referred to as a master batch method). The masterbatch method is a preferable method because the catalyst (C) and the carboxyl compound (D), which are relatively small amounts of components, are easily mixed uniformly in the thermoplastic resin composition. The thermoplastic resin used for the preparation of the masterbatch may be a thermoplastic resin (A), or a thermoplastic resin (E) having no functional group having reactivity with an epoxy group (simply a thermoplastic resin). (It may also be referred to as (E).), Or both may be used in combination.
The preparation of the masterbatch and the production of the thermoplastic resin composition by mixing the masterbatch and the thermoplastic resin (A) can be performed using the above-explained extruder or kneader.

When the thermoplastic resin used for the preparation of the masterbatch is the thermoplastic resin (A), in the preparation process of the masterbatch, the total amount of the thermoplastic resin (A) that is finally blended in the thermoplastic resin composition Some of them are used. The thermoplastic resin (A) is 30 to 85% by mass based on the total amount of 100% by mass of the thermoplastic resin (A), polymer (B), catalyst (C) and carboxyl compound (D) in the masterbatch. In addition, the total amount of the polymer (B), the catalyst (C) and the carboxyl compound (D) is preferably 15 to 70% by mass. The thermoplastic resin (A) is 40 to 80% by mass, and the total amount of the polymer (B), the catalyst (C) and the carboxyl compound (D) is more preferably 20 to 60% by mass, and the thermoplastic resin. (A) is 45 to 75% by mass, and the total amount of the polymer (B), the catalyst (C) and the carboxyl compound (D) is more preferably 25 to 55% by mass.
By using such a masterbatch, the thermoplastic resin composition has a particularly large melt viscosity and melt tension, and gives a molded product having excellent dimensional stability.
When a thermoplastic resin composition is produced using a masterbatch containing the thermoplastic resin (A) prepared as described above, the amount of the thermoplastic resin (A) to be mixed with the masterbatch is finally determined. The amount of the thermoplastic resin (A) used for preparing the masterbatch is subtracted from the total amount of the thermoplastic resin (A) blended in the thermoplastic resin composition.

The masterbatch can be prepared using the thermoplastic resin (E) without using the thermoplastic resin (A). The thermoplastic resin (E) is 30 to 85% by mass based on the total amount of 100% by mass of the thermoplastic resin (E), polymer (B), catalyst (C) and carboxyl compound (D) in the masterbatch. In addition, the total amount of the polymer (B), the catalyst (C) and the carboxyl compound (D) is preferably 15 to 70% by mass. The thermoplastic resin (E) is 40 to 80% by mass, and the total amount of the polymer (B), the catalyst (C) and the carboxyl compound (D) is more preferably 20 to 60% by mass, and the thermoplastic resin. (E) is 45 to 75% by mass, and the total amount of the polymer (B), the catalyst (C) and the carboxyl compound (D) is more preferably 25 to 55% by mass.
By using such a masterbatch, the thermoplastic resin composition has a particularly large melt viscosity and melt tension, and gives a molded product having excellent dimensional stability.
When producing a thermoplastic resin composition using a masterbatch that does not contain the thermoplastic resin (A) prepared as described above, the amount of the thermoplastic resin (A) mixed with the masterbatch is the final amount. Thus, the total amount of the thermoplastic resin (A) blended in the thermoplastic resin composition is obtained.

  When the master batch is manufactured by using the thermoplastic resin (A) and the thermoplastic resin (E) in combination, the ratio of the thermoplastic resin (A) or (E) in the above master batch manufacturing procedure is prepared as the master batch. The total amount of the thermoplastic resin (A) and the thermoplastic resin (E) used in the above may be designed.

  The thermoplastic resin used for preparing the masterbatch is preferably partly or wholly the thermoplastic resin (A). The reason is that the thermoplastic resin composition tends to have particularly good characteristics as described above.

  Examples of thermoplastic resins (E) used for masterbatch preparation include low density polyethylene resin, high density polyethylene resin, polypropylene resin, ethylene / propylene copolymer, ethylene vinyl acetate copolymer, polyethylene / ethyl acrylate Polyolefin resins such as copolymers, polystyrene resins, acrylonitrile / styrene copolymers, styrene resins such as methyl methacrylate / styrene copolymers, acrylonitrile / butadiene / styrene copolymers, and acrylic resins such as polymethyl methacrylate resins. Etc. Polyolefin resin and polystyrene resin are preferable as the thermoplastic resin (E).

  The thermoplastic resin composition includes a thermoplastic pigment (A), a polymer (B) and a catalyst (C), and optionally a carboxyl compound (D) and a thermoplastic resin (E). A plasticizer, a fluidity adjusting agent, a crystal nucleating agent, or other known components that can be blended in a thermoplastic resin may be added.

A thermoplastic resin composition can be used for manufacture of various molded articles using an extrusion molding machine or an injection molding machine. Molded products obtained from thermoplastic resin compositions include extruded products such as sheets and films, calendered products, deformed extruded products such as pipes and baseboards, injection molded products, blow molded products such as bottles, and draw molding. Products.
Since the thermoplastic resin composition of the present invention is excellent in resistance to drawdown, the method of producing a molded product with an extruder is a preferable method in that the features of the present invention are effectively used. As a preferable molded product, a transparent sheet / transparent film obtained by an extruder, and an irregularly shaped product are exemplified.

(Production of polymer 1)
The oil jacket temperature of a 1 liter pressurized stirred tank reactor equipped with an oil jacket was kept at 200 ° C. On the other hand, 69 parts by mass of styrene (hereinafter referred to as St), 30 parts by mass of glycidyl methacrylate (hereinafter referred to as GMA), 1 part by mass of methyl methacrylate (hereinafter referred to as MMA), 15 parts by mass of xylene and diter as a polymerization initiator. A monomer mixed liquid consisting of 0.5 parts by mass of shary butyl peroxide (hereinafter referred to as DTBP) was charged into a raw material tank. The monomer mixture is continuously supplied from the raw material tank to the reactor at a constant supply rate (48 g / min, average residence time in the reactor: 12 minutes) so that the content liquid mass in the reactor becomes constant at about 580 g. The reaction solution was continuously withdrawn from the outlet of the reactor. At that time, the internal temperature of the reactor was kept at about 210 ° C.
After 36 minutes have passed since the temperature inside the reactor has stabilized, the extracted reaction solution is continuously removed by a thin film evaporator maintained at a reduced pressure of 30 kPa and a temperature of 250 ° C. Polymer 1 which does not contain was recovered. About 7 kg of polymer 1 was recovered over 180 minutes.
The number average molecular weight (hereinafter referred to as Mn) of the polymer 1 in terms of polystyrene determined from a gel permeation chromatograph (hereinafter referred to as GPC) is 2900, and the weight average molecular weight (hereinafter referred to as Mw) is 9900. Met. The average number of epoxy groups (hereinafter referred to as Fn) contained per molecule of the polymer was 6.1.

(Production of polymer 2)
Except for using a monomer mixed solution of St 38 parts by mass, butyl acrylate (hereinafter referred to as BA) 8 parts by mass, GMA 25 parts by mass, MMA 29 parts by mass, xylene 15 parts by mass, and DTBP 0.3 parts by mass. A polymer 2 was produced in the same manner as in the production of the union 1.
The Mn of the polymer 2 in terms of polystyrene determined from GPC was 2900, and Mw was 10800. Fn was 5.1.

(Production of polymers 3 and 4)
Polymers 3 and 4 were produced by the same production method as that for polymer 1 except that the composition of the raw material monomers was as shown in Table 1. The values of Mn, Mw and Fn are shown in Table 1.

(Preparation of masterbatches 1-17)
As a master batch thermoplastic resin (hereinafter also referred to as a vehicle), Easter 6863 (hereinafter referred to as PET-G) manufactured by Eastman Chemical Co., which is an amorphous copolyester resin, was used. 69-927 parts by mass of PET-G, 30 parts by mass of polymer 1, 0.075 parts by mass of zinc stearate were uniformly premixed with a Henschel mixer, and then the same-direction parallel-shaft twin-screw extruder (Plastic Engineering Research) Master batch 1 was obtained by melt-kneading in ST-40).
Moreover, except having made the kind and quantity of a raw material as Table 2, the masterbatch 2-17 was prepared by the same method as preparation of the masterbatch 1. FIG.

(Manufacture of thermoplastic resin composition 1)
The thermoplastic resin and the masterbatch were mixed using the same direction parallel shaft twin screw extruder. A thermoplastic resin composition having the composition shown in Table 3 and a comparative composition having the composition shown in Table 4 were prepared at 280 ° C. In Table 3 and Table 4, R-PET means recycled PET (YPR clear pellets manufactured by Yono Pet Recycle Co., Ltd.). The column of “Composition content” in Table 3 and Table 4 shows the type and amount of each component contained in the composition.

(Evaluation of moldability of thermoplastic resin composition 1)
The moldability of the thermoplastic resin composition and the comparative composition was measured for melt viscosity and die swell using a capillary rheometer (Capillograph Type 1C manufactured by Toyo Seiki Co., Ltd.). A die having a hole diameter of 1 mm and a thickness of 10 mm was used under the conditions of a measurement temperature of 280 ° C. and a shear rate of 182 sec ⁻¹ . Table 5 shows the measurement results of melt viscosity and die swell of Examples 1 to 14 and Comparative Examples 1 to 7. The die swell is the thickness of the resin composition extruded from the hole of the die, and the larger the value, the easier it is to manufacture a molded product with good dimensional stability.

In Examples 1 to 3, it was confirmed that the value of the die swell was larger than that of Comparative Example 1 and the melt tension was increased. Further, as shown in FIG. 1, in Examples 1, 2 and 3 (concentrations of aluminum stearate as catalyst (C) of 5 ppm, 25 ppm and 37.5 ppm) using polymer 1 as component (B), It was found that the value of the die swell was larger than those of Comparative Examples 2 and 6 using the coalesced 1 (the aluminum stearate concentrations were 0 ppm and 75 ppm).
In Examples 5 to 7 and 12, even in the case of zinc stearate, sodium benzoate, and sodium benzoate / zinc stearate mixed catalyst, a remarkable thickening effect was confirmed as in Example 1.

In Examples 8 to 9 using the polymer 2 as the component (B), it was confirmed that the thickening effect by the addition of the catalyst was improved as compared with the comparative example 3 using the polymer 2.
In Examples 10 to 11 using the polymer 3 as the component (B), it was confirmed that the thickening effect by adding the catalyst was improved as compared with the comparative example 4 using the polymer 3.
In Examples 13 to 14 using the polymer 4 as the component (B), it was confirmed that the thickening effect by addition of the catalyst was improved as compared with the comparative example 7 using the polymer 4.

(Production of thermoplastic resin composition 2)
The polylactic acid resin (hereinafter referred to as PLA) and the polymer 1 were mixed using the same direction parallel shaft twin screw extruder. A thermoplastic resin composition having the composition shown in Table 6 was prepared at 200 ° C. PLA shown in Table 6 was PLA # 5403 manufactured by Toyota Motor Corporation.

(Formability evaluation 2 of thermoplastic resin composition)
The moldability of the thermoplastic resin composition and the comparative composition was measured for melt viscosity and die swell using a capillary rheometer (Capillograph Type 1C manufactured by Toyo Seiki Co., Ltd.). A die having a hole diameter of 1 mm and a thickness of 10 mm was used under the conditions of a measurement temperature of 200 ° C. and a shear rate of 182 sec ⁻¹ . Table 6 shows the melt viscosity and die swell measurement results of Example 15 and Comparative Examples 8-9.

Example 15 in which polymer 1 and component (C) zinc stearate were blended included Comparative Example 8 that did not contain either polymer 1 or component (C), polymer 1 but component (C). It was confirmed that the melt viscosity was higher than that of Comparative Example 9 not containing.

Since the thermoplastic resin composition of the present invention is a material having high melt tension and excellent dimensional stability during melt molding, it is an extrusion-molded product such as a sheet and a film, a profile extrusion-molded product, a draw-molded product, Suitable for blow molded products.

The figure which shows the relationship between the catalyst (C) (aluminum stearate) density | concentration in a composition, and a moldability (die swell evaluation).

Claims (14)

Thermoplastic resin (A) having a functional group having reactivity with an epoxy group, polymer (B) having an epoxy group, and catalyst for promoting the reaction between the functional group having reactivity with an epoxy group and the epoxy group ( C), and the ratio of the polymer (B) and the catalyst (C) based on the thermoplastic resin (A) is 0.1 to 5% by mass and 1.0 to 50 ppm, respectively. . The thermoplastic resin (A) is selected from the group consisting of a polyester resin having a functional group reactive with an epoxy group, a polycarbonate resin, a polyamide resin, a polyphenylene ether resin, and a polylactic acid resin. The thermoplastic resin composition as described. The thermoplastic resin composition according to claim 1, wherein the polymer (B) is a vinyl polymer having an epoxy group. The thermoplastic resin composition according to claim 1, wherein the polymer (B) is a polymer having 1.2 or more polymer-average molecular epoxy groups. The thermoplastic resin composition according to claim 1, wherein the polymer (B) is a polymer having a number average molecular weight of 300 to 30,000. The thermoplastic resin composition according to claim 1, wherein the catalyst (C) is a carboxylic acid metal salt compound. The thermoplastic resin composition according to claim 6, wherein the catalyst (C) is a benzoic acid metal salt compound or a stearic acid metal salt compound. The compound (D) other than the thermoplastic resin (A) having one carboxyl group is also contained, and the ratio of the compound (D) based on the thermoplastic resin (A) is 0.3 to 10 ppm. The thermoplastic resin composition described in 1. The thermoplastic resin composition according to claim 8, wherein the compound (D) is benzoic acid or stearic acid. The thermoplastic resin composition according to claim 8, obtained by mixing the thermoplastic resin (A) and the following master batch.
Master batch: obtained by mixing thermoplastic resin (A), polymer (B), catalyst (C) and compound (D), (B) component, (C) component, (D) component and (A) The ratio of the component is the sum of the component (B), the component (C) and the component (D) on the basis of 100% by mass of the total amount of the component (B), the component (C), the component (D) and the component (A). The composition which is 15-70 mass% of quantity, and is 30-85 mass% of (A) component. The thermoplastic resin composition according to claim 8, obtained by mixing the thermoplastic resin (A) and the following master batch.
Master batch: obtained by mixing thermoplastic resin (E), polymer (B), catalyst (C) and compound (D) having no functional group having reactivity with an epoxy group, (B) component, The ratio of the component (C), the component (D) and the component (E) is based on the total amount of 100% by mass of the component (B), the component (C), the component (D) and the component (E). The composition which is 15-70 mass% of total amounts of a component, (C) component, and (D) component, and (E) component 30-85 mass%. The thermoplastic resin composition according to claim 11, wherein the thermoplastic resin (E) is selected from the group consisting of a polyolefin resin and a polystyrene resin. A molded product obtained by molding the thermoplastic resin composition according to claim 1. A sheet, a film, or a deformed product obtained by molding the thermoplastic resin composition according to claim 1 with an extruder.

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