JP5930667B2 - Styrenic resin composition for hyperbranched film and styrene resin film - Google Patents

Description

  The present invention is a highly branched product obtained by a continuous polymerization method in which a monovinyl compound essentially containing styrene and a solvent-soluble polyfunctional vinyl copolymer having a plurality of double bonds in one molecule are continuously supplied to a polymerization reactor. TECHNICAL FIELD The present invention relates to a styrene resin composition for a highly branched plate-like extruded foam containing an ultra-high molecular weight copolymer and a linear polymer, and a styrene resin film obtained therefrom, and the styrene resin composition Can produce a film having high strength and excellent moldability and stretchability during film formation, and strength and deep drawability during secondary molding. .

  A film made of a styrene-based resin composition is widely used in food packaging and envelope window materials because of its excellent transparency and printability. In recent years, it has been laminated with a polystyrene foam sheet and secondarily formed into a desired shape by thermoforming (vacuum forming, compressed air vacuum forming, hot plate forming, etc.), and is widely used as a food tray, container and the like. However, when deep drawing is performed on a styrene resin film, there is a problem that the film is insufficiently stretched and the film is torn during molding or thickness unevenness occurs.

  In order to improve the elongation and thickness unevenness of the film in deep drawing, an appropriate melt tension is required in terms of uniform melt stretching, and a balance with melt stretchability representing elongation in the molten state is important.

  As a means for controlling the melt tension and melt stretchability, it is known that a method of incorporating an ultrahigh molecular weight component into a styrene resin composition is effective.

  As a method of obtaining a resin composition containing an ultrahigh molecular weight component, for example, there is a styrene polymer composition containing a component having a molecular weight of 2 million or more described in Patent Document 1 within a certain range. In order to obtain this composition, a method in which polymerization is allowed to proceed at a low temperature before polymerization or a method in which an ultrahigh molecular weight polymer separately polymerized by anionic polymerization or the like is blended have been proposed. There are problems such as inferior properties and high costs when blending separately polymerized components.

  In order to avoid the above problem, for example, there is a styrenic polymer containing a molecular weight component of 1 million or more containing a polyfunctional vinyl compound unit described in Patent Document 2 within a certain range. In order to contain a molecular weight component, it has been proposed to polymerize by adding a very small amount of an aromatic polyfunctional vinyl compound typified by an aromatic divinyl compound to a vinyl monomer. However, when this means is applied to continuous bulk polymerization, when a long-term reaction is continued, there is a problem that gelation proceeds in a region where the flow called a boundary film existing on the wall of the polymerization reactor is stopped, When trying to avoid the above, the amount of the polyfunctional aromatic vinyl compound was limited, and it was difficult to produce a desirable amount of ultrahigh molecular weight component.

  Furthermore, Patent Document 3 discloses a method in which an ultrahigh molecular weight component having a branched structure is contained in a styrene copolymer using a polyfunctional polymerization initiator. However, in this method, the entire styrene polymer is expensive. The molecular weight tends to increase, and if a large amount of chain transfer agent is used to avoid this, the effect becomes insufficient. Patent Document 4 discloses a method for controlling the degree of polymerization of a styrenic resin by using a polyfunctional aromatic vinyl compound and a chain transfer agent in the same manner as in the case of using a polyfunctional initiator. In addition to offsetting the effect, the use of mercaptans as chain transfer agents has a problem that the range of use is limited due to the problem of specific odor. Patent Document 5 discloses that a styrene-based resin composition composed of linear polystyrene and multi-branched polystyrene obtained using a multi-branched macromonomer has excellent melt tension, but improvement in melt stretchability is It is insufficient.

Japanese Examined Patent Publication No. 62-61231 JP-A-2-170806 JP-A-8-59721 JP 2002-241413 A JP 2003-292707 A

  In order to improve the thermoformability of the film, the present invention is excellent in the balance between melt tension and melt stretchability, has no gel-like material, and contains a highly branched ultrahigh molecular weight copolymer and a linear polymer. It aims at providing the styrene resin composition for films, and the film obtained from it.

  That is, this invention is the styrene resin composition for hyperbranched films as described below, the manufacturing method of a styrene resin film, and a styrene resin film.

(1) A raw material obtained by adding 100 ppm to 3000 ppm of a solvent-soluble polyfunctional vinyl copolymer having an average of two or more vinyl groups in one molecule and having a branched structure to a monovinyl compound essentially containing styrene. The solvent-soluble polyfunctional vinyl copolymer and the monovinyl compound, which are obtained by continuously supplying a solution to a polymerization reactor in which one or more solutions are continuously arranged to advance the polymerization reaction, are produced. A styrene resin composition comprising a hyperbranched ultra-high molecular weight copolymer and a linear polymer produced by polymerization of the monovinyl compound, having a weight average molecular weight (Mw) of 200,000 to 500,000, and a Z average The ratio (Mz / Mw) of the molecular weight (Mz) to the weight average molecular weight (Mw) is 2.2 to 5.0, and the branching ratio gM at a molecular weight of 1,000,000 to 1,500,000 is 0.85 to 0.40. Be Branched film for styrenic resin composition.

（式中、Ｒ¹はジビニル化合物に由来する炭化水素基を示す。） (2) The solvent-soluble polyfunctional vinyl copolymer is obtained by polymerizing a monovinyl compound copolymerizable with a divinyl compound, and further contains a pendant vinyl group-containing unit derived from the divinyl compound represented by the following formula (a1). It is contained in the structural unit in the range of 0.10 to 0.50 as the molar fraction, and the ratio of the inertial radius (nm) in the weight average molecular weight to the molar fraction is in the range of 10 to 80. (1) Styrenic resin composition for highly branched film.

(In the formula, R ¹ represents a hydrocarbon group derived from a divinyl compound.)

(3) A method for producing a styrene resin film, comprising extruding the styrene resin composition for a hyperbranched film according to any one of (1) and (2) above.

(4) A styrene-based resin film obtained by the production method according to (3) above.

  The highly branched styrene resin composition for a highly branched film containing the highly branched ultrahigh molecular weight copolymer and the linear polymer of the present invention is excellent in the balance between melt tension and melt stretchability. Excellent moldability, suitable for deep drawing, and uniform wall thickness.

  Hereinafter, the present invention will be described in detail. As a method for producing a styrene resin composition for a highly branched film of the present invention (hereinafter also referred to as a styrene resin composition), a monovinyl compound containing styrene and a solvent-soluble polyfunctional vinyl copolymer (hereinafter referred to as a polyfunctional vinyl). (Also called a copolymer) and, if necessary, a solvent, a polymerization catalyst, a chain transfer agent, and the like are added and mixed to remove one or more reactors arranged in series and / or in parallel and unreacted monomers, etc. A so-called continuous bulk polymerization method in which monomers are continuously fed into an equipment equipped with a devolatilization step and the polymerization proceeds in a stepwise manner is preferably used. Examples of the reactor type include a fully mixed tank reactor, a column reactor having plug flow properties, and a loop reactor in which a part of the polymerization liquid is withdrawn while the polymerization proceeds. There are no particular restrictions on the order of arrangement of these reactors, but in order to suppress the formation of gel-like materials in continuous production, the polyfunctional vinyl copolymer is unreacted and is not present in the reactor wall film. It is important not to develop a state of staying at a high concentration, and it is preferable to select a fully mixed tank reactor as the first reactor. The devolatilization process includes a vacuum devolatilization tank with a heater, a vented devolatilization extruder, and the like. The polymer in the molten state that has exited the devolatilization step is transferred to the granulation step. In the granulation step, the molten resin is extruded in a strand form from a porous die and processed into a pellet shape by a cold cut method, an air hot cut method, or an underwater hot cut method. One or more polymerization reactors are arranged in succession, but in the case of one, one may be used alone, and in the case of two or more, at least two are arranged in series (in series).

  The raw material solution contains a monovinyl compound containing styrene and a polyfunctional vinyl copolymer. The polyfunctional vinyl copolymer, which is a constituent element of the styrene resin composition of the present invention, can be added from the middle of the above reactor as necessary in a state dissolved in monovinyl compounds, a polymerization solvent or the like. .

  The monovinyl compound essentially containing styrene used as a raw material of the styrene resin composition of the present invention (hereinafter also referred to as styrene monomer) may be 100% styrene, and includes styrene and other monovinyl compounds. It may be a mixture. Other monovinyl compounds may be those having an olefinic double bond copolymerizable with styrene, such as aromatic vinyl monomers such as paramethylstyrene, acrylic acid monomers such as acrylic acid and methacrylic acid, and acrylonitrile. , Vinyl cyanide monomers such as methacrylonitrile, acrylic monomers such as butyl acrylate and methyl methacrylate, α, β-ethylenically unsaturated carboxylic acids such as maleic anhydride and fumaric acid, and imides such as phenylmaleimide and cyclohexylmaleimide Based monomers. These other vinyl monomers can be used alone or in combination of two or more. And it is preferable that the ratio of styrene and another monovinyl compound is 50-100 mol% of styrene, and 0-50 mol% of other monovinyl compounds, in order to make use of the characteristic of a styrene resin composition.

  The polyfunctional vinyl copolymer used as a raw material for the styrenic resin composition of the present invention provides a highly branched styrene resin having a high degree of branching by being copolymerized with a styrenic monomer. .

  The polyfunctional vinyl copolymer can be obtained according to the methods disclosed in JP-A No. 2004-123873, JP-A No. 2005-213443, WO 2009/110453, and the like. Specifically, a divinyl compound and at least one monovinyl compound are used for copolymerization to obtain a copolymer having a reactive pendant vinyl group represented by the formula (a1). Furthermore, as described in the above-mentioned patent document, those having other terminal groups other than vinyl groups introduced at the terminals can also be used, particularly for compounds having an unsaturated bond in the molecule such as phenoxy methacrylates. In addition to (a1), it is possible to use a terminal-modified one because it can act as a crosslinking point. In this case, since the terminal unsaturated bond-containing structural unit (a2) also has a vinyl group, the total molar fraction (a3) with the structural unit of the formula (a1) indicates the total amount of vinyl groups present. It will be.

  Examples of divinyl compounds used to obtain polyfunctional vinyl copolymers include divinyl aromatic compounds represented by divinylbenzene and aliphatic and alicyclic (meth) acrylates represented by ethylene glycol di (meth) acrylate. Examples are shown.

  Moreover, as a monovinyl compound used here, the monovinyl compounds containing monovinyl aromatic compounds, such as styrene as mentioned above, are mentioned.

  As a method for producing a polyfunctional vinyl copolymer, for example, two or more kinds of compounds selected from divinyl aromatic compounds, monovinyl aromatic compounds and other monovinyl compounds are used as promoters selected from Lewis acid catalysts and ester compounds. It can be obtained by cationic copolymerization in the presence. Further, when a (meth) acrylate divinyl or monovinyl compound is used, the reaction does not proceed in cationic polymerization, and therefore, it can be obtained by radical polymerization in the presence of a radical catalyst such as peroxide.

  The amount of divinyl compound and monovinyl compound used is determined so as to give the composition of the polyfunctional vinyl copolymer used in the present invention. The divinyl compound is preferably used in an amount of 10 to 90 mol% of the total monomers. Preferably 30 to 90 mol% is used. The monovinyl compound is preferably used in an amount of 90 to 10 mol%, more preferably 70 to 10 mol% of the total monomers. Here, in cationic polymerization like 2-phenoxyethyl methacrylate, what acts as a terminal modifier is not calculated as a monomer.

  The Lewis acid catalyst used in the production of the polyfunctional vinyl copolymer is not particularly limited as long as it is a compound composed of a metal ion (acid) and a ligand (base) and can receive an electron pair. Can be used. From the viewpoints of control of molecular weight and molecular weight distribution and polymerization activity, boron trifluoride ether (diethyl ether, dimethyl ether, etc.) complexes are most preferably used. The Lewis acid catalyst is used in the range of 0.001 to 10 mol, more preferably 0.001 to 0.01 mol, per 1 mol of the monomer compound. An excessive amount of the Lewis acid catalyst is not preferable because the polymerization rate becomes too high and it becomes difficult to control the molecular weight distribution.

  Examples of the cocatalyst include one or more selected from ester compounds. Among them, an ester compound having 4 to 30 carbon atoms is preferably used from the viewpoint of controlling the polymerization rate and the molecular weight distribution of the copolymer. From the viewpoint of availability, ethyl acetate, propyl acetate and butyl acetate are preferably used. The cocatalyst is used in the range of 0.001 to 10 mol, more preferably 0.01 to 1 mol, relative to 1 mol of the monomer compound. When the amount of the cocatalyst used is excessive, the polymerization rate decreases and the yield of the copolymer decreases. On the other hand, when the amount of the cocatalyst used is too small, the selectivity of the polymerization reaction is lowered, the molecular weight distribution is increased, the gel is generated, and the polymerization reaction is difficult to control.

  In addition, as a catalyst used for producing a polyfunctional vinyl copolymer by radical polymerization, simple compounds such as azo compounds represented by azobisisobutyronitrile, dibenzoyl peroxide, t-butylperoxybenzoate and the like can be used. Examples of functional peroxides and bifunctional or higher functional peroxides such as 1,1-bis (t-butylperoxy) cyclohexane are exemplified, and they are used alone or in combination of two or more. be able to.

  The polyfunctional vinyl copolymer used in the present invention can be obtained by the above production method, but it is necessary to leave a part of the vinyl group of the divinyl compound used as a monomer without polymerizing. . Then, on average, 2 or more, preferably 3 or more vinyl groups are present in one molecule. This vinyl group exists mainly as a structural unit represented by the above formula (a1). Then, by leaving a part of the vinyl group without being polymerized, the crosslinking reaction can be suppressed and solvent solubility can be imparted. Here, solvent-soluble means that it is soluble in toluene, xylene, THF (tetrahydrofuran), dichloroethane or chloroform. Specifically, in 100 g of these solvents, 5 g or more is dissolved at 25 ° C. It does not occur. On the other hand, a part of the divinyl compound needs to be crosslinked or branched by the reaction of two vinyl groups, whereby a copolymer having a branched structure can be obtained. Thus, in the present invention, one of the two vinyl groups is reacted for a part of the divinyl compound, one is left unpolymerized, and the other two are reacted together with the two vinyl groups. The polyfunctional vinyl copolymer to be used can be obtained. The polymerization method for obtaining such a polyfunctional vinyl copolymer is known as described above, and can be produced as described above.

  The weight average molecular weight (Mw) of the polyfunctional vinyl copolymer is preferably 1,000 to 100,000, and more preferably 5,000 to 70,000. If it is less than 1,000, the effect of suppressing the progress of gelation in continuous polymerization is reduced as in the case of using aromatic divinyl compounds and polyfunctional (meth) acrylates, and it is difficult to obtain sufficient effects in continuous polymerization. .

  The unit containing a vinyl group derived from a divinyl compound introduced into the polyfunctional vinyl copolymer has a structural unit represented by the above formula (a1), and the molar fraction of the structural unit (a1) is 0.10. It is good that it is -0.50. When it is less than 0.10 mol, it is difficult to obtain a high-branched styrene copolymer having a high molecular weight necessary for film use. On the other hand, when it exceeds 0.50 mol, the molecular weight of the hyperbranched styrenic copolymer is excessively increased and gelation easily occurs, and tearing occurs when the styrenic resin composition is processed into a film. It becomes easy.

Here, the structural unit (a1), the double bond (a2) derived from the terminal modifier, and the total molar fraction (a3) of both were measured using 13 J-NMR and JC-LA600 type nuclear magnetic resonance spectrometer. The structure was determined by 1H-NMR analysis. Chloroform-d1 was used as a solvent, and the tetramethylsilane resonance line was used as an internal standard.
As described above, those having a terminal modification with a compound having an unsaturated bond in the molecule, in addition to the structural unit represented by the formula (a1), the terminal unsaturated bond-containing structural unit (a2) also has a vinyl group. Therefore, it is preferable that the total molar fraction (a3) of both is 0.10 to 0.50.

  In addition, the polyfunctional vinyl copolymer requires a ratio of the radius of inertia (nm) in the weight average molecular weight to the molar fraction of the structural unit (a1) or the total molar fraction (a3) for this application. In order to adjust the hyperbranched ultrahigh molecular weight copolymer for imparting high melt tension and melt stretchability without gelation, it is preferably in the range of 10-80. When the above ratio exceeds 80, gelation does not proceed, but it is difficult to sufficiently obtain a high molecular weight highly branched styrene copolymer. On the other hand, when the molecular weight is smaller than 10, the molecular weight of the highly branched styrene-based copolymer is excessively increased, and appearance defects or tears due to minute gels are likely to occur during film production.

Here, after adjusting the sample to a 0.5% THF solution, the radius of inertia was filtered with a membrane filter, and the filtrate was measured using a GPC multi-angle light scattering method. Further, the sample was adjusted to 0.2% THF solution and allowed to stand for 1 day. After that, it is diluted with THF to four kinds of concentration (0.02, 0.05, 0.10, 0.12 wt%) solutions, and dn / dc value (inherent refractive index increment) is used with these solutions. : A value representing how much the refractive index of the polymer solution changes with respect to the change in the concentration of the solute), and the inertia radius of the sample was calculated from the obtained dn / dc value.
The polyfunctional vinyl copolymer is a polymer having a distribution in molecular weight, and naturally, since the inertia radius also has a distribution, the inertia radius in the weight average molecular weight is adopted as the average value of the overall inertia radius. is there.

  The ratio of the molar fraction of the structural unit (a1) or the total molar fraction (a3), which is an index representing the radius of inertia and the double bond content defined here, is a highly branched ultrahigh molecular weight copolymer. It can be said that this is an index indicating how many reaction points are present in the spread of the polyfunctional vinyl copolymer as a nucleus in the polymerization reaction solution. If this ratio is too small, the reaction point is in the vicinity and gelation is likely to occur, and if this ratio is too large, it is difficult to increase the molecular weight of the branched component.

  As a compounding ratio of the polyfunctional vinyl copolymer with respect to a styrene-type monomer, it is 100 ppm-3000 ppm on a weight basis, and 100 ppm-1000 ppm are more preferable. When the blending ratio of the polyfunctional vinyl copolymer is less than 100 ppm, the amount of the hyperbranched ultrahigh molecular weight copolymer formed is insufficient, and it is difficult to obtain the sufficient effect of the present invention. On the other hand, when it exceeds 3000 ppm, there is a possibility of causing poor appearance or tearing due to a fine gel during film production.

  By copolymerizing the polyfunctional vinyl copolymer and a styrene monomer, a hyperbranched ultrahigh molecular weight copolymer that is a copolymer of the polyfunctional vinyl copolymer and the styrene monomer, and styrene The styrene resin composition of the present invention, which is a mixture with a linear polymer produced only from a monomer, is obtained. When two or more kinds of styrenic monomers are used, the linear polymer becomes a copolymer.

  The weight average molecular weight (Mw) of the styrene resin composition of the present invention is 200,000 to 500,000, preferably 250,000 to 400,000. If the Mw is less than 200,000, the strength of the film is insufficient, and if the Mw is greater than 500,000, the resin viscosity increases and it becomes difficult to extrude the film. The Mw of the styrene resin composition should be controlled by the reaction temperature of the polymerization step, the residence time, the type and amount of polymerization initiator, the type and amount of chain transfer agent, the type and amount of solvent used during polymerization, etc. Can do.

The weight average molecular weight (Mw), the Z average molecular weight (Mz), and the number average molecular weight (Mn) were measured using gel permeation chromatography (GPC) under the following conditions.
GPC model: Shodex GPC-101 manufactured by Showa Denko KK
Column: Polymer Laboratories PLgel 10 μm MIXED-B
Mobile phase: Tetrahydrofuran Sample concentration: 0.2% by mass
Temperature: 40 ° C oven, 35 ° C inlet, 35 ° C detector
Detector: differential refractometer The molecular weight is measured by calculating the molecular weight at each elution time from the elution curve of monodisperse polystyrene, and calculating the molecular weight in terms of polystyrene.

  The ratio (Mz / Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw) is 2.2 to 5.0, and preferably 2.6 to 4.0. When Mz / Mw is less than 2.2, the content of the hyperbranched ultrahigh molecular weight copolymer becomes insufficient, and the sufficient effect of the present invention cannot be obtained. When Mz / Mw exceeds 5.0, the molecular weight of the hyperbranched ultra-high molecular weight copolymer is increased, and a gel is easily generated in the production process.

  The branching ratio gM in the component having a molecular weight of 1,000,000 to 1,500,000 of the styrenic resin composition of the present invention is 0.85 to 0.40, and preferably 0.80 to 0.50. The branching ratio gM represents the degree of branching of the highly branched ultrahigh molecular weight copolymer contained in the styrene resin composition, and the lower the branching ratio gM, the more branches. If the branching ratio gM exceeds 0.85, the branching is insufficient and the sufficient effect of the present invention cannot be obtained. Even if the branching ratio gM is less than 0.40 and branching is increased, no further improvement effect can be obtained.

The branching ratio gM is measured with a gel permeation chromatography multi-angle laser light scattering photometer (GPC-MALS method), and the molecular weight and the rotation radius are measured, and the rotation radius <r ² > _br of the styrenic resin composition is linear. The branching ratio gM = <r ² > _br / <r ² > _lin was calculated from the rotation radius <r ² > _{lin of} polystyrene, and was calculated as an average value between 1 million and 1.5 million molecular weight. In addition, since a polymer with a large branch has a small turning radius, the value of the branching ratio gM is small. A polymer with few branches has a value close to 1. GPC-MALS was measured under the following conditions.
GPC model: Shodex DS-4 manufactured by Showa Denko KK
Column: Polymer Laboratories PLgel 10 μm MIXED-B
Mobile phase: Tetrahydrofuran Sample concentration: 0.2% by mass
Temperature: Room temperature Detector: Differential refractometer MALS Model: DAWN DSP-F manufactured by Wyatt Technology
Wavelength: 633 nm (He-Ne)
The branching ratio gM is a value calculated when the branching ratio gM of standard linear polydisperse polystyrene (manufactured by Showa Denko: NBS706) is 1.

  Mz / Mw of the styrenic resin composition is related to the content of the hyperbranched ultrahigh molecular weight copolymer, and the branching ratio gM is related to the degree of branching. It can be controlled by adjusting the blending ratio of the polymer and the polymerization conditions. In the present invention, by using a polyfunctional vinyl copolymer, a highly branched ultra-high molecular weight copolymer can be efficiently produced from the initial stage of polymerization, and the degree of freedom in polymer design depending on the polymerization conditions is great.

  The total amount of residual styrene monomer and polymerization solvent in the styrene resin composition of the present invention is preferably 500 μg / g or less, and more preferably 350 μg / g or less. If the total amount of residual styrene monomer and polymerization solvent in the styrene-based resin composition is large, these components volatilize at the outlet of the extruder or at the time of thermoforming, and adhere to the surface of the film or molded product, causing problems such as poor appearance. Therefore, it is preferable to reduce as much as possible.

The amount of the residual styrene monomer and the polymerization solvent was measured by dissolving 500 mg of resin in 10 ml of DMF (dimethylformamide) containing cyclopentanol as an internal standard substance and using gas chromatography under the following conditions.
Gas chromatograph: HP-5890 (manufactured by Hewlett-Packard Company)
Column: HP-WAX, 0.25 mm × 30 m, film thickness 0.5 μm
Injection temperature: 220 ° C
Column temperature: 60 ° C to 150 ° C, 10 ° C / min
Detector temperature: 220 ° C
Split ratio: 30/1
The residual styrene monomer and the polymerization solvent can be reduced depending on the configuration of the devolatilization step and the operating conditions of the devolatilization step, and are adjusted to a preferable range by adopting a configuration such as two-stage devolatilization or two-stage water injection devolatilization. be able to.

  The methanol-soluble component of the styrenic resin composition of the present invention is preferably 0.5 to 3.5% by mass, and more preferably 1.0 to 3.0% by mass. If the methanol soluble content is less than 0.5% by mass, the stretchability at the time of film formation deteriorates, and if it exceeds 3.5% by mass, the heat resistance of the film tends to decrease. The methanol-soluble component refers to a component that is soluble in methanol in the resin composition. For example, in addition to a styrene oligomer (styrene dimer, styrene trimer) that is by-produced in the polymerization process or devolatilization process of a styrene resin, white oil, Various additives such as silicone oil, low molecular weight components such as residual styrene monomer and polymerization solvent are included. Methanol-soluble matter can be adjusted by the amount of styrene oligomer (styrene dimer, styrene trimer) generated as a by-product in the polymerization process, the amount of various additives such as white oil, the amount of residual styrene monomer and polymerization solvent. .

The methanol-soluble component is precisely weighed (mass P) of 1 g of resin, dissolved by adding 40 mL of methyl ethyl ketone, and rapidly added by 400 mL of methanol to precipitate and precipitate the methanol-insoluble component (resin component). After leaving still for about 10 minutes, it is gradually filtered through a glass filter to separate methanol-insoluble matter, dried in a vacuum dryer at 120 ° C. under reduced pressure for 2 hours, and then allowed to cool in a desiccator for about 25 minutes. By measuring the mass N of the dried methanol-insoluble matter, it was determined by the following formula.
Methanol-soluble content (mass%) = (P−N) / P × 100

  The melt mass flow rate (MFR) measured under the conditions of 200 ° C. and 49 N load of the styrene resin composition and styrene resin material of the present invention is preferably 0.5 to 10.0 g / 10 min. It is more preferably 0.0 to 6.0 g / 10 min. If it is less than 0.5 g / 10 minutes, the extrudability of the film deteriorates, and if it exceeds 10 g / 10 minutes, drawdown tends to occur during the extrusion of the film, which is not preferable. MFR can be measured based on JIS K-7210.

  It is preferable that the melt tension value measured at 200 ° C. of the styrene resin composition of the present invention or the styrene resin material obtained by blending the additive described later with this styrene resin composition is 5 to 15 gf. More preferably, it is -12gf. The maximum melt draw ratio is preferably 100 or more, and more preferably 120 or more. If the melt tension value is too low, the thickness of the film becomes non-uniform, and if the melt tension value is too high, the maximum melt stretch ratio will be insufficient. On the other hand, if the maximum melt draw ratio is too low, the film is not sufficiently stretched during deep drawing, and the film is easily broken during molding. As long as the balance with the melt tension can be achieved, the upper limit value of the maximum melt draw ratio is not limited.

  The melt tension value uses “Capillograph 1B type” manufactured by Toyo Seiki, barrel temperature 200 ° C., barrel diameter 9.55 mm, capillary length: L = 10 mm, capillary diameter: D = 1 mm (L / D = 10), The resin is extruded at an extrusion speed of 10 mm / min in the barrel, the load measuring part is set 60 cm below the die, the strand-shaped resin flowing out from the capillary is set in the winder, and the winding line speed is 4 m / min. Gradually increase the speed from the minute and measure the load until the strand breaks. Since the load is stabilized at a constant value as the winding linear speed is increased, the range in which the load is stable is averaged to obtain a melt tension value. Further, the ratio of the winding linear velocity (m / min) when the strand broke and the flow velocity (m / min) in the capillary was defined as the maximum melt draw ratio (times).

  The Vicat softening temperature of the styrenic resin composition of the present invention is preferably 92 to 102 ° C, and more preferably 95 to 100 ° C. If the Vicat softening temperature is less than 92 ° C, the heat resistance of the film is insufficient, and if it exceeds 102 ° C, the thermoforming cycle becomes longer, which is not preferable. The Vicat softening temperature can be adjusted by the methanol-soluble content of the styrenic resin composition. The Vicat softening temperature was determined according to JIS K-7206 at a heating rate of 50 ° C / hr and a test load of 50N.

  When producing the styrene resin composition of the present invention, from the viewpoint of controlling the polymerization reaction, a polymerization initiator such as a polymerization solvent or an organic peroxide or a chain transfer agent such as an aliphatic mercaptan is used as necessary. can do.

  The polymerization solvent is used for reducing the viscosity of the reaction product in continuous bulk polymerization, and examples of the organic solvent include alkylbenzenes such as benzene, toluene, ethylbenzene and xylene, ketones such as acetone and methyl ethyl ketone, hexane, Aliphatic hydrocarbons such as cyclohexane can be used.

  In particular, when it is desired to increase the amount of the polyfunctional vinyl copolymer added, it is preferable to use a polymerization solvent from the viewpoint of suppressing gelation. Thereby, the addition amount of the polyfunctional vinyl copolymer shown previously can be increased dramatically, and a gel is hardly generated.

  Although the usage-amount of a polymerization solvent is not specifically limited, It is preferable that it is 1-50 mass% normally as a composition in a polymerization reactor from a viewpoint of controlling gelatinization, and 3-20 mass. % Is more preferable. When it exceeds 50 mass%, productivity is remarkably lowered or the molecular weight of the styrene resin is excessively lowered.

  As the polymerization initiator, a radical polymerization initiator is preferable. For example, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, 2,2- Peroxyketals such as di (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-di (t-amylperoxy) cyclohexane, cumene hydroperoxide, t-butyl hydroperoxide, etc. Alkyl peroxides such as hydroperoxides, t-butylperoxyacetate, t-amylperoxyisononanoate, t-butylcumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t -Dialkyl peroxides such as hexyl peroxide, t-butylperoxyacetate Peroxyesters such as t-butyl peroxybenzoate and t-butylperoxyisopropyl monocarbonate, peroxycarbonates such as t-butyl peroxyisopropyl carbonate and polyether tetrakis (t-butyl peroxycarbonate) N, N′-azobis (cyclohexane-1-carbonitrile), N, N′-azobis (2-methylbutyronitrile), N, N′-azobis (2,4-dimethylvaleronitrile), N, N '-Azobis [2- (hydroxymethyl) propionitrile] and the like can be mentioned, and these can be used alone or in combination.

  Furthermore, a chain transfer agent can be used for adjusting the molecular weight of the styrene resin composition of the present invention, and examples thereof include aliphatic mercaptans, aromatic mercaptans, pentaphenylethane, α-methylstyrene dimer, and terpinolene.

  As described above, the styrenic resin composition of the present invention can be obtained by adding a polyfunctional vinyl copolymer to a styrenic monomer and continuously polymerizing it. Therefore, a prepolymerized styrenic resin, additives other than the above liquid paraffins, and the like can be melt blended with an extruder or dry blended in a pellet state.

  Examples of the styrenic resins and additives include GP-PS resins for improving fluidity, HI-PS resins containing rubber for improving strength, rubber-reinforced aromatic vinyl resins such as MBS resins, Aromatic vinyl-based thermoplastic elastomers such as SBS can be mentioned. When adding a resin containing a rubbery material, care must be taken because the transparency may be extremely deteriorated if the ratio exceeds 40% by mass. Examples of the additive include higher fatty acids such as stearic acid, zinc stearate, calcium stearate, magnesium stearate and salts thereof, lubricants such as ethylene bisstearyl amide, and antioxidants.

  The styrenic resin composition of the present invention is for film molding and is suitably used as a film. The film is preferably produced by a T-die extrusion method or an inflation method after melt-kneading the styrenic resin composition with an extruder. The extruder and the stretching machine are not particularly limited, and known ones can be used, and it is general to orient the film by adjusting the expansion ratio in the tenter type stretching or inflation method and stretching. To be done.

  Although the average thickness of a film changes with uses and is not specifically limited, Usually, it is 5-50 micrometers.

  Since the styrene resin composition film of the present invention has high strength and excellent deep drawability during secondary molding, it can be used as a laminate film on polystyrene foam used for food trays, etc. From printability, it can be used as food packaging or envelope window material.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples.

Synthesis example (polyfunctional vinyl copolymer A)
3.1 mol (399.4 g) of divinylbenzene, 0.7 mol (95.1 g) of ethylvinylbenzene, 0.3 mol (31.6 g) of styrene, 2.3 mol (463.5 g) of 2-phenoxyethyl methacrylate Then, 974.3 g of toluene was put into a 3.0 L reactor, 42.6 g of boron trifluoride diethyl ether complex was added at 50 ° C., and reacted for 6.5 hours. After stopping the polymerization reaction with a sodium hydrogen carbonate solution, the oil layer was washed three times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried and weighed to obtain 372.5 g of a polyfunctional vinyl copolymer A. This polyfunctional vinyl copolymer A has a weight average molecular weight Mw of 8,000, a molar fraction of the structural unit (a1) containing a vinyl group derived from a divinyl compound is 0.44, and a terminal component derived from 2-phenoxyethyl methacrylate at the end. The double bond (a2) was 0.03, and the combined molar fraction (a3) of both was 0.47. Further, the radius of inertia of the copolymer at a weight average molecular weight of 8,000 was 6.4 nm. The ratio of the mole fraction of the double bond of this copolymer to the radius of inertia is 13.6, and the polyfunctional vinyl in this synthesis example is compared with the fact that the inertia radius at a linear molecular weight of 8000 is 15 nm. It can be seen that the copolymer has a branched structure.

Production Examples (Examples and Comparative Examples)
(Method for producing styrene resin compositions PS-1 to PS-10)
The polymerization reactor was configured by connecting in series a first reactor that was a complete mixing tank, a second reactor, and a third reactor that was a plug flow reactor with a static mixer. The capacity of each reactor was 39 L for the first reactor, 39 L for the second reactor, and 16 L for the third reactor. A raw material solution was prepared with the raw material composition described in Table 1, and the raw material solution was continuously supplied to the first reactor at a flow rate described in Table 1. The polymerization initiator and the crosslinking agent were added to the raw material solution at the inlet of the first reactor so as to have the addition concentrations shown in Table 1 (mass-based concentration with respect to the raw styrene), and mixed uniformly. The polymerization initiators listed in Table 1 are as follows, and t-dodecyl mercaptan was used as a chain transfer agent. As the crosslinking agent, the polyfunctional vinyl copolymer A or divinylbenzene (DVB) obtained in the synthesis example was used.
Polymerization initiator-1: 1,1-di (t-butylperoxy) cyclohexane (Perhexa C manufactured by NOF Corporation)
Polymerization initiator-2: 2,2-di (4,4-t-butylperoxycyclohexyl) propane (Pertetra A manufactured by NOF Corporation)
In the third reactor, a temperature gradient was provided along the flow direction, and the temperature was adjusted so that the temperature shown in Table 1 was obtained at the intermediate part and the outlet part.
Subsequently, to the solution containing the polymer continuously taken out from the third reactor, white oil was added / mixed so as to have the concentration shown in Table 1 with respect to the polymer, and a preheater constituted by two stages in series. After introducing unreacted styrene and ethylbenzene by adjusting the temperature of the preheater to the resin temperature shown in Table 1 and adjusting to the pressure shown in Table 1, The strand was extruded from the die into a strand shape, and the strand was cooled and cut into a pellet by a cold cut method. PS-1 to PS-3 are examples, and PS-4 to 10 are comparative examples. The pellets obtained in the examples are pellets of a styrene resin composition for a highly branched film.

In addition, when the presence or absence of a gel-like substance in continuous operation was confirmed under each condition, a lot of gel-like substances were included in the strand extruded from the porous die at the point of 24 hours under the conditions of PS-6 and PS-10. It was difficult to continue driving.
Further, from the molecular weights Mw and Mz of the outlets of the reactors and the pellets, the use of the polyfunctional vinyl copolymer of the present invention enables the highly branched ultrahigh molecular weight copolymer to be efficiently produced from the initial stage of polymerization. Recognize.

  Table 2 shows the characteristics of the obtained styrene-based resin composition. Moreover, the measuring method in an Example is shown below.

  The average thickness (μm) of the film was determined by measuring the thickness of the film with n = 5 in the MD and TD directions, respectively, using a digital thickness meter manufactured by Toshiba Seiki.

  The tensile strength (breaking strength, elongation at break) of the film was measured at a test speed of 20 mm / min according to JIS K-7113 using a sample obtained by punching the obtained film in the MD and TD directions with a No. 1 dumbbell.

Example 1
90% by mass of a styrene resin composition (PS-1) and 10% by mass of an impact-resistant styrene resin (Toyostyrene E640N manufactured by Toyo Styrene Co., Ltd.) were sufficiently mixed, and then an inflation molding machine (40 mm diameter single screw extrusion). Machine, a die temperature of 75 mmφ) was extruded at a resin temperature of 220 ° C. and a die temperature of 200 ° C. to obtain an inflation film having a film width of 230 mm and a thickness of 25 μm. The properties of the obtained film are shown in Table 2.
Next, the film was laminated on a foamed polystyrene sheet (thickness 2.0 mm, density 70 kg / m ³ , bubble cell diameter 0.2 to 0.3 mm) by a thermal lamination method to obtain a laminated sheet.
From the obtained laminated sheet, containers having different inner diameters and different depths were vacuum-formed, and the thickness uniformity of the film was evaluated (○: uniform thickness, Δ: uneven thickness, ×: during molding) Film break).

Examples 2-3 and Comparative Examples 1-5
Evaluation was performed in the same manner as in Example 1 except that the styrenic resin composition having the name shown in Table 2 was used.

  The evaluation results of the obtained film are shown in Table 2.

Claims (4)

100 ppm to 3000 ppm of an aromatic solvent-soluble polyfunctional vinyl copolymer having an average of two or more vinyl groups in one molecule and having a branched structure was added to a monovinyl compound in which styrene is essential. The solvent-soluble polyfunctional vinyl copolymer obtained by continuously supplying a raw material solution to a polymerization reactor in which one or more raw materials are continuously arranged to advance the polymerization reaction and the monovinyl compound are polymerized. A styrene resin composition comprising a hyperbranched ultra-high molecular weight copolymer and a linear polymer produced by polymerization of the monovinyl compound, having a weight average molecular weight (Mw) of 200,000 to 500,000, and a Z average The ratio (Mz / Mw) of the molecular weight (Mz) to the weight average molecular weight (Mw) is 2.2 to 5.0, and the branching ratio gM at a molecular weight of 1,000,000 to 1,500,000 is 0.80 to 0.40. To Styrene resin composition for highly branched film. An aromatic solvent-soluble polyfunctional vinyl copolymer obtained by polymerizing a divinyl compound and a monovinyl compound copolymerizable with a divinyl compound represented by the following formula (a1) is a pendant vinyl group-containing unit. It is contained in the structural unit in the range of 0.10 to 0.50 as the molar fraction, and the ratio of the inertial radius (nm) in the weight average molecular weight to the molar fraction is in the range of 10 to 80. The styrenic resin composition for a hyperbranched film according to claim 1.

(In the formula, R ¹ represents a hydrocarbon group derived from a divinyl compound.)   The manufacturing method of the styrene resin film characterized by extruding the styrene resin composition for hyperbranched films of any one of Claims 1-2.   A styrene resin film obtained by the production method according to claim 3.