JP5315759B2 - Method for producing foamed molded product in polypropylene resin mold - Google Patents

Description

  The present invention relates to a method for producing a polypropylene resin in-mold foam molded article.

  Polypropylene resin expanded particles are dispersed in a pressure-resistant container such as water in a dispersion medium such as water, and then a foaming agent is added and maintained at a constant temperature near the melting point of the polypropylene resin under high pressure. After impregnating, it can be produced by a method of releasing in a low-pressure atmosphere. Moreover, when using water as a dispersion medium, it is also possible to use water as a foaming agent. Such a method is called a decompression foaming method or an autoclave method.

  The in-mold foam molded product obtained by filling the polypropylene resin foam particles thus obtained in a mold and heat-molding with water vapor or the like is an arbitrary shape that is an advantage of the in-mold foam molded product, Features such as light weight and heat insulation. This in-mold foam molded article is superior in chemical resistance, heat resistance, and strain recovery rate after compression, compared to the in-mold foam molded article obtained using polystyrene resin foam particles. In addition, the dimensional accuracy, heat resistance, and compressive strength are superior to the in-mold foam molded article using polyethylene resin expanded particles. Due to these characteristics, in-mold foam molded articles obtained using polypropylene resin foam particles are used in various applications such as heat insulating materials, shock-absorbing packaging materials, automobile interior members, and automobile bumper core materials. In particular, an in-mold foam molded body having a high foaming ratio of 20 times or more is often used as a buffer packaging material because it is lightweight.

  Important properties required for an in-mold foam molded article obtained using polypropylene resin foam particles include fusion between foam particles, surface aesthetics, and shrinkage recovery.

  The fusion property between the expanded particles (hereinafter, also simply referred to as “fusing property”) is the degree of fusion between the expanded particles in the in-mold foam molded product. Insufficient strength. In particular, in many cases, the melt-bonding property is insufficient inside the in-mold foamed molded product.

  The surface beauty (hereinafter also simply referred to as surface property) is such that the surface of the in-mold foam molded article is smooth. The deterioration of the surface property is caused by indentations formed in the groove portions between the foam particles on the surface of the in-mold foam molded body, which is considered to be due to insufficient foaming of the foam particles, and streaks thought to be caused by shrinkage of the in-mold foam molded body. Caused by grooves,

  In general, a polypropylene resin-in-mold foam-molded product obtained by using polypropylene-based resin foam particles shrinks when molded and taken out from the mold. The shrinkage of the in-mold foam-molded body can be recovered by a so-called curing process in which the in-mold foam-molded body is kept in a heated atmosphere for a certain time. Even after curing, the in-mold foam-molded product does not recover to the size of the mold, but when the shrinkage rate of the in-mold foam-molded product after curing is smaller than that of the mold, the shrink recovery property is excellent.

  Among the above properties, it is said that the secondary foaming force of the foamed particles affects the fusing property and the surface property. When the expanded particles are heated to the molding temperature in the in-mold molding, the expanded particles expand, but the ratio of the expanded volume is called secondary expansion force. As the secondary foaming power of the foamed particles is increased, an in-mold foam-molded article having excellent fusion properties and surface properties can be obtained. The ethylene-propylene copolymer is more flexible than the propylene homopolymer and has a lower melting point. Therefore, at the same temperature, the expanded particles obtained from the ethylene-propylene copolymer can easily produce expanded particles having a higher expansion ratio than the expanded particles obtained from the propylene homopolymer, and have excellent secondary foaming power. Have. For this reason, the in-mold foam molded product obtained from the expanded particles obtained from the ethylene-propylene copolymer has excellent fusing properties and surface properties.

  In the above-described depressurization foaming method, particularly when a highly safe inorganic gas such as carbon dioxide or water is used as a foaming agent, polypropylene resin foam particles having a high expansion ratio of 20 times or more are produced by the depressurization foaming method. In order to do this, it is necessary to increase the container pressure. Moreover, the cell diameter and the closed cell rate of the obtained expanded particles are small, which causes the shrinkage recovery property of the in-mold expanded molded product to be lowered. For this reason, there has been proposed a method (two-stage foaming method) in which expanded particles having a low expansion ratio are once manufactured, and the expanded particles are heated to produce expanded particles having a high expansion ratio (Patent Document 1). ).

In Patent Document 1, when producing expanded particles having a high expansion ratio by the two-stage expansion method, when the expansion ratio is E and the number of bubbles per 1 mm ² is n, 2 <E ^1/3 × n ^1/2 < It is described that when expanded particles having a relationship of 45 are used as raw material expanded particles (first-stage expanded particles), it is possible to produce two-stage expanded particles that give a molded article having excellent shrinkage recovery properties.

Using the ethylene-propylene copolymer that can easily obtain expanded particles with a high expansion ratio as a base resin, the two-stage expanded particles produced under the conditions specified in Patent Document 1 have excellent fusion properties. It was confirmed to give an in-mold molded foam having. However, it has been found that the shrink recovery properties of the in-mold molded foam may not be sufficient.
JP 59-133233 A

  An object of the present invention is obtained by two-stage foaming using, as a base resin, an ethylene-propylene copolymer containing 3% by weight or more and 6% by weight or less of ethylene capable of imparting excellent fusibility to the foamed particles. Provided is a method for producing a polypropylene resin-in-mold foam-molded article using polypropylene-based resin foam particles, which can provide a polypropylene resin-in-mold foam-molded article having excellent shrinkage recovery properties. It is to be.

  The present inventors are expanded particles obtained by using a polypropylene resin containing 3 to 6% by weight of ethylene as a copolymer component as a base resin, and having a specific expansion ratio and average cell diameter. It has been found that when a polypropylene resin expanded particle obtained by further expanding the expanded polypropylene resin expanded particle is used, a polypropylene resin in-mold expanded molded article having excellent fusing property and shrinkage recovery can be obtained. That is, this invention is a manufacturing method of the following polypropylene resin in-mold foam-molded article.

[1] From an ethylene-propylene random copolymer having a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of 5 or less and containing 3 to 6 wt% of ethylene as a copolymerization component comprising a polypropylene resin as a base resin, the expansion ratio is less than 14.9 times 9.7 times or more, and the following formula (1), and further foaming the original PP beads satisfying (2) A process for producing a polypropylene resin-in-mold foam-molded product obtained by using polypropylene resin foam particles having a higher expansion ratio than the original foam particles.
[2] The method for producing an expanded foam in a polypropylene resin mold according to [1] , wherein a melt flow rate (MFR) of the polypropylene resin is 3 g / 10 min or more and 8 g / 10 min or less.
[3] The process for producing an in-mold expanded polypropylene resin product according to [1] or [2] , wherein the number average molecular weight (Mn) of the polypropylene resin is from 50,000 to 150,000.

  According to the production method of the present invention, it is possible to obtain a polypropylene resin in-mold foam-molded product having a high expansion ratio and having excellent fusion properties and shrinkage recovery properties.

The polypropylene resin used in the present invention contains 3% by weight to 6% by weight of ethylene as a copolymerization component. When ethylene is contained in an amount of 3% by weight or more and 6% by weight or less as a copolymerization component, polypropylene resin foamed particles and polypropylene resin in-mold foam-molded articles can be easily obtained. A preferable ethylene content is 3.5 wt% or more and 5 wt% or less. In addition, content of the copolymerization component based on ethylene in a polypropylene resin can be measured using ¹³ C-NMR.

  The polypropylene resin used in the present invention preferably contains 80% by weight or more of propylene as a monomer, and may contain a copolymerization component other than ethylene. Other copolymer components include 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3,4-dimethyl-1-butene, 1-butene, Α-olefins having 4 to 12 carbon atoms such as heptene, 3-methyl-1-hexene, 1-octene, 1-decene; cyclopentene, norbornene, tetracyclo [6,2,11,8,13,6] -4- Cyclic olefins such as dodecene; dienes such as 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 1,4-hexadiene, methyl-1,4-hexadiene, 7-methyl-1,6-octadiene; Vinyl, vinylidene chloride, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, maleic acid, ethyl acrylate, butyl acrylate, meta Methyl acrylic acid, maleic anhydride, styrene, methyl styrene, vinyl toluene, and vinyl monomers such as divinylbenzene and the like, may be used these one or two or more.

  As the polypropylene resin used in the present invention, either a random copolymer or a block copolymer can be used. In particular, it is preferable to use an ethylene-propylene random copolymer or an ethylene-propylene-butene random terpolymer having high versatility. An ethylene-propylene random copolymer or ethylene-propylene-butene having an ethylene content of 3 to 6% by weight, more preferably 3.5 to 6% by weight, particularly 3.5 to 5% by weight Random terpolymers are preferred.

  In the present invention, a polypropylene resin obtained by using a catalyst such as a metallocene catalyst or a post metallocene catalyst can also be used. In the present invention, a modified product obtained by oxidative decomposition (degradation treatment) of polypropylene resin with an organic peroxide can also be used.

  The polypropylene resin used in the present invention is preferably in an uncrosslinked state, but may be crosslinked by treatment with an organic peroxide or radiation. Two or more polypropylene resins may be mixed.

  The melt flow rate (MFR) of the polypropylene resin used in the present invention is preferably 3 g / 10 min or more and 20 g / 10 min or less, more preferably 3 g / 10 min or more and 15 g / 10 min or less, It is more preferably 3 g / 10 min or more and 10 g / 10 min or less, particularly preferably 3 g / 10 min or more and 8 g / 10 min or less. If the MFR is within this range, the molding temperature and molding time at the time of in-mold foam molding are well balanced, and the surface has good surface beauty, particularly when the mold has a thin part, the part has good surface beauty. There is a tendency.

  MFR is measured under the conditions of an orifice diameter of 2.0959 ± 0.005 mmφ, an orifice length of 8.000 ± 0.025 mm, a load of 2160 g, and 230 ± 0.2 ° C. using an MFR measuring instrument described in JIS-K7210. .

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polypropylene resin used in the present invention is preferably 5 or less. When Mw / Mn exceeds 5, the secondary foaming power tends to decrease, and the fusion property and shrinkage recovery property of the molded product tend to be inferior. Mw / Mn is more preferably 4.5 or less, more preferably 4.0 or less, and particularly preferably 1.5 or more and 4.0 or less. The polypropylene resin used in the present invention has a number average molecular weight (Mn) of 10,000 or more, further 30,000 or more and 200,000 or less, further 50,000 or more and 150,000 or less, particularly 70,000 or more and 130,000 or less. It is preferable.

Mn and Mw are measured under the following conditions.
measuring equipment:
Waters Alliance GPC 2000 Type Gel Permeation Chromatography (GPC)
column:
2 TSKgel GMH ₆ -HT,
Two TSKgel GMH ₆ -HTL (each inner diameter 7.5 mm x length 300 mm, manufactured by Tosoh Corporation)
Mobile phase: o-dichlorobenzene (containing 0.025% BHT)
Column temperature: 140 ° C
Flow rate: 1.0 mL / min
Sample concentration: 0.15% (W / V) -o-dichlorobenzene Injection amount: 500 μL
Molecular weight calibration: Polystyrene conversion (calibration with standard polystyrene)

  The melting point of the polypropylene resin used in the present invention is preferably 130 ° C. or higher and 150 ° C. or lower, more preferably 132 ° C. or higher and 145 ° C. or lower. When the melting point is within the above range, a good polypropylene-based in-mold foam molded product tends to be obtained even with a commonly used 0.4 MPa pressure-resistant molding machine.

  The method for measuring the melting point is as follows. Using a differential scanning calorimeter (DSC), 5-6 mg of polypropylene resin particle sample is heated from 40 ° C. to 220 ° C. at a temperature rising rate of 10 ° C./min to melt the resin. Next, crystallization is performed by lowering the temperature from 220 ° C. to 40 ° C. at 10 ° C./min. After crystallization, the temperature is further increased from 40 ° C. to 220 ° C. at 10 ° C./min. The melting peak temperature in the DSC curve obtained at the second temperature increase is taken as the melting point.

  In addition to polypropylene resins, other thermoplastic resins such as low density polyethylene, linear low density polyethylene, polystyrene, polybutene, ionomer, etc. may be mixed and used within a range that does not lose the properties of the polypropylene resin. good.

  The polypropylene resin is usually melted by using an extruder, a kneader, a Banbury mixer, a roll, etc., so that it is easy to produce foamed particles, and the resin particle shape such as a cylindrical shape, an elliptical shape, a spherical shape, a cubic shape, a rectangular parallelepiped shape, etc. It is preferable to process it. As for the size of the resin particles, the weight of one particle is preferably 0.1 mg to 30 mg, and more preferably 0.3 mg to 10 mg. The weight of one polypropylene resin particle is the average resin particle weight obtained from 100 randomly selected resin particles, and is expressed in mg / grain.

  In addition, as described in JP-A-58-145739 and JP-A-10-77359, resin particles having a low-melting-point polypropylene resin layer or polyethylene resin layer on the surface are used by a coextrusion method or the like. You can also.

  When an additive is added to the polypropylene resin, it is preferably mixed with the polypropylene resin using a blender or the like before the production of the polypropylene resin particles. An example of the additive is a cell nucleating agent. When using a hydrocarbon-based blowing agent such as propane, butane, pentane or hexane, 0.005 parts by weight or more of an inorganic nucleating agent such as talc, silica or calcium carbonate with respect to 100 parts by weight of the polypropylene resin. It is preferable to add 5 parts by weight or less. Moreover, when using inorganic foaming agents, such as air, nitrogen, a carbon dioxide gas, and water, it is preferable to use the said inorganic nucleating agent and / or a water absorbing substance. When water is used as a dispersion medium, water is impregnated into the polypropylene resin, and the impregnated water acts as a foaming agent together with other foaming agents or alone. The water-absorbing substance acts to increase the amount of impregnated water.

  Specific examples of the water-absorbing substance include water-soluble inorganic substances such as sodium chloride, calcium chloride, magnesium chloride, borax and zinc borate, water-absorbing organic substances such as melamine, isocyanuric acid, melamine / isocyanuric acid condensate, polyethylene glycol, polyethylene oxide and the like. Polyethers, addition products of polyethers to polypropylene, and alloys thereof, alkali metal salts of ethylene (meth) acrylic acid copolymers, alkali metal salts of butadiene (meth) acrylic acid copolymers, carboxylated nitrile rubber Examples thereof include hydrophilic polymers such as alkali metal salts, alkali metal salts of isobutylene-maleic anhydride copolymer and alkali metal salts of poly (meth) acrylic acid.

  The amount of water-absorbing substance added varies depending on the target foaming ratio, the foaming agent used, and the type of water-absorbing substance used, but when using a water-soluble inorganic substance, 0.01 wt. The amount is preferably not less than 1 part by weight and not more than 1 part by weight. When a hydrophilic polymer is used, it is preferably not less than 0.1 part by weight and not more than 5 parts by weight with respect to 100 parts by weight of the polypropylene resin. Two or more of these water-soluble inorganic substances and hydrophilic polymers may be used in combination. The average cell diameter of the polypropylene resin foamed particles can be adjusted by adjusting the kind and amount of the inorganic nucleating agent and the water-absorbing substance.

  Furthermore, when producing polypropylene resin particles, if necessary, colorant, antistatic agent, antioxidant, phosphorus processing stabilizer, lactone processing stabilizer, metal deactivator, benzotriazole UV absorber, benzoate Add additives such as light stabilizers, hindered amine light stabilizers, flame retardants, flame retardant aids, acid neutralizers, crystal nucleating agents, amide additives, etc. within a range that does not impair the properties of the polypropylene resin. be able to.

  The said polypropylene resin particle can be made into a polypropylene resin expanded particle using the method known conventionally. For example, the following method can be mentioned.

  Polypropylene resin particles are dispersed in a dispersion medium in a pressure vessel and carbon dioxide is added as a foaming agent. Next, at a temperature higher than the temperature at which the polypropylene resin particles soften, preferably at a melting point of polypropylene resin particles of −25 ° C. or higher, a melting point of the polypropylene resin particles of + 25 ° C. or lower, more preferably at a melting point of polypropylene resin particles of −15 ° C. or higher. The melting point of the resin resin particles is heated to a temperature in the range of 15 ° C. or lower, and the pressure is applied to impregnate the polypropylene resin particles with the foaming agent. Thereafter, one end of the pressure vessel is opened, and the polypropylene resin particles are produced by releasing the polypropylene resin particles into a lower pressure atmosphere than in the pressure vessel. The expansion ratio of the expanded polypropylene resin foamed particles can be adjusted by adjusting the heating temperature, the pressure applied, the temperature of the atmosphere to be discharged, and the pressure.

  There is no particular limitation on the pressure-resistant container in which the polypropylene resin particles are dispersed, and any pressure-resistant container that can withstand the pressure in the container and the temperature in the container at the time of producing the foamed particles may be used.

  As the dispersion medium, methanol, ethanol, ethylene glycol, glycerin, water, and the like can be used, and it is preferable to use water among them.

  In order to prevent coalescence of polypropylene resin particles in the dispersion medium, it is preferable to use a dispersant. Examples of the dispersant include inorganic dispersants such as tricalcium phosphate, tribasic magnesium phosphate, basic magnesium carbonate, calcium carbonate, barium sulfate, kaolin, talc, and clay.

  Further, it is preferable to use a dispersion aid together with the dispersant. Examples of dispersing aids include N-acyl amino acid salts, alkyl ether carboxylates, carboxylate types such as acylated peptides, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, sulfosuccinates, etc. Sulfate type, sulfate oil, alkyl sulfate, alkyl ether sulfate, sulfate ester type such as alkylamide sulfate, phosphoric acid such as alkyl phosphate, polyoxyethylene phosphate, alkyl allyl ether sulfate An anionic surfactant such as an ester type can be exemplified. Also, polycarboxylic acid type polymer surfactants such as maleic acid copolymer salts and polyacrylates, polyvalent anionic polymer surfactants such as polystyrene sulfonates and naphthalsulfonic acid formalin condensate salts, etc. Can be used.

  As a dispersion aid, it is preferable to use one or a mixture of two or more selected from alkyl sulfonates and alkyl benzene sulfonates, more preferably alkyl sulfonates, and 10 carbon atoms as hydrophobic groups. It is particularly preferable to use an alkyl sulfonate having a linear carbon chain of ˜18 because the dispersant adhering to the expanded particles can be reduced.

  Among these, it is preferable to use one or more selected from tricalcium phosphate, tribasic magnesium phosphate, barium sulfate or kaolin as a dispersant, and n-paraffin sulfonic acid soda as a dispersion aid. The amount of the dispersant and the dispersion aid varies depending on the type and the type and amount of the polypropylene resin used, but usually 0.2 parts by weight or more and 3 parts by weight or less of the dispersant with respect to 100 parts by weight of the dispersion medium. It is preferable to add 0.001 part by weight or more and 0.1 part by weight or less of a dispersion aid. Moreover, in order to make the dispersibility in a dispersion medium favorable, it is preferable to usually use 20 to 100 parts by weight of polypropylene resin particles with respect to 100 parts by weight of the dispersion medium.

  In addition, as described in JP-A-2002-167460, the surface of the resin particles can be modified with a peroxide or the like when the polypropylene resin particles are dispersed.

  In producing the polypropylene-based resin expanded particles used in the present invention, it is preferable to use an inorganic gas such as carbon dioxide, air, or nitrogen having high safety as the foaming agent. Carbon dioxide is particularly preferable. A foaming agent other than inorganic gas may be used in combination. Examples of the blowing agent other than the inorganic gas include aliphatic hydrocarbons such as propane, isobutane, normal butane, isopentane, and normal pentane, and mixtures thereof.

  In the production method of the present invention, for example, polypropylene resin particles are dispersed in a dispersion medium in a pressure vessel, heated to a temperature higher than the temperature at which the polypropylene resin particles are softened, pressurized, and then one end of the pressure vessel is opened. The so-called initially obtained expanded particles (hereinafter referred to as “one-stage expanded particles” or “original expanded polypropylene resin particles”) obtained by releasing polypropylene resin particles into an atmosphere at a lower pressure than in the pressure vessel. In some cases) (this process may be referred to as “two-stage foaming”), and a polypropylene resin foam particle (hereinafter “two-stage foam particle”) having a higher expansion ratio than the original foam particle. May be used).

  The expansion ratio of the original expanded polypropylene resin particles (single-stage expanded particles) is 5 times or more and 18 times or less, preferably 7 times or more and 15 times or less. When the expansion ratio of the first-stage expanded particles is less than 5 times, it is difficult to obtain expanded particles with a higher expansion ratio even by two-stage expansion. Further, the shrinkage recovery property of the in-mold foam molded product obtained from the two-stage foamed particles is lowered. When the expansion ratio of the first-stage expanded particles exceeds 18 times, it is necessary to increase the pressure in the pressure-resistant container when manufacturing the first-stage expanded particles, and the manufacturing equipment becomes expensive. In addition, the resulting single-stage foamed particles have a small cell diameter and closed cell ratio, which causes a decrease in the properties of the polypropylene resin-in-mold foam-molded product, such as a decrease in shrinkage recovery of the polypropylene-based resin mold-in-mold. It becomes. In the present invention, the expansion ratio of the expanded polypropylene resin particles refers to the true magnification, not the apparent magnification, and the measurement method will be described later.

Cell diameter stage expanded particles used in the present invention have an average cell diameter that satisfy the following formula (1).
Average cell diameter (μm) ≧ 240 −8 × foaming ratio (1)

If one step foamed particles have an average cell diameter out of the range of formula (1), shrinkage recovery of the finally obtained molded article decrease.

Stage expanded particles used in the present invention, that have a mean cell diameter that satisfy the following formula (2). When cell diameter one step expanded particles are not in these ranges, Ru tended the surface of the resulting polypropylene resin mold foamed articles is reduced.
Average cell diameter (μm) ≦ 300−8 × foaming ratio (2)

In the present invention, the average bubble diameter is an apparent average bubble diameter as described later. FIG. 1 illustrates the range of expansion ratio and average cell diameter of single-stage expanded particles used in the production method of the present invention. In FIG. 1, the inside of the frame with parallel oblique lines is the range of the expansion ratio and average cell diameter of the single-stage expanded particles used in the production method of the present invention. For reference, FIG. 1 shows the expansion ratio and bubble diameter of single-stage expanded particles used in the examples of JP-A-59-133233. The expanded particles used in the examples of JP-A-59-133233 are outside the range of the expansion ratio and the bubble diameter of the present invention.

  Such single-stage expanded particles are further expanded to produce polypropylene resin expanded particles having a higher expansion ratio than the original expanded particles. The foaming method is not particularly limited, and examples thereof include a method of impregnating a single-stage foamed particle with a foaming agent and applying an internal pressure, and then heating and foaming with steam or the like. The foaming agent is not particularly limited, and the above foaming agents can be used, but it is preferable to use air. When using air, the pressure may be increased stepwise so that the final room temperature pressure in the single-stage expanded particles is 0.15 to 0.7 MPa, preferably 0.2 to 0.5 MPa. preferable. The foaming agent may be impregnated at room temperature, or the foaming agent may be impregnated under heating. When heated, the foaming agent tends to impregnate quickly.

  The one-stage expanded particles to which the internal pressure is applied are expanded by heating with steam or the like while stirring. The two-stage expanded particles obtained by two-stage expansion can be further expanded to produce expanded particles having a higher expansion ratio.

  The expansion ratio of the expanded polypropylene resin particles used in the present invention is not particularly limited, but is 2 to 60 times, preferably 3 to 40 times. In particular, a range of 20 to 40 times, further 25 to 35 times, further 25 to 33 times, and further 26 to 33 times is preferable. When the bulk magnification is used, the expansion ratio of the expanded particles used in the present invention is 3 to 90 times, preferably 4 to 60 times. In particular, a range of 30 to 60 times, further 35 to 55 times, further 35 to 50 times, and further 40 to 50 times is preferable.

  In the DSC curve obtained by the differential scanning calorimeter (DSC) measurement (sample 3 to 6 mg, temperature range 40 ° C. to 220 ° C., temperature rising rate 10 ° C./min), the polypropylene resin expanded particles used in the present invention have a low temperature. It is preferable to have two melting peaks on the side and the high temperature side. When two melting peaks are present, when the expanded polypropylene resin particles are subjected to in-mold foam molding, the range of molding conditions such as a heating temperature range tends to be widened.

The ratio of the high temperature side heat of fusion (Q _H / (Q _H + Q _L ) × 100, which can be calculated from the low temperature side heat of fusion (Q _L ) and the high temperature side heat of fusion (Q _H ) corresponding to the two melting peaks of the DSC curve. ) (Hereinafter sometimes referred to as DSC ratio) is preferably in the range of 10 to 40%. Here, the low-temperature melting heat (Q _L ) corresponds to the region surrounded by the tangent drawn from the local maximum point between the low-temperature melting peak and the high-temperature melting peak to the baseline near the melting start temperature and the low-temperature melting peak. The amount of heat to be. Further, the high temperature side heat of fusion (Q _H ) is an amount of heat corresponding to a region surrounded by a tangent drawn from the maximum point to the base line near the melting end temperature and the high temperature side melting peak.

  When the DSC ratio is less than 10%, the closed cell ratio of the polypropylene resin foamed particles is low, and the shrinkage recovery property of the polypropylene resin in-mold foam molded product tends to decrease. If the DSC ratio exceeds 40%, the secondary foaming force may not be sufficiently obtained when the polypropylene resin foamed particles are subjected to in-mold foam molding, and the polypropylene resin mold is inferior in fusion between the polypropylene resin foamed particles. An inner foamed molded product may be obtained.

  When the polypropylene resin expanded particles are used for in-mold foam molding, the following known methods can be used. A) a method for use as it is, b) a method for injecting an inorganic gas such as air into foamed particles in advance to impart foaming ability, and c) a method for filling foamed particles in a mold in a compressed state and molding. Among these, the method (b) in which an inorganic gas such as air is press-fitted into the foamed particles in advance to impart foamability is preferable.

Specifically, an in-mold foam molded product can be obtained by the following molding method.
1) The foaming ability is imparted by pressurizing the polypropylene resin foamed particles with air in a pressure resistant container and pressing the air into the polypropylene resin foamed particles.
2) The obtained expanded particles are filled in a molding space that is composed of two molds and can be closed but cannot be sealed.
3) Molding is performed using steam or the like as a heating medium at a steam pressure of about 0.2 to 0.4 MPa and a heating time of about 3 to 30 seconds to fuse the polypropylene resin expanded particles.
4) Cool the mold with water 5) Open the mold and take out the in-mold foam molded body.

  The expansion ratio of the obtained in-mold foam molded product is not particularly limited, but is 3 to 90 times, preferably 4 to 60 times.

  The in-mold foam-molded product obtained by the production method of the present invention can be used for applications such as a heat insulating material, a buffer packaging material, an automobile interior member, and a core material for an automobile bumper. It is a particularly desirable usage method to use an in-mold foam molded product obtained by using the production method of the present invention for a buffer packaging material in which an in-mold foam molded product having a high expansion ratio is often used.

  Next, the present invention will be described based on examples and comparative examples. Unless otherwise indicated, “part” and “%” are based on weight. In addition, the evaluation method of an expanded particle and an in-mold expansion molding is as follows.

(Expansion ratio of polypropylene resin expanded particles)
About ³ to 10 g of polypropylene resin foamed particles are taken, dried at 60 ° C. for 6 hours, and then the weight W (g) and the submerged volume V (cm ³ ) are measured. The expansion ratio is calculated by the following equation from the resin density 0.9 (g / cm ³ ) of the polypropylene resin.
Foaming ratio = V / (W / 0.9)

(Average bubble diameter)
Ten pieces are arbitrarily taken out from the polypropylene resin foamed particles, and the foamed particles are cut with sufficient care so that the cell membrane is not broken. In a magnified photomicrograph (× 100 magnification) of the cut surface, a line segment corresponding to a length of 2 mm is drawn on the portion excluding the surface layer portion, and the number of bubbles passing through the line segment is counted. Similarly, for the other nine expanded particles, the number of bubbles is counted, and the average of the number of bubbles of 10 expanded particles is defined as the average number of bubbles. The average cell diameter of the expanded particles is calculated by dividing 2 mm by the average number of cells of 10 expanded particles.

(Foaming ratio of foamed molded product in polypropylene resin mold)
It is calculated by the following formula from the dry weight W (g) of the foamed molded product in the polypropylene resin mold, the submerged volume V (cm ³ ), and the resin density of the polypropylene resin 0.9 (g / cm ³ ).
Foaming ratio of in-mold foam molding = V / (W / 0.9)

(Recovery of shrinkage of foamed molded product in polypropylene resin mold)
The shrinkage recovery property was evaluated using a polypropylene resin in-mold foam molded product obtained from a flat plate mold having an outer dimension of 400 mm × 300 mm × 20 mm. This flat polypropylene resin mold was molded, allowed to stand at room temperature for 1 hour, and then cured at 75 ° C. for 3 hours. Furthermore, it left still at room temperature for 1 hour, and measured the length of the longitudinal direction of a polypropylene resin type in-mold foaming molding. The length of the expanded foam in a polypropylene resin mold relative to the length of the mold was determined to calculate the shrinkage rate. Shrinkage recovery was evaluated according to the following criteria.
◎: Shrinkage rate 4% or less ○: Shrinkage rate 4% or more and 5% or less △: Shrinkage rate 5% or more and 6% or less ×: Shrinkage rate 6% or less

(Surface properties of foam molded products in polypropylene resin molds)
The surface of the foamed molded product in the polypropylene resin mold, whose shrinkage recovery property was evaluated, was observed. The surface property was evaluated according to the following criteria.
◯: Wrinkles, less intergranular, beautiful Δ: Slight wrinkles, intergranular but good x: Wrinkles, sink marks and poor appearance

(Fusibility of foamed molded product in polypropylene resin mold)
It evaluated using the polypropylene-type resin in-mold expansion-molding body which evaluated shrinkage recovery property. About 5 mm of notch was put into the polypropylene resin mold in-mold foam with a cutter knife, and it was bent and broken along the notch. The state of the fracture surface was visually observed and evaluated according to the following criteria.
○: On the fractured surface, the ratio of fracture at the expanded particle interface is 40% or less.
X: On the fracture surface, the ratio of fracture at the expanded particle interface is greater than 40%.

(Examples 1-9, Comparative Examples 1-3)
Polypropylene resin (ethylene content: 4.0% by weight, MFR: 5.2 g / 10 min, Mn: 100,000, Mw / Mn: 3.7, melting point: 137 ° C.) was used. By adjusting the type and amount of the nucleating aid, single-stage expanded particles having the expansion ratio, average cell diameter and DSC ratio shown in Table 1 were produced. The obtained single-stage expanded particles showed two melting points at approximately 131 ° C. and 151 ° C. in differential scanning calorimetry.

After drying the obtained expanded particles (single-stage expanded particles) at 60 ° C. for 6 hours, impregnating with pressurized air in a pressure resistant container to make the internal pressure about 0.4 to 0.5 MPa, Two-stage foaming was performed by contacting with steam of about 0.05 to 0.08 MPa (G) to obtain two-stage foamed particles having an expansion ratio of 30 times. Table 1 shows the average particle size of the obtained two-stage expanded particles. Example 3 is not an example of the present invention but a reference example.

  The two-stage foamed particles were again pressurized with air in a pressure resistant container to give an internal pressure of about 0.17 MPa. The obtained foamed particles are filled into a flat mold (400 mm × 300 mm × 20 mm) and molded with 0.26 MPa (G) steam to obtain a foamed polypropylene resin mold with a foaming ratio of 44 times. It was. Table 1 shows the fusing property, shrinkage recovery property, and surface property of the obtained polypropylene resin in-mold foam molding. FIG. 1 shows the expansion ratio and the bubble diameter of the single-stage expanded particles in Examples and Comparative Examples.

表１から明らかなように本発明の製造方法によれば優れた収縮回復性を有するポリプロピレン系樹脂型内発泡成形体を与えることができる。

As is apparent from Table 1, according to the production method of the present invention, a polypropylene resin in-mold foam molded article having excellent shrinkage recovery properties can be provided.

It is a graph which shows the range of the expansion ratio and average cell diameter of the one-stage expanded particle used for this invention.

Claims (3)

A polypropylene system comprising an ethylene-propylene random copolymer having a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) of 5 or less and containing 3 to 6% by weight of ethylene as a copolymer component. the resin as a base resin, the expansion ratio is less than 14.9 times 9.7 times or more, and the following formula (1), obtained by further foaming the original PP beads satisfying (2) A method for producing a foamed molded product in a polypropylene resin mold, characterized in that polypropylene resin foamed particles having a higher expansion ratio than the original foamed particles are used.
Average cell diameter (μm) ≧ 240 −8 × foaming ratio (1)
Average cell diameter (μm) ≦ 300−8 × foaming ratio (2) The method for producing an in-mold foam-molded polypropylene resin product according to claim 1 , wherein the melt flow rate (MFR) of the polypropylene resin is 3 g / 10 min or more and 8 g / 10 min or less. The method for producing a foamed molded product in a polypropylene resin mold according to claim 1 or 2 , wherein the number average molecular weight (Mn) of the polypropylene resin is from 50,000 to 150,000.

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