JP6512580B2 - Method for producing polystyrene resin foam board - Google Patents

Description

  The present invention relates to a method for producing a polystyrene resin foam plate.

  Conventionally, as a manufacturing method of polystyrene resin foam board used for heat insulation materials, such as a wall, a floor, a roof of a building, and a core material of a tatami mat, a cell regulator etc. are added to polystyrene resin material, for example, Heat-melt-kneaded, add a physical foaming agent to form a foamable resin composition, and extrude this foamable resin composition from a high pressure zone to a low pressure zone to cause foaming, and further add to the die outlet of the extruder There is known a method of obtaining a polystyrene resin foam plate by forming it into a plate shape by using a molding tool or the like. In addition, in this production method, a saturated hydrocarbon having an ozone destruction coefficient of 0 and a small global warming coefficient is used as a foaming agent.

  On the other hand, in the polystyrene resin foam board used for the said construction materials etc., for example, the high flame retardance which satisfies the combustibility standard of the extrusion polystyrene foam heat insulating board of JIS A 9511 (2006) is requested | required.

  Here, in order to impart a high degree of flame retardancy to the foam plate, a brominated flame retardant such as hexabromocyclododecane or a brominated bisphenol compound has been blended in the foam plate. In addition, since the saturated hydrocarbon used as the blowing agent is flammable, the amount used as the blowing agent is limited. Therefore, in order to produce a foam board having a high expansion ratio, an easily dissipative physical foam agent which dissipates quickly from the foam board has been used in combination as another foam agent. In recent years, among these foaming agents, environmentally friendly techniques using carbon dioxide, aliphatic alcohols, water and the like in combination with saturated hydrocarbons have been developed (see Patent Documents 1 to 3).

JP 2001-323097 A Japanese Patent Application Publication No. 2003-12848 Unexamined-Japanese-Patent No. 2004-43681

  Polymeric brominated butadiene-styrene copolymers have been developed as flame retardants to be incorporated into foam plates. When using the brominated butadiene-styrene copolymer as the flame retardant, carbon dioxide, water, etc. having a low plasticizing effect on polystyrene resin is particularly used as the other foaming agent, polystyrene resin based on the flame retardant In the case of producing a foam having a high expansion ratio, or in the case of producing a foam having a large cross-sectional area, the appearance is deteriorated (foam surface, because a plastic effect on the surface is difficult to be exhibited. In some cases, there is a possibility of improvement in these points, and the like, which may lead to the formation of a hooking pattern) and a decrease in production stability (lip clogging due to hooking of the foam end).

  The present invention has been made in view of the above-described conventional problems, and it is possible to obtain a foam board excellent in foam appearance and production stability even when using a polymer type brominated flame retardant An object of the present invention is to provide a method for producing a resin foam plate.

The present invention provides a method for producing a polystyrene resin foam board described below.
In the method for producing a polystyrene-based resin foam plate, including the step of extruding and foaming a foamable molten resin composition formed by kneading a <1> polystyrene-based resin, a physical blowing agent, and a flame retardant and molding it into a plate shape. And a brominated butadiene-styrene copolymer, wherein the physical blowing agent comprises 10 to 60 mol% of a saturated hydrocarbon having 3 to 6 carbon atoms, and 5 to 50 mol% of 1-chloro-3,3,3- Consisting of trifluoropropene and 50 mol% or less (including 0) of other foaming agents (however, 100 mol of saturated hydrocarbon, 1-chloro-3,3,3-trifluoropropene and other foaming agents in total) %, The total blending amount of the physical foaming agent is 0.8 to 2.0 mol with respect to 1 kg of the polystyrene resin, and the 1-chloro-3,3,3-trifluoro compound Method for producing a polystyrene resin foam sheet, wherein the amount of the pen is 0.1~0.6mol to the polystyrene resin 1 kg.
<2> The other foaming agent is mainly composed of one or more foaming agents selected from ethanol, carbon dioxide and water, and the proportion of the other foaming agent in the physical foaming agent is 5 to 50 mol% The manufacturing method of the polystyrene resin foam board as described in <1> characterized by these.
<3> The polystyrene-based polymer according to <1> or <2>, wherein the saturated hydrocarbon is butane, and the amount thereof is 0.1 to 0.7 mol with respect to 1 kg of the polystyrene-based resin. Manufacturing method of resin foam board.
<4> The polystyrene resin foam board according to any one of <1> to <3>, wherein an apparent density of the polystyrene resin foam board is 20 kg / m ³ or more and less than 40 kg / m ³ Manufacturing method.
<5> The polystyrene-based resin according to any one of <1> to <4>, wherein a width of the polystyrene-based resin foam plate is 800 mm or more, and a cross-sectional area perpendicular to the extrusion direction is 200 cm ² or more. Manufacturing method of resin foam board.

  According to the method for producing a polystyrene resin foam board of the present invention, it is environmentally friendly and hard to burn in addition to saturated hydrocarbon as a foaming agent together with a polymer type brominated butadiene-styrene copolymer as a flame retardant By blending a specific physical foaming agent having properties under specific conditions, it is possible to provide a method for producing a polystyrene resin foam board capable of obtaining a foam board excellent in foam appearance and production stability. It becomes.

  The process for producing a polystyrene resin foam board according to the present invention comprises the step of extruding and foaming a foamable molten resin composition formed by kneading a polystyrene resin, a physical foaming agent and a flame retardant, and molding it into a plate shape. A method for producing a plate, wherein the flame retardant comprises a brominated butadiene-styrene copolymer and the physical blowing agent is a saturated hydrocarbon having 3 to 6 carbon atoms, 1-chloro-3,3,3-trifluoro, and Consisting of propene and, if necessary, other blowing agents.

(Polystyrene resin)
The polystyrene-based resin in the present invention is a polymer mainly composed of styrene, and not only a styrene homopolymer but also a copolymer of styrene and a vinyl-based monomer copolymerizable with styrene can be used. Specifically, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-maleic anhydride copolymer, polystyrene-polyphenylene ether copolymer, a mixture of polystyrene and polyphenylene ether, etc. may be mentioned. Moreover, you may mix and use 2 or more types of these polystyrene resin. The polystyrene resin may contain a multifunctional monomer unit component such as divinylbenzene or a multibranched macromonomer. Among these polystyrene resins, polystyrene is preferable from the viewpoint of foamability.

  The polystyrene resin in the present invention has a styrene component of 50 mol% or more, preferably 60 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more.

  The polystyrene-based resin may contain other polymers within the range in which the objects and effects of the present invention are achieved. Other polymers include polyethylene-based resins (one or a mixture of two or more selected from the group consisting of ethylene homopolymers and ethylene copolymers having an ethylene unit component content of 50 mol% or more), and polypropylene Resins (one or a mixture of two or more selected from the group consisting of propylene homopolymers and propylene copolymers having a propylene unit component content of 50 mol% or more), polyphenylene ether resins, polymethyl methacrylate Etc., styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer hydrogenated substance, styrene-isoprene-styrene block copolymer water Additives, thermoplastic elastomers such as styrene-ethylene copolymer, etc. It is. These other polymers are mixed according to the purpose so as to be less than 50% by mass, preferably 30% by mass or less, and more preferably 10% by mass or less in the polystyrene resin. can do.

  Moreover, in order to improve the heat insulation of a foam board, what contains an amorphous polyethylene terephthalate-type copolymer can be used as polystyrene-type resin. In this case, the non-crystalline polyethylene terephthalate resin is preferably blended in the polystyrene resin so as to be 5% by mass or more and less than 50% by mass.

The polystyrene resin preferably has a melt viscosity of about 500 to 2500 Pa · s, more preferably 600 to 2000 Pa · s, and still more preferably 700 to 1500 Pa · s, from the viewpoint of foamability and moldability. s. In addition, the said melt viscosity is the value measured on the conditions of temperature 200 degreeC, and a shear rate of 100 second ^-1 based on JISK 7199: 1999.

(Flame retardants)
The flame retardant in the present invention contains at least a brominated butadiene-styrene copolymer. As the brominated butadiene-styrene copolymer, conventionally known ones such as a block copolymer, a random copolymer, a graft copolymer and the like can be used.

  Moreover, as a styrene-type monomer which comprises the said copolymer, styrene, brominated styrene, chlorinated styrene, 2-methylstyrene, 4-methylstyrene, 2,4- dimethylstyrene, alpha-methylstyrene etc. are mentioned. Among these, styrene, 4-methylstyrene, α-methylstyrene or a mixture thereof is preferable, and styrene is more preferable. Among these, in consideration of compatibility with a polystyrene resin, a block copolymer of a polystyrene polymer block and a brominated polybutadiene block is more preferable.

  In general, a brominated butadiene-styrene block copolymer which is a representative brominated butadiene-styrene copolymer can be represented by the following general formula (1).

（式中、Ｘ、Ｙ及びＺは、正の整数である。）

(Wherein, X, Y and Z are positive integers)

  Such a brominated butadiene-styrene block copolymer is produced, for example, by brominating a butadiene-styrene block copolymer. Examples of the brominated butadiene-styrene block copolymer preferably used in the present invention include commercial products such as Emerald Innovation 3000 manufactured by Chemtura, and FR122P manufactured by ICL-IP.

Generally, a brominated butadiene-styrene copolymer used as a flame retardant has a mass average molecular weight of about 1.0 × 10 ^{3 to} 2.0 × 10 ⁵ , preferably 2.0 × 10 ³ , in terms of polybutadiene. Brominated a butadiene styrene polymer of 1.0 × 10 ⁵ , more preferably 5.0 × 10 ^{3 to} 1.0 × 10 ⁵ , still more preferably 5.0 × 10 ^{4 to} 1.0 × 10 ⁵ Manufactured by In consideration of the dispersibility in the polystyrene resin, the mass average molecular weight of the brominated butadiene-styrene copolymer is preferably 0.9 × 10 ^{5 to} 3.0 × 10 ⁵ , 1 in terms of polystyrene. further preferably ^{.0 × 10 5 ~2.0 × 10 5} .

  Further, from the viewpoint of the flame retardancy-imparting effect, the bromine content in the brominated butadiene-styrene copolymer is preferably 60% by mass or more, and more preferably 63% by mass or more. In addition, the said bromine content rate can be calculated | required based on JISK7392 (2009).

  In the present invention, other flame retardants can be used in addition to the brominated butadiene-styrene copolymer within the scope of the purpose of the present invention and the effects thereof. As other flame retardants, for example, tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol-S-bis (2,3-dibromo-2-methylpropyl ether), Tetrabromobisphenol-F-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-S-bis (2,3-bis) Brominated bisphenol compounds represented by dibromopropyl ether), tetrabromobisphenol-F-bis (2,3-dibromopropyl ether), tris (2,3-dibromopropyl) isocyanurate, mono (2,3,3 4-tribromobutyl) isocyanurate, di (2,3,3 In addition to brominated isocyanurate represented by -tribromobutyl) isocyanurate and tris (2,3,4-tribromobutyl) isocyanurate, tris (2,3-dibromopropyl) cyanurate, cresyl di 2, 6- Nitrogen-containing cyclic compounds such as xylenyl phosphate, antimony trioxide, diantimony pentoxide, ammonium sulfate, zinc stannate, cyanuric acid, pentabromotoluene, isocyanuric acid, triallylisocyanurate, melamine cyanurate, melamine, melam, melem etc. Inorganic compounds such as silicone compounds, boron oxide, zinc borate and zinc sulfide, phosphates such as triphenyl phosphate, red phosphoruss, ammonium polyphosphates, phosphates such as hypophosphites Compounds etc. may be mentioned. These compounds may be used alone or in combination of two or more. When a flame retardant other than a brominated butadiene-styrene copolymer is used, among these, tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol-A- It is preferable to use in combination one or more selected from bis (2,3-dibromopropyl ether) and tris (2,3-dibromopropyl) isocyanurate.

  The amount of the flame retardant other than the above-mentioned brominated butadiene-styrene copolymer is preferably 30% by mass or less, more preferably 20% by mass or less, and 10% by mass or less based on the total amount of the flame retardant added. More preferable.

  Although the total compounding quantity of the said flame retardant is suitably determined according to the desired flame retardance, the polystyrene resin extrusion foaming which satisfies the combustibility standard of the extrusion polystyrene foam heat insulating board of JIS A 9511 (2006R) statement In order to obtain a body, it is preferable to mix | blend 0.1-5 mass parts with respect to 100 mass parts of polystyrene-type resin, More preferably, it is 0.5-3 mass parts. By setting it in the said range, the extrusion foam of a favorable surface state can be obtained, without a flame retardant inhibiting foamability.

(Physical blowing agent)
The physical blowing agent in the present invention comprises a saturated hydrocarbon having 3 to 6 carbon atoms, 1-chloro-3,3,3-trifluoropropene and, if necessary, other blowing agents.

[Saturated hydrocarbon]
As the saturated hydrocarbon having 3 to 6 carbon atoms used in the present invention, for example, propane, n-butane, isobutane, cyclobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, cyclohexane and the like can be used. These saturated hydrocarbons can be used alone or in combination of two or more.

  Moreover, the compounding quantity of a saturated hydrocarbon is the range of 10-60 mol%, when the sum total of a saturated hydrocarbon, 1-chloro- 3,3,3- trifluoro propene, and another foaming agent is 100 mol%.

  In the present invention, among the above-mentioned saturated hydrocarbons, n-butane and isobutane are preferable, and the blending amount thereof is 0.1 to 0.7 mol, preferably 0.2 to 0.6 mol, per 1 kg of polystyrene resin. It is a range.

  By making the compounding quantity of saturated hydrocarbon more than said lower limit, the foam shrinkage | contraction after extrusion can be suppressed and a flame retardance can be maintained by below the said upper limit carrying out.

[1-chloro-3,3,3-trifluoropropene]
The compounding amount of 1-chloro-3,3,3-trifluoropropene used in the present invention is 100 mol% of the total of saturated hydrocarbon, 1-chloro-3,3,3-trifluoropropene and other foaming agents. When it is set, it is in the range of 5 to 50 mol%, preferably 10 to 50 mol%.

  Moreover, the compounding quantity with respect to 1 kg of polystyrene resin is 0.05-0.6 mol, Preferably it is the range of 0.1-0.6 mol.

  By making the compounding quantity of 1-chloro- 3,3,3- trifluoro propene more than said lower limit, the foam which has the appearance of a favorable surface property can be obtained. Further, by setting the content to the above upper limit value or less, excellent foamability can be exhibited, and a foam having a good appearance without occurrence of an excessive bubble called a spot can be obtained.

[Other blowing agents]
As the other foaming agent in the present invention, any foaming agent other than the above can be used without particular limitation, and the compounding amount thereof is a saturated hydrocarbon, 1-chloro-3,3,3-trifluoropropene and others. When the total of the foaming agents in the above is 100 mol%, it is 50 mol or less (including 0), preferably in the range of 5 to 50 mol%.

  As other foaming agents, foaming agents which do not inhibit the flame retardancy of the foam and are environmentally friendly can be used. As the other foaming agent, it is preferable to preferably use one having one or more foaming agents selected from ethanol, carbon dioxide and water as a main component. In addition, the compounding quantity in a physical foaming agent at the time of using what has 1 or 2 or more foaming agents selected from ethanol, a carbon dioxide, and water as a main component is 5-50 mol%, More preferably, it is 10-45 mol It is in the range of%. In addition, the proportion of one or more foaming agents selected from ethanol, carbon dioxide and water in the other foaming agents is preferably 50 mol% or more in 100 mol% of the other foaming agents, and is 80 mol% or more More preferably, the further blowing agent consists of one or more blowing agents selected from carbon dioxide and water.

  A low density resin foam board can be obtained by setting the blending amount of the other foaming agent to the above lower limit value or more. Further, by setting the content to the above upper limit value or less, it is possible to obtain a good foamed state at the time of molding, and it is possible to obtain a resin foam plate having an excellent appearance (surface property).

  Moreover, the total compounding quantity of the said physical foaming agent in this invention is 0.8-2.0 mol with respect to 1 kg of polystyrene resin, Preferably it is the range of 1.0-1.6 mol. By setting the total content of the physical foaming agent to 0.8 mol or more, it is possible to obtain a foam board having an appropriate density as a foam insulation board, and by setting it to 2.0 mol or less, an excellent appearance (surface property) Can be obtained.

(Additive)
In the production method of the present invention, in addition to the above-mentioned polystyrene resin, physical blowing agent and flame retardant, other additives and the like can be blended as long as the purpose and effect of the present invention are not impaired. As these things, a bubble regulator, a heat stabilizer, a flame retardant adjuvant, a coloring agent, an antioxidant, a radiation inhibitor, a filler, a lubricating agent etc. can be mentioned, for example.

  Examples of the cell regulator include inorganic substances such as talc, kaolin, mica, silica, calcium carbonate, barium sulfate, titanium oxide, clay, aluminum oxide, bentonite, diatomaceous earth and the like. In addition, two or more of the cell regulators can be used in combination. In addition, it is preferable that it is 0.01-7.5 mass parts with respect to 100 mass parts of polystyrene resin, and, as for the compounding quantity of a bubble regulator, it is more preferable that it is 0.1-5 mass parts.

  Examples of the heat stabilizer include one or more heat stabilizers selected from epoxy compounds, phenol compounds, hindered amine compounds, and phosphite compounds. In addition, it is preferable that the total compounding quantity of this heat stabilizer is 0.01-30 mass parts with respect to 100 mass parts of flame retardants.

  The flame retardant aid includes at least one flame retardant aid selected from diphenyl alkane, diphenyl alkene, and polyalkylbenzene. By blending these, the oxygen index of the resulting foam can be improved.

  Examples of the diphenyl alkanes include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, and the like. And 4-diethyl-3,4-diphenylhexane. Examples of diphenyl alkenes include 2,4-diphenyl-4-methyl-1-pentene and 2,4-diphenyl-4-ethyl-1-pentene. Examples of polyalkylenebenzenes include poly-1,4-diisopropylbenzene (CCPIB). Among these, poly-1,4-diisopropylbenzene (CCPIB) is preferable. In addition, it is preferable that it is 1-20 mass parts with respect to 100 mass parts of flame retardants, and, as for the compounding quantity of a flame retardant adjuvant, it is more preferable that it is 2-10 mass parts.

  Examples of radiation suppression agents include fine powdery ones having a radiation suppression effect, specifically, metal oxides such as titanium oxide, metals such as aluminum, carbon black such as carbon black, graphite, etc. Can be illustrated. These can be used alone or in combination of two or more. The addition amount of the radiation inhibitor is used in the range of 0.5 to 5 parts by mass, preferably 1 to 4 parts by mass with respect to 100 parts by mass of the polystyrene resin.

(Manufacturing method of polystyrene resin foam board)
Hereinafter, one embodiment of the manufacturing method of the polystyrene resin foam board of the present invention is described. The method for producing a polystyrene resin foam board according to the present invention adopts a method including a step of extruding and foaming a foamable molten resin composition formed by kneading a polystyrene resin, a physical foaming agent and a flame retardant into a plate shape Ru.

  Specifically, polystyrene resins and flame retardants and, if necessary, additives such as a cell regulator, a heat stabilizer, and a flame retardant auxiliary are supplied to an extruder, heated and kneaded, and a physical foaming agent The foamable polystyrene-based resin melt composition obtained by pressing the mixture into an extruder and kneading it is extruded from, for example, a flat die through a high pressure extruder into a low pressure zone (usually in the air) and foamed, A forming die (a guider) or a forming die (a guider) configured by a plate made of upper and lower two polytetrafluoroethylene resins or the like installed so as to gradually expand from the inlet to the outlet) The plate is formed into a plate by passing a forming tool such as a forming roll to produce an original plate, and further, the width and length of the original plate are adjusted by cutting the original plate, thereby extruding the plate-like polystyrene resin Foam It includes a method of manufacture.

(Apparent density)
Apparent density of the polystyrene type resin foamed plate obtained by the present invention is preferably less than 20 kg / ^{m 3} or more 40 kg / ^{m 3,} more preferably less than 25 kg / ^{m 3} or more 40 kg / ^{m 3.} By setting the apparent density to 20 kg / m ³ or more, a polystyrene resin foam board having desired characteristics can be produced, and sufficient mechanical strength can be obtained. Further, by setting the density to less than 40 kg / m ³ , it is possible to obtain a polystyrene resin foam board having excellent lightness and heat insulation.

The apparent density can be determined based on JIS K7222 (2005), by converting the value obtained by dividing the mass of a polystyrene-based resin foam plate by the volume obtained from the external dimensions of the foam plate into unit conversion (kg / m ³ ).

(Width and vertical cross section)
The foam board is plate-shaped, depending on the application, the width is not less 800mm or more, the cross-sectional area of the extrusion direction vertical cross section can be required for 200 cm ² larger size. Usually, a foam board is manufactured by producing an original plate of one size or more larger than a desired size, cutting the original plate, and adjusting the width and length, and in some cases, the thickness. Here, if the width of the original plate greatly fluctuates during the production and the width becomes narrower than the definition, a foam plate of a defined size can not be obtained, and the yield is deteriorated. In the production of a foam board, as described above, the higher the expansion ratio and the larger the cross-sectional area, the more the foam tends to be difficult. According to the method for producing a polystyrene resin foam board of the present invention, stably producing a foam board having a good appearance even when producing a foam board having such a large thickness and a large cross-sectional area Can.

The width of the polystyrene resin foam board in the present invention is more preferably 910 mm or more. It is preferable that the vertical sectional area of the polystyrene type resin foamed plate in the present invention is 200 cm ² or more, more preferably 500 cm ² or more, more preferably 800 cm ² or more.

(Closed cell rate)
The closed cell rate of the polystyrene resin foam board in the present invention is preferably 60% or more, more preferably 65% or more, still more preferably 70% or more, from the viewpoint of obtaining physical properties such as excellent heat insulation and mechanical strength. Preferably it is 80% or more, most preferably 90% or more.

In addition, the closed cell rate: S (%) is measured using an air comparison type hydrometer 930 type manufactured by Toshiba Beckman Co., Ltd., in accordance with the procedure C described in ASTM D 2856-70 (recertified in 1976). The actual volume of the test piece to be measured (the sum of the volume of the closed cell and the volume of the resin part): Vx (cm ³ ) can be calculated by the following equation (1).
S (%) = (Vx-W / ρ) × 100 / (Va-W / ρ) (1)
However, Va, W, and rho in the above-mentioned formula are as follows.
Va: Apparent volume (cm ³ ) of the test piece used for measurement
W: Weight of test piece (g)
ρ: density of resin composition that constitutes the test piece (g / cm ³ )

The density ρ (g / cm ³ ) of the resin composition can be obtained by degassing the bubbles of the test piece used for measurement and the test piece used for measurement by a heat press and then cooling it. It can be determined from the sample volume (cm ³ ).

(Thermal conductivity)
0.020 to 0.040 W / m · K is preferable, and 0.022 to 0.028 W / m · K is more preferable for the thermal conductivity of the polystyrene resin foam board in the present invention. When the thermal conductivity of the foam plate is in the above range, excellent heat insulation can be obtained. In addition, the measurement of thermal conductivity is measured based on the flat plate heat flow meter method (two heat flow meter method, high temperature side 38 ° C, low temperature side 8 ° C, average temperature 23 ° C) described in JIS A 1412-2 (1999). be able to.

  Hereinafter, the method for producing a polystyrene resin foam board of the present invention will be specifically described by way of examples. However, the present invention is not limited to the examples.

[apparatus]
The first die with an inner diameter of 150 mm and the second extruder with an inner diameter of 200 mm are connected in series, and a flat die with a resin discharge port (die lip) with a rectangular cross section in the width direction of 4 mm × width 370 mm is second A shaping device (space 100 mm) constituted by a plate made of a pair of upper and lower polytetrafluoroethylene resins installed parallel to the flat die connected to the outlet of the extruder is attached The extrusion device used was used.

In addition, the following were used for each material introduce | transduced into the said manufacturing apparatus.
[Polystyrene resin]
Polystyrene: weight average molecular weight Mw = 270,000, melt viscosity 1100 Pa · s (a mixed resin of 50% by weight of polystyrene having a weight average molecular weight Mw = 320,000 and 50% by weight of polystyrene having a weight average molecular weight Mw = 200,000)
The melt viscosity is a value measured under the conditions of a temperature of 200 ° C. and a shear rate of 100 seconds ⁻¹ using a flow characteristic measuring device of Capirograph 1D (manufactured by Toyo Seiki Seisakusho Co., Ltd.).

[Flame retardants]
Br-SBS: Brominated butadiene-styrene block copolymer (manufactured by ICL-IP, product name "FR-122P")
660: Tris (2,3-dibromopropyl) isocyanurate (manufactured by Suzuyu Kagaku, product name “FCP-660”)

[Physical blowing agent]
Saturated hydrocarbon: Isobutane 1-chloro-3,3,3-trifluoropropene (HFO 1233zd): (manufactured by Honeywell, product name "Solstice 1233zd (E)") Other blowing agents: carbon dioxide, water, ethanol

[Additive]
Bubble regulator: Talc (Matsumura Sangyo, product name "High Filler # 12")
Heat stabilizer: 50% by mass of novolac type epoxy compound (product name: "EPICLON N680" manufactured by DIC), bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-diphosphite (product name manufactured by ADEKA) "PEP36") 25% by mass, octadecyl-3- (3,5-di-)
1446167193104_0
-4-hydroxyphenyl)
1446167193104_1
(BASF made, product name "Irganox 1076") 25 mass%
Flame retardant aid: Poly-1,4-diisopropylbenzene (product of UNITED INITIATORS, product name "CCPIB")

(Manufacturing conditions)
A polystyrene resin, a flame retardant, a flame retardant aid, a heat stabilizer, and a cell regulator are supplied to the first extruder of the apparatus so as to obtain the composition and amount shown in Table 1, and the mixture is heated to 200 ° C. These were kneaded, and the physical foaming agent of the composition and amount shown in Table 1 was supplied to the melt from the foaming agent inlet and further kneaded. Then, the expandable resin melt is sequentially supplied to the second extruder, and the expanded resin temperature suitable for foaming as shown in the table in the table (measured at the position of the bonding portion between the extruder and the die) After adjusting to the temperature of the foamable resin melt, the die lip is extruded from the die lip into the guider at a discharge amount of 800 kg / hr, passed through the inside of the guider and shaped (shaped) into a plate shape, and further, the width of the original plate Adjusting the length, rectangular solid polystyrene-based resin foam plates (width: 1000 mm, length: 2000 mm, thickness: 100 mm, extrusion direction cross section: 1000 cm ² ) of Examples 1 to 5 and Comparative Examples 1 to 3 were obtained. Obtained. Immediately after the production, the foam plate was transferred to a constant temperature and humidity chamber at 23 ° C. and a relative humidity of 50%, and the foam plate was allowed to stand in the constant temperature and humidity chamber.

  Apparent density, thickness, cross-sectional area, closed cell ratio (the above items after 5 days after production), thermal conductivity (production) of the polystyrene resin foam boards of Examples 1 to 7 and Comparative Examples 1 to 3 obtained. After 5 days and after 30 days) were measured by the following methods, and the flame resistance, appearance (surface property and spot) and production stability were evaluated according to the following criteria. The results are shown in Tables 1 and 2.

(Apparent density)
The apparent density was measured based on JIS K7222 (2005).

(Thickness)
The thickness of the width direction center part and both ends of the extrusion direction vertical cut surface was read with a caliper, and the value obtained by arithmetically averaging the measured values was taken as the thickness.

(Section area)
The cross-sectional area of the extrusion direction perpendicular | vertical cross section was calculated | required as a product of the thickness of a foam board, and the width | variety of a foam board. In addition, the width | variety of the foam board was calculated | required as an arithmetic mean value of the width | variety of five places selected at random from the foam board.

(Closed cell rate)
From the center in the width direction of the extruded foam, cut out a sample having a size of 20 mm × 40 mm (width) × 25 mm (thickness) without a shaped skin, and the closed cell ratio of each sample according to the procedure C of ASTM-D 2856-70. Was measured.

(Thermal conductivity)
Test pieces of 200 mm long × 200 mm wide × 50 mm thick are cut out from the vicinity of the central part of the foam plate 5 and 30 days after production, and the flat plate heat flow meter method (JIS A 1412-2 (1999)) It measured based on the heat flow meter 2 sheet system, the high temperature side 38 degreeC, the low temperature side 8 degreeC, and the average temperature 23 degreeC.

(Flame retardance)
It was evaluated according to the flammability standard of the extruded polystyrene foam insulation board described in JISA 9511 (2006R).

(Appearance (surface property))
The surface condition of the produced foam was visually evaluated according to the following criteria.
:: no unevenness is observed on the surface, and the surface smoothness is particularly excellent. ×: unevenness is observed on the surface and the surface is not smooth

(Appearance (spot))
The surface condition of the produced foam was visually evaluated according to the following criteria.
○: No spot (oversized cell) of 5 mm or more was found inside the extruded foam, ×: A spot (oversized cell) more than 5 mm was present inside the extruded foam

(Manufacturing stability)
The surface condition of the produced extruded foam was visually evaluated according to the following criteria.
Good: Stable and uniform product can be obtained during long time extrusion foaming x: Cracking may occur at the end of the width of die lip during long time extrusion foaming and stable uniform product can be obtained Can not

  From the results shown in Tables 1 and 2, Example 1 in which 0.15 mol / kg of 1-chloro-3,3,3-trifluoropropene as a physical foaming agent was added and water and ethanol were used in combination as other foaming agents. It was confirmed that ~ 3 is superior in appearance and production stability as compared with the comparative example. In addition, it was confirmed that Example 4 in which carbon dioxide was additionally used as another foaming agent was also excellent in appearance and production stability as compared with the comparative example. Furthermore, in Examples 5 to 7, 0.6 mol / kg of the physical foaming agent 1-chloro-3,3,3-trifluoropropene within the range specified in the present invention without using other foaming agents. Even if the amount was increased up, good foam board was obtained due to high compatibility of 1-chloro-3,3,3-trifluoropropene and polystyrene resin.

  On the other hand, in Comparative Examples 1 and 2 in which 1-chloro-3,3,3-trifluoropropene is not used as a physical blowing agent, the appearance (surface hooking) and the production stability (edge hooking) Deterioration of lip clogs was confirmed. Moreover, the comparative example 3 which mix | blended 0.7 mol / kg more than the prescription | regulation amount of this invention of 1-chloro- 3,3,3- trifluoro propene generate | occur | produces a spot in a foam, and aggravates an external appearance or manufacture stability Was confirmed.

  From these results, according to the method for producing a polystyrene resin foam board of the present invention, by blending a specific physical foaming agent as a flame retardant together with a brominated butadiene-styrene copolymer under specific conditions, It was confirmed that a polystyrene resin foam board excellent in appearance as well as being excellent in physical properties balance such as apparent density, heat insulation and flame retardancy can be obtained.

Claims (5)

In a method for producing a polystyrene resin foam plate, the method comprising extruding and foaming a foamable molten resin composition formed by kneading a polystyrene resin, a physical blowing agent and a flame retardant into a plate shape,
The flame retardant comprises a brominated butadiene-styrene copolymer,
The physical blowing agent is 10 to 60 mol% of a saturated hydrocarbon having 3 to 6 carbon atoms, 5 to 50 mol% of 1-chloro-3,3,3-trifluoropropene, and 50 mol% or less (including 0) And other foaming agents (provided that the total amount of saturated hydrocarbon, 1-chloro-3,3,3-trifluoropropene and other foaming agents is 100 mol%),
The total content of the physical blowing agent is 0.8 to 2.0 mol per 1 kg of the polystyrene resin, and the content of the 1-chloro-3,3,3-trifluoropropene is the polystyrene. It is 0.1-0.6 mol with respect to 1 kg of resin, The manufacturing method of the polystyrene resin foam board characterized by the above-mentioned.   The other foaming agent is mainly composed of one or more foaming agents selected from ethanol, carbon dioxide and water, and the proportion of the other foaming agent in the physical foaming agent is 5 to 50 mol%. The manufacturing method of the polystyrene resin foam board of Claim 1 characterized by these.   The said saturated hydrocarbon is a butane, The compounding quantity is 0.1-0.7 mol with respect to 1 kg of said polystyrene resins, The manufacture of the polystyrene resin foam board of Claim 1 or 2 characterized by the above-mentioned. Method. The apparent density of the said polystyrene resin foam board is 20 kg / m < ³ > or more and 40 kg / m < ³ >, The manufacturing method of the polystyrene resin foam board as described in any one of Claim 1 to 3 characterized by the above-mentioned. The width of the said polystyrene resin foam board is 800 mm or more, and the extrusion direction perpendicular | vertical cross-sectional area is 200 cm < ² > or more, manufacture of the polystyrene resin foam board as described in any one of Claim 1 to 4 characterized by the above-mentioned. Method.