Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
  • B29C44/34—Auxiliary operations
  • B29C44/3469—Cell or pore nucleation
  • B29C44/348—Cell or pore nucleation by regulating the temperature and/or the pressure, e.g. suppression of foaming until the pressure is rapidly decreased
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/07—Flat, e.g. panels
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/30—Extrusion nozzles or dies
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/30—Extrusion nozzles or dies
  • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
  • B29K2023/10—Polymers of propylene
  • B29K2023/12—PP, i.e. polypropylene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/25—Solid
  • B29K2105/253—Preform
  • B29K2105/256—Sheets, plates, blanks or films
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
  • B29K2995/0015—Insulating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
  • C08J2201/03—Extrusion of the foamable blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/08—Supercritical fluid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment

Definitions

• the present invention relates to a foam board for a heat insulating building material of a polyolefin resin composition and a method for producing the same.
• Foams of polyolefin resin compositions are characterized by their excellent balance between performance and cost, and the recyclability of resins that have been sought in recent years. Widely used in packaging cushioning applications.
• a polypropylene resin or a foam board of polyethylene resin is applied to the inside of a floor or wall of a building, exhibits excellent heat insulating performance, and is widely accepted in the market.
• the first production method is a so-called bead method, in which a foaming agent such as hydrocarbon is added to a polyolefin resin composition pellet dispersed in water or the like in a pressurized sealed container. After impregnation under high temperature and high pressure, it is rapidly released to atmospheric pressure, so-called pre-expanded particles are produced, the pre-expanded particles are filled in a mold, and heated and cooled to obtain a molded product in the mold. is there.
• a foaming agent such as hydrocarbon
• Foam boards made of polyolefin resin composition can be produced by this bead method, but the foam produced by the usual bead method has an average cell diameter of about 200 to 500 xm. Insufficient thermal performance cannot be obtained for use as a heat insulating building material.
• the bead method is a batch production method, and it is necessary to perform in-steam molding after the pellet production process and pre-expanded particle production process. There is a drawback that the manufacturing cost is higher than possible.
• the second production method is a so-called extrusion method, and the polyolefin is used as an extruder.
• Resin composition particles are added, and if necessary, using a hydrocarbon or chemical foaming agent as a foaming agent, melt and knead under heating and pressurization, and then obtain a foam through a die designed in a predetermined shape Is the method.
• Patent Document 1 a polyfunctional monomer and a thermal decomposable foaming agent are added to a polypropylene resin, melt-mixed in advance, and irradiated with an electron beam to crosslink the polypropylene resin. And a method of further decomposing and foaming the pyrolyzable foaming agent by heating it further.
• the main component is polypropylene, and the following (1)
• Patent Document 3 discloses that a thermoplastic polymer (A) and ultrahigh molecular weight polyolefin (b-1) having an intrinsic viscosity [77] of 10 to 40 dl / g are 10 to 50% by weight [r? ] Is 0.:! ⁇ 5dl/g Polyolefin (b-2) 90-50% by weight [The total of (b-1) and (b-2) is 100% by weight.
• Patent Document 4 a supercritical inert gas, which is a foaming agent, is melted in an extruder by melting a resin composition composed of a thermoplastic resin and a fluoroalkane ester of an aliphatic carboxylic acid. Added to form a completely compatible state of the thermoplastic resin composition and the inert gas. In the gas dissolution process, in the extruder, maintain a pressure above the critical pressure of the inert gas as the blowing agent. In the cooling process that lowers the temperature of the molten resin while holding it, in a die heated above the glass transition temperature of the resin, the pressure is released from the pressure above the critical pressure of the inert gas to the atmospheric pressure.
• Patent Document 1 Japanese Patent Application Laid-Open No. 07-173317
• Patent Document 2 W ⁇ 99Z07752 Publication
• Patent Document 3 Japanese Patent Application Laid-Open No. 2004-217755
• Patent Document 4 Japanese Patent Laid-Open No. 10-175248
• Patent Document 1 has a problem that it is not suitable for continuous mass production because of the large number of steps including a molding step, a crosslinking step, and a foaming step.
• recycling of plastic molded products has been required due to environmental problems, etc., but melt re-pelletization etc. in the process of recycling the polyolefin resin composition used in such a method.
• decomposition of the cross-linked product and graph product occurs relatively easily, so the melting characteristics necessary for foaming cannot be maintained, and the recyclability is poor. It was.
• foams (cells) of the foam are uniformly dispersed because a foam with a relatively low expansion ratio of about 5 times can be easily obtained. Although it is a foam, sufficient heat insulating performance has not been obtained yet. For this reason, in order to obtain even better heat insulation performance, it is conceivable to increase the expansion ratio to 10 times or more. However, if the expansion ratio is 10 times or more, it is difficult to obtain a foam having a uniform and fine cell structure. However, there was a problem that it was impossible to obtain a proper heat insulation performance.
• polystyrene is mainly used as a thermoplastic resin.
• a polyolefin resin having crystallinity is foamed.
• the resin composition at the time of foaming is influenced by the characteristics of the crystalline resin that the melt viscosity and melt tension drop rapidly due to crystal melting.
• the viscosity and melt tension of the product are significantly reduced, and bubbles (cells) cannot be sufficiently grown and bubbles are broken. In other words, since the cells could not grow sufficiently, it was difficult to obtain a foam having a uniform and fine cell structure at a high expansion ratio of 10 times or more.
• the object of the present invention is to have excellent extrusion foamability, excellent heat insulation performance, recyclability, low cost and stable continuous production.
• An object of the present invention is to provide a foam board for a heat insulating building material made of a polyolefin resin composition. Means for solving the problem
• the present invention has been intensively researched and developed to achieve the above object.
• a polyolefin resin containing a polypropylene resin a polyolefin resin containing a linear polypropylene resin having a specific range of melt tension is used.
• a foaming agent containing at least carbon dioxide in a supercritical state preferably under specific conditions, an unprecedented foam board for heat insulating building materials having a foaming ratio of 10 times or more can be obtained.
• the present invention has been achieved.
• the present invention has the gist characterized by the following.
• a polyolefin resin composition containing a linear polypropylene resin having a melt tension of 5 to 30 g at 230 ° C is used with a foaming agent containing at least carbon dioxide in a supercritical state, and the expansion ratio is 10
• a foam board for heat-insulating building materials characterized by being foamed more than twice.
• the foam board for heat-insulating building materials according to (1) above having an average cell diameter of 200 ⁇ m or less and a uniform cell diameter distribution with a cell diameter distribution coefficient of 30% or less.
• a method for producing a foam board for heat-insulating building materials are described in this specification is produced.
• Extruder force The method for producing a foam board for heat-insulating building materials according to (6) or (7) above, wherein the extrusion discharge amount is 1 to 1000 kg / hr.
• a heat insulating building material of a polyolefin resin composition that has excellent extrusion foamability, excellent heat insulation performance, is recyclable, and can be stably produced at low cost.
• a foam board is provided.
• the polyolefin resin in the polyolefin resin composition of the present invention contains a polypropylene resin, and the polypropylene resin essentially has a melt tension (MT) at 230 ° C of 5 to 30 g.
• the melt tension can be determined by using a caprograph, with a measurement temperature of 230 ° C, an extrusion speed of 10 mm / min, and a take-up speed of 3. lm / min. If the melt tension is less than 5g, cell breakage will occur at the time of foaming.
• the melt tension is too high, the cell membrane is prevented from growing, and sufficient cell growth is not performed during foaming, making it difficult to obtain a foam having a sufficient foaming ratio of 10 times or more. Les.
• the melt tension is preferably 6.5 to 20 g, more preferably 7.5 to 10 g.
• the polypropylene resin preferably satisfies the following formula (I) between the melt tension at 230 ° C. and the melt flow rate (MFR) at 230 ° C.
• melt tension and MFR of the polypropylene resin contained in the polyolefin resin composition in the present invention satisfy the above formula (1), the melt fluidity of the resin is simultaneously increased with respect to the increase of the melt tension.
• the resin pressure at the time of extrusion during foaming is appropriately maintained, and the cell membrane is sufficiently stretched during foaming, so that a high-magnification foam can be easily obtained.
• the polyolefin resin composition of the present invention may contain other resins in addition to the polypropylene resin having the above specific characteristics.
• the polypropylene resin having the specific melt tension, and preferably the specific MFR is preferably 50% by mass or more, particularly in the polyolefin resin composition of the present invention. Is preferably contained in an amount of 80% by mass or more in order to satisfactorily achieve the object of the present invention. If the content of the polypropylene resin in the mixed resin is less than 50% by mass, the resulting foam may have insufficient mechanical strength and heat resistance.
• Examples of the other resin contained in the polyolefin resin composition of the present invention include, for example, polyethylene resin, propylene homopolymer, propylene and one other than propylene copolymerizable with propylene. And a copolymer with olefin.
• the ⁇ -olefin is not particularly limited, but for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1— Otaten etc. are listed. These other resins may be used alone or in combination of two or more.
• a propylene homopolymer having a relatively large molecular weight a copolymer of propylene and ethylene mainly composed of propylene, and a mixed resin of polypropylene resin and polyethylene resin are preferably used.
• the polypropylene resin having the specific characteristics and the other resins used together with the polypropylene resin contained in the polyolefin resin composition of the present invention are substantially linear. It is preferable that in the present invention, the term “linear” means that each molecular chain of the propylene polymer (propylene polymer) constituting the polypropylene resin is a component of the propylene polymer (propylene polymer). This means that the unit propylene monomer and the olefin monomer copolymerizable therewith are practically an aggregate of those polymerized in a single string.
• the foam board for building material in the present invention is foamed using a foaming agent containing at least carbon dioxide in a supercritical state.
• foaming is preferably performed using 4 to 20 parts by mass, particularly preferably 5 to 15 parts by mass of a foaming agent containing carbon dioxide in a supercritical state with respect to 100 parts by mass of the polyolefin resin composition. is there. If the amount of carbon dioxide used is less than 4 parts by mass, the foaming ratio is liable to decrease. On the other hand, if it exceeds 20 parts by mass, large voids due to excess carbon dioxide are likely to occur in the foam.
• the polyolefin resin composition used in the present invention contains a polypropylene resin having the above-mentioned specific physical properties, but the polyolefin resin composition does not impair achievement of the object of the present invention.
• One or more of various additives such as antimony flame retardants, lubricants, metal damage inhibitors, antistatic agents, fillers, colorants, cell nucleating agents, crystal nucleating agents, etc. may be added. .
• the cell nucleating agent is not particularly limited, but talc, calcium carbonate. And clay, kaolin, mica, magnesium oxide, zinc oxide, carbon black, glass, quartz, silica, alumina, novaquilite, hydrated alumina, iron, iron oxide, silicon dioxide, titanium oxide and the like.
• the crystal nucleating agent is not particularly limited, and generally includes a rosin-based crystal nucleating agent, a sorbitol-based crystal nucleating agent, and a phosphate ester-based crystal nucleating agent. It is The rosin-based crystal nucleating agent is not particularly limited as long as it is a rosin-based resin, and examples thereof include dibenzylidene sorbitol (DBS) manufactured by Shin Nippon Rika Co., Ltd. The phosphoric acid ester salt nucleating agent is not particularly limited, and examples thereof include NA_11 manufactured by Asahi Denka Kogyo Co., Ltd. These crystal nucleating agents may be used alone or in combination.
• a foam board for a heat-insulating building material of the present invention includes a linear polypropylene resin having the above-mentioned specific physical properties using a foaming apparatus having an extruder and a die attached to the tip.
• the resin composition is mixed with a blowing agent containing at least carbon dioxide in a supercritical state, and is manufactured by melt extrusion at a temperature of 160 to 250 ° C.
• the melt extrusion temperature is less than 160 ° C, the dissolution and diffusion of supercritical carbon dioxide into the resin is poor, and conversely, when it exceeds 250 ° C, deterioration of the polypropylene resin such as molecular chain breakage due to heat begins to occur. Therefore, it is not preferable.
• the resin pressure (pressure loss) in the immediate vicinity of the die opening in the extruder is preferably 6 to 20 MPa, released into the atmosphere, and extruded and foamed.
• the pressure loss is more preferably 7 to 15 MPa, and most preferably 9 to 15 MPa. If the pressure loss is less than 6 MPa, the supercritical carbon dioxide dissolved in the polyolefin resin composition is easily vaporized inside the extruder and inside the die, and foaming occurs inside the apparatus, and It is not preferable because it causes foaming, excessive growth, reduction of expansion ratio, remarkably low appearance and appearance.
• the extrusion discharge rate in the extruder is preferably 1 to 1000 kg / hr.
• the amount of extrusion discharge depends on the specifications of the extruder. In general, l to 50 kg / hr is preferable. In a type having a relatively large screw diameter, about 20 to 1000 kg / hr is preferable. If the discharge rate is too large or too small, it will be difficult to maintain a pressure loss suitable for foaming at the die part, and it will not be possible to obtain a foam with a sufficient magnification, or the cells may break. I'll be relaxed.
• two screws having a screw diameter (D) of preferably 40 to 80 mm and a screw length of (L) (LZD) of preferably 15 to 40 are used.
• a tandem type extruder configured on the basis of being combined in series is preferable.
• the resin pressure loss condition and the discharge amount of the die part suitable for foaming can be controlled independently by the number of rotations of each screw, and the above-described polyolefin resin composition of the present invention can be controlled.
• the foam board having excellent characteristics and excellent characteristics can be manufactured.
• the shape of the die used in the extruder is not limited, but the number, shape, and thickness of the opening are designed so that the pressure loss per opening is 6 to 20 MPa as described above.
• a slit die or a multi-hole die is preferable. By selecting a die that satisfies these conditions, it is possible to obtain a foam board for a heat-insulating building material that exhibits sufficient thermal performance.
• the diameter of the opening in the extruder that is preferably circular is 0.:!-2. Omm is preferred, and 0 ⁇ 3 to 0 ⁇ 7mm is more preferred. It is preferable that a plurality of openings are provided on the front surface of the die, the die depth being preferably 0.1 to 10 mm.
• the diameter is less than 0.1 mm, the strand diameter of the foam structure is too small, and it is easy to tear off when taken. 2. If the diameter exceeds Omm, the strand diameter is too large. This is preferable because post-molding of the shape becomes difficult. Also, slit-shaped dies having a width of 0.:! To 2.0 mm and a length of 0.1 to 1000 mm can be used.
• the above polyolefin resin composition is used, for example, in a carbon dioxide supply line having a supercritical carbon dioxide supply capability in the middle of a cylinder barrel.
• the foamable polyolefin resin composition is heated to a predetermined temperature and uniformly melted and kneaded, and then a predetermined amount of supercritical carbon dioxide is supplied from a supply line to form a board shape. Foam by extruding into A body board is manufactured.
• the shape and size may be adjusted using a cutting machine, a sandwiching conveyor, or the like in order to adjust the product form of the foam board for heat insulating building materials.
• a sheet-like material such as an aluminum sheet non-woven fabric or leather is bonded to one side or both sides of the foam board as a face material, and the strength, heat resistance, flame retardancy, etc. Various performances may be imparted.
• the foam board for heat-insulating building materials of the present invention can have the cell diameter and cell distribution coefficient described later even when the expansion ratio is 10 times or more, and further 15 times or more, particularly Even a foaming ratio of 20 times or more is preferable because it has the cell diameter and cell distribution coefficient and sufficient member thermal performance. Further, it is preferable to use a high expansion ratio because the specific gravity of the foam can be reduced and the cost of the raw materials used can be reduced. On the other hand, if the expansion ratio is too high, the mechanical strength of the foam is reduced. For example, when used as a building material, the foam tends to be damaged by external addition during construction. Nare ,. Therefore, the expansion ratio is preferably 100 times or less, particularly 50 times or less.
• the foam board for heat-insulating building materials of the present invention preferably has an average cell diameter of 200 ⁇ m or less and 150 ⁇ m or less, and more preferably 50 to 100 / im.
• the cell diameter distribution coefficient can be 30% or less, more preferably 25% or less, and particularly 20% or less. When the average cell diameter is 200 / m or less and the cell diameter distribution coefficient is 30% or less, the heat insulation performance is particularly excellent when used as a building material.
• the average cell diameter means that the foam is cut into small test pieces, and the cross-sectional area is randomly determined from an image observed with an electron microscope (SEM) at a magnification of 50 times.
• the average cell diameter can be obtained by calculating the average cell diameter using the following formula by drawing 10 straight lines with a length of 2 mm and counting the number of cells on the straight line.
• the cell diameter distribution coefficient is determined from 10 to 20 pieces from an image observed by cutting the foam into test pieces and observing the cross-sectional area with an electron microscope (SEM) at a magnification of 50 times. The average cell diameter and the standard deviation of the cell diameters are calculated, and the cell diameter distribution coefficient can be obtained by the following formula based on these values.
• Cell system distribution coefficient%) (Standard deviation of cell diameter) / (Average value of cell diameter) X 100
• the foam board for heat-insulating building materials of the present invention has a thermal conductivity of 20 to 40 mWZmK measured in accordance with JIS-A1412, and can obtain a foam board for heat-insulating building materials having suitable heat insulation properties. it can.
• the thermal conductivity is more preferably 20 to 37 mW / mK.
• the thermal insulation performance is not only inferior, but the thermal insulation value is 0.9 or more to obtain a thermal resistance value of 0.9 or more, which is a preferable thermal performance evaluation standard for a thermal insulation construction board. Therefore, when this is used as, for example, a heat insulating material for floors, it becomes larger than the size of the wooden frame of the floor, which may cause problems during construction, which is not preferable.
• Polypropylene resin A with MFR force 3 at 230 ° C of 3 (g / l0 min) and melt tension at 230 ° C of 7.6 g was supercritical carbon dioxide feeder ( Tandem type single shaft equipped with carbon dioxide supply line from C 02—3) and equipped with die 1 (8 x 48-row multi-hole die with an opening diameter of 0.5 mm) at the second stage tip Supply to an extruder (KGT-50-65 manufactured by Rikita Co., Ltd.), set the carbon dioxide supply rate to 1.2 kgZ hours, and contain 6 parts by mass with respect to 100 parts by mass of polypropylene resin.
• Example 2 A foam board 1 for a heat insulating building material of a polyolefin resin composition was obtained.
• the carbon dioxide supply rate is set to 1.5 kg / hour
• the extrusion amount is adjusted with the screw speed of the first-stage extruder so that 7.5 mass parts is contained per 100 mass parts of the polypropylene resin A
• a polyolefin resin composition was prepared in the same manner as in Example 1 except that the resin pressure at the die 1 site was adjusted to 8.9 MPa with the screw rotation speed of the second-stage extruder and extruded and foamed.
• the foam board 2 for heat-insulating building materials was obtained.
• the carbon dioxide supply rate is set at 1.9 kg / hour
• the extrusion rate is adjusted with the screw speed of the first-stage extruder so as to contain 6 parts by mass with respect to 100 parts by mass of the polypropylene resin A
• the die The polyolefin resin composition was prepared in the same manner as in Example 1 except that the resin pressure at one part was adjusted to the screw rotation speed of the second stage extruder so that the pressure was 8.8 MPa, and extrusion foaming was performed.
• a foam board 4 for heat insulating building materials was obtained.
• a foamed board 6 for a heat-insulating building material of a polyolefin resin composition was obtained in the same manner as in Example 1 except that the resin pressure at 1 part of the die was 6.5 MPa.
• polypropylene resin C (homopolypropylene resin A) having 45 parts by mass of polypropylene resin A, MFR at 230 ° C of 6 g / 10 min, and melt tension at 230 ° C of 1/8 g.
• a foamed board 7 for a heat insulating building material of a polyolefin resin composition was obtained in the same manner as in Example 1 except that the resin pressure was 55 parts by mass and the resin pressure at one part of the die was 8.65 MPa.
• a foamed board 8 for a heat-insulating building material of a polyolefin resin composition was obtained in the same manner as in Example 1 except that the resin pressure at 1 part of the die was 16. IMPa.
• Example 1 The same tandem type single-screw extruder used in Example 1 for polypropylene resin C (homopolypropylene resin) with MFR force of S6gZlO at 230 ° C and melt tension of 1.8g at 230 ° C Set the carbon dioxide supply rate to 1.2 kg / hour, and adjust the extrusion amount with the screw speed of the first-stage extruder so that it contains 6 parts by mass with respect to 100 parts by mass of the polypropylene resin. Then, the foam pressure board 6 for the heat insulating building material of the polypropylene resin composition was obtained by adjusting the screw rotation speed of the second stage extruder so that the resin pressure at the die 1 site was 4.5 MPa and by extrusion foaming. .
• the performance of a commercially available polyethylene foam board manufactured by the bead method with an expansion ratio of 90 times was evaluated.
• the performance ((a) density, (a) of the polyolefin (polypropylene) resin foam obtained in Examples 1 to 5 and Comparative Examples 1 and 2 and Comparative Example 3 in Comparative Example 3 b) Compressive strength, (c) Average cell diameter, (d) Thermal conductivity, (e) Cell diameter distribution coefficient) were evaluated by the following methods.
• the foam of the polyolefin resin composition of the present invention has a variety of excellent performance and cost. It can be widely used mainly for heat insulating building materials, automotive parts, and packaging cushioning materials. It should be noted that the entire contents of the Japanese Patent Application 2005-192375, filed on June 30, 2005, and the claims, drawings, and abstract are cited herein, and the description of the present invention is disclosed. It is included as an indication.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
• Building Environments (AREA)
• Extrusion Moulding Of Plastics Or The Like (AREA)

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• 2006
  • 2006-06-29 WO PCT/JP2006/313028 patent/WO2007004524A1/ja active Application Filing
  • 2006-06-29 KR KR1020077030391A patent/KR20080042046A/ko not_active Application Discontinuation
  • 2006-06-29 CN CNA2006800194674A patent/CN101203552A/zh active Pending
  • 2006-06-29 JP JP2007524003A patent/JPWO2007004524A1/ja active Pending

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