EXPANDED POLYPROPYLENE RESIN PARTICLE

Abstract

An expanded polypropylene resin particle includes a polypropylene resin composition that serves as a base material resin. The polypropylene resin composition includes a first polypropylene resin having a melting point of 140° C. or less, a second polypropylene resin having a melting point of 145° C. or more, and a polyethylene resin having a melting point of 120° C. to 135° C. The first polypropylene resin accounts for 50 to 75 weight %, the second polypropylene resin accounts for 25 to 50 weight %, and the polyethylene resin accounts for 1 to 10 weight %, wherein the weight % is based on a total amount of the first polypropylene resin, the second polypropylene resin, and the polyethylene resin.

Claims

1. An expanded polypropylene resin particle comprising: a polypropylene resin composition that serves as a base material resin, the polypropylene resin composition comprising: 50 to 75 weight % of a first polypropylene resin having a melting point of 140° C. or less; 25 to 50 weight % of a second polypropylene resin having a melting point of 145° C. or more; and 1 to 10 weight % of a polyethylene resin having a melting point of 120° C. to 135° C., wherein the weight % is based on a total amount of the first polypropylene resin, the second polypropylene resin, and the polyethylene resin.

2. The expanded polypropylene resin particle according to claim 1, wherein the first polypropylene resin is a propylene-ethylene-1-butene random copolymer.

3. The expanded polypropylene resin particle according to claim 1, wherein the second polypropylene resin is a propylene-ethylene random copolymer or a propylene-ethylene-1-butene random copolymer.

4. The expanded polypropylene resin particle according to claim 1, wherein the melting point of the polyethylene resin is 125° C. to 135° C.

5. The expanded polypropylene resin particle according to claim 1, wherein a melting point of the polypropylene resin composition is 140° C. to 150° C.

6. The expanded polypropylene resin particle according to claim 1, wherein the first polypropylene resin and the second polypropylene resin are Ziegler-Natta polypropylene resins.

7. A polypropylene resin in-mold expanded molded product produced by using expanded polypropylene resin particles according to claim 1.

8. The polypropylene resin in-mold expanded molded product according to claim 7, wherein the polypropylene resin in-mold expanded molded product satisfies the following relationship of a density and a 50%-strained compressive strength:
[50%-strained compressive strength(MPa)]≧0.0069×[Molded product density(g/L)]+0.018.

9. A method of producing expanded polypropylene resin particles, comprising: (i) placing polypropylene resin particles, water, and an inorganic gas foaming agent in a pressure-resistant container, the polypropylene resin particles comprising a polypropylene resin composition that serves as a base material resin, wherein the polypropylene resin composition comprises: 50 to 75 weight % of a first polypropylene resin having a melting point of 140° C. or less; 25 to 50 weight % of a second polypropylene resin having a melting point of 145° C. or more; and 1 to 10 weight % of a polyethylene resin having a melting point of 120° C. to 135° C., wherein the weight % is based on a total amount of the first polypropylene resin, the second polypropylene resin, and the polyethylene resin, (ii) obtaining a dispersion liquid by dispersing the polypropylene resin particles and the inorganic gas foaming agent in the water while stirring the polypropylene resin particles and the inorganic gas foaming agent, (iii) increasing a temperature and a pressure in the pressure-resistant container, and (iv) releasing the dispersion liquid in the pressure-resistant container into a region having a pressure lower than an internal pressure of the pressure-resistant container, thereby foaming the polypropylene resin particles.

10. The method according to claim 9, wherein the first polypropylene resin is a propylene-ethylene-1-butene random copolymer.

11. The method according to claim 9, wherein the second polypropylene resin is a propylene-ethylene random copolymer or a propylene-ethylene-1-butene random copolymer.

12. The method according to claim 9, wherein the melting point of the polyethylene resin is 125° C. to 135° C.

13. The method according to claim 9, wherein a melting point of the polypropylene resin composition is 140° C. to 150° C.

14. The method according to claim 9, wherein the first polypropylene resin and the second polypropylene resin are Ziegler-Natta polypropylene resins.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0040] FIG. 1 is a view illustrating a DSC curve of second temperature rise obtained when, in differential scanning calorimetry (DSC), (i) a temperature of a polypropylene resin composition X in accordance with one or more embodiments of the present invention is raised from 40° C. to 220° C. at a heating rate of 10° C./min., (ii) the temperature is cooled from 220° C. to 40° C. at a rate of 10° C./min., and (iii) the temperature is raised again from 40° C. to 220° C. at a rate of 10° C./min.

[0041] FIG. 2 is a view illustrating a DSC curve (temperature vs heat absorption quantity) obtained by a differential scanning calorimetry (DSC) in which a temperature of an expanded polypropylene resin particle in accordance with one or more embodiments of the present invention is raised from 40° C. to 220° C. at a heating rate of 10° C./min. The DSC curve shows two melting peaks and two melting heat quantity regions. The two melting heat quantity regions are a low temperature-side melting heat quantity region Ql and a high temperature-side melting heat quantity region Qh.

DESCRIPTION OF EMBODIMENTS

[0042] In one or more embodiments of the present invention, each of expanded polypropylene resin particles is obtained from a polypropylene resin composition X (“polypropylene resin composition”) containing a polypropylene resin A (“first polypropylene resin”), a polypropylene resin B (“second polypropylene resin”), and a polyethylene resin C (“polyethylene resin”).

[0043] The polypropylene resin A used in one or more embodiments of the present invention is a polypropylene resin which has a melting point of 140° C. or lower.

[0044] The polypropylene resin A used in one or more embodiments of the present invention preferably has a structural unit(s) of 1-butene in an amount of 2 weight % or more to 15 weight % or less with respect to 100 weight % entire structural units. If a structural unit of 1-butene is less than 2 weight %, then a molding temperature during in-mold foaming molding tends not to decrease. If a structural unit of 1-butene is more than 15 weight %, then a compressive strength of an in-mold expanded molded product to be obtained tends to decrease.

[0045] The polypropylene resin A used in one or more embodiments of the present invention can contain, in addition to 1-butene, a structural unit of a comonomer which is copolymerizable with propylene. Examples of the comonomer encompass at least one type of α-olefin, such as ethylene, 1-pentene, 1-hexene, and 4-methyl-1-butene, any of which has 2 carbon atoms or any of 4 carbon atoms through 12 carbon atoms. Among these, the comonomer is preferably ethylene.

[0046] The polypropylene resin A used in one or more embodiments of the present invention is preferably, in regard to ethylene, such that a structural unit of ethylene is present in amount of 2 weight % or more to 10 weight % or less with respect to 100 weight % entire structural units. The polypropylene resin A preferably satisfies the above conditions, because, with such a polypropylene resin A, (i) a molding temperature during in-mold foaming molding can be easily made low and (ii) compressive strength of an in-mold expanded molded product to be obtained does not decrease but can be kept high. Note that “100 weight % entire structural units” means that the sum of a structural unit obtained from propylene, a structural unit obtained from 1-butene, and a structural unit obtained from another/other comonomer(s) such as ethylene accounts for 100 weight %.

[0047] For the above reason, the polypropylene resin A according to one or more embodiments of the present invention is preferably at least one selected from the group consisting of (i) a propylene-1-butene random copolymer and (ii) a propylene-ethylene-1-butene random copolymer.

[0048] The polypropylene resin A used in one or more embodiments of the present invention has a melting point of 140° C. or lower, preferably 130° C. or higher to 140° C. or lower, and more preferably 132° C. or higher to 138° C. or lower. If the melting point of the polypropylene resin A is more than 140° C., then a molding temperature during in-mold foaming molding tends not to decrease. If the melting point of the polypropylene resin A is lower than 130° C., then compressive strength of an in-mold expanded molded product to be obtained tends to decrease.

[0049] A catalyst for use in polymerization of the polypropylene resin A in accordance with one or more embodiments of the present invention is not limited to any particular one. Examples of the catalyst encompass a Ziegler catalyst (more specifically, a Ziegler-Natta catalyst) and metallocene catalyst.

[0050] In general, in comparison with a polypropylene resin polymerized with the use of a metallocene catalyst, a polypropylene resin polymerized with the use of a Ziegler catalyst has lower rigidity by melting point matching. Specifically, a comparison of rigidity of a Ziegler polypropylene resin and rigidity of a metallocene polypropylene resin having an identical melting point shows that the rigidity of the Ziegler polypropylene resin is lower. Therefore, the use of a polypropylene resin polymerized with the use of a Ziegler catalyst may generally be disadvantageous in order to obtain such advantageous effects according to one or more embodiments of the present invention as (i) reducing a molding temperature during in-mold foaming molding to a low temperature and (ii) maintaining compressive strength of a polypropylene resin in-mold expanded molded product to be obtained. However, with one or more embodiments of the present invention, it is possible to easily obtain the advantageous effects even in a case where a polypropylene resin polymerized with the use of a Ziegler catalyst is used. That is, in one or more embodiments, it is more preferable to use a polypropylene resin A which is polymerized with the use of a Ziegler catalyst. In one or more embodiments, a polypropylene resin polymerized with the use of a Ziegler catalyst is also preferable in view of the fact that (i) such a polypropylene resin is industrially more available than a polypropylene resin polymerized with the use of a metallocene catalyst and (ii) such a polypropylene resin can be put to a wider range of use. Although usable also as a polypropylene resin B described later, a polypropylene resin polymerized with the use of a Ziegler catalyst brings about the advantageous effects more remarkably when being used as a polypropylene resin A.

[0051] The polypropylene resin B used in one or more embodiments of the present invention is a polypropylene resin which has a melting point of 145° C. or higher.

[0052] Examples of the polypropylene resin B used in one or more embodiments of the present invention encompass (i) a propylene homopolymer and (ii) a copolymer including: propylene; and a comonomer which is copolymerizable with propylene.

[0053] The polypropylene resin B in accordance with one or more embodiments of the present invention is preferably a copolymer including propylene and a comonomer copolymerizable with the propylene in view of the fact that such a polypropylene resin B allows a molding temperature during in-mold foaming molding to be easily made low. Examples of such a comonomer which is copolymerizable with propylene encompass α-olefin, such as ethylene, 1-butene, 1-pentene, 1-hexene, and 4-methyl-1-butene, any of which has 2 carbon atoms or any of 4 carbon atoms through 12 carbon atoms. Among these, ethylene is preferable. These comonomers can be individually copolymerized with propylene, or these comonomers in combination can be copolymerized with propylene.

[0054] The polypropylene resin B in accordance with one or more embodiments of the present invention is preferably a propylene-ethylene random copolymer or a propylene-ethylene-1-butene random copolymer in view of the fact that such a polypropylene resin B allows a molding temperature during in-mold foaming molding to be easily made low and makes it possible to maintain high compressive strength of an in-mold expanded molded product to be obtained without causing the compressive strength to decrease.

[0055] A melting point of the polypropylene resin B in accordance with one or more embodiments of the present invention is 145° C. or higher, preferably 145° C. or higher to 160° C. or lower, and more preferably 147° C. or higher to 158° C. or lower. If the melting point of the polypropylene resin B is lower than 145° C., then compressive strength of an in-mold expanded molded product to be obtained tends to decrease. If the melting point is more than 160° C., then a molding temperature during in-mold foaming molding tends to be high.

[0056] A catalyst for use in polymerization of the polypropylene resin B is not limited to any particular one. Examples of the catalyst encompass a Ziegler catalyst (more specifically, a Ziegler-Natta catalyst) and metallocene catalyst. However, in one or more embodiments, a polypropylene resin B polymerized with the use of a Ziegler catalyst is preferable in view of the fact that such as polypropylene resin B is easily available industrially and can be put to a wider range of use.

[0057] A melt flow rate (hereinafter referred to as “MFR”) of each of the polypropylene resin A and the polypropylene resin B used in one or more embodiments of the present invention is not particularly limited, but is preferably more than 3 g/10 min. to less than 10 g/10 min., and more preferably 5 g/10 min. or more to 9 g/10 min. or less. If the MFR of the polypropylene resin A or the polypropylene resin B is more than 3 g/10 min. to less than 10 g/10 min., then (i) an in-mold expanded molded product tends to have a good surface appearance and (ii) a molding cycle during molding tends to be short. Note that the MFR of each of the polypropylene resin A and the polypropylene resin B in accordance with one or more embodiments of the present invention is measured with the use of an MFR measuring instrument described in JIS-K7210 and under conditions involving (i) an orifice having a diameter of 2.0959±0.005 mm and a length of 8.000±0.025 mm, (ii) a load of 2160 g, and (iii) a temperature of 230° C.±0.2° C.

[0058] In one or more embodiments of the present invention, a polyethylene resin C is used with the aim of allowing a molding temperature to be easily made low and enhancing the appearance of a molded product.

[0059] A melting point of the polyethylene resin C in accordance with one or more embodiments of the present invention is 120° C. or higher to 135° C. or lower, preferably 125° C. or higher to 135° C. or lower, more preferably 122° C. or higher to 134° C. or lower, and even more preferably 125° C. or higher to 133° C. or lower. If the melting point of the polyethylene resin C is lower than 120° C., then compressive strength of an in-mold expanded molded product to be obtained tends to decrease. If the melting point is more than 135° C., then a molded product tends to have a poor appearance.

[0060] The polyethylene resin C in accordance with one or more embodiments of the present invention is preferably a high-density polyethylene resin having a density of 0.95 g/cm.sup.3 or more in view of the fact that the polyethylene resin C can prevent a decrease in compressive strength. Further, the polyethylene resin C is preferably a polyethylene resin having a high molecular weight rather than polyethylene wax having a low molecular weight.

[0061] The MFR of the polyethylene resin C used in one or more embodiments of the present invention is not particularly limited, but is preferably 0.1 g/10 min. or more to 10 g/10 min. or less, and more preferably 0.5 g/10 min. or more to 9 g/10 min. or less. If the MFR of the polyethylene resin C is 0.1 g/10 min. or more to 10 g/10 min. or less, then an in-mold expanded molded product tends to have a good surface appearance. Note that the MFR of the polyethylene resin C in accordance with one or more embodiments of the present invention is measured with the use of an MFR measuring instrument described in JIS-K7210 and under conditions involving (i) an orifice having a diameter of 2.0959±0.005 mm and a length of 8.000±0.025 mm, (ii) a load of 2160 g, and (iii) a temperature of 190° C.±0.2° C.

[0062] In one or more embodiments of the present invention, in view of allowing a molding temperature during in-mold foaming molding to be easily made low and maintaining high compressive strength of an in-mold expanded molded product to be obtained without causing the compressive strength to decrease, a ratio at which the constituent elements of the polypropylene resin composition X, i.e., the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C, are mixed is preferably such that the polypropylene resin A accounts for 50 weight % or more to 75 weight % or less, the polypropylene resin B accounts for 25 weight % or more to 50 weight % or less, and the polyethylene resin C accounts for 1 weight % or more to 10 weight % or less in a case where a total amount of the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C is 100 weight %. The ratio is more preferably such that the polypropylene resin A accounts for 55 weight % or more to 70 weight % or less, the polypropylene resin B accounts for 30 weight % or more to 45 weight % or less, and the polyethylene resin C accounts for 2 weight % or more to 9 weight % or less in a case where a total amount of the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C is 100 weight %. In a case where the polypropylene resin A accounts for less than 50 weight %, a molding temperature tends to increase. In a case where the polypropylene resin A accounts for more than 75 weight %, a high compressive strength tends not to be maintained. In a case where the polypropylene resin B accounts for less than 25 weight %, a high compressive strength tends not to be maintained. In a case where the polypropylene resin B accounts for more than 50 weight %, a molding temperature tends to increase. In a case where the polyethylene resin C accounts for less than 1 weight %, the effect of decreasing a temperature of a molded product and the effect of improving an appearance of a molded product tend not to be obtained. In a case where the polyethylene resin C accounts for more than 10 weight %, a high compressive strength tends not to be maintained.

[0063] In one or more embodiments of the present invention, it is possible to use an additive as necessary in addition to the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C. Examples of the additive encompass: a resin other than a polypropylene resin and a polyethylene resin; an expansion nucleating agent; a hydrophilic compound; a colorant; an antistatic agent; a flame retarder; an antioxidant; and electrically conductive agent. In such a case, a base material resin can be constituted by a mixture of the polypropylene resin A, the polypropylene resin B, the polyethylene resin C, and the additive.

[0064] In one or more embodiments of the present invention, it is preferable to add, to a base material resin, an expansion nucleating agent which is to become an expansion nucleus during expansion.

[0065] Specific examples of the expansion nucleating agent for use in one or more embodiments of the present invention encompass silica (silicon dioxide), silicate, alumina, diatomaceous earth, calcium carbonate, magnesium carbonate, calcium phosphate, feldspar, apatite, and barium sulfate. Examples of silicate encompass talc, magnesium silicate, kaolin, halloysite, dickite, aluminum silicate, and zeolite. These expansion nucleating agents can be used individually or in combination.

[0066] In view of uniformity of cell diameters, an amount of the expansion nucleating agent contained in accordance with one or more embodiments of the present invention is preferably equal to or greater than 0.005 parts by weight and equal to or less than 2 parts by weight, more preferably equal to or greater than 0.01 parts by weight and equal to or less than 1 part by weight, and even more preferably equal to or greater than 0.03 parts by weight and equal to or less than 0.5 parts by weight with respect to 100 parts by weight of the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C combined.

[0067] In one or more embodiments of the present invention, adding a hydrophilic compound to a base material resin brings about the effect of promoting an increase in expansion ratio of expanded polypropylene resin particles, and is therefore preferable.

[0068] Specific examples of a hydrophilic compound for use in one or more embodiments of the present invention encompass water-absorbing organic matters such as glycerin, polyethylene glycol, glycerin fatty acid ester, melamine, isocyanuric acid, and a melamine-isocyanuric acid condensate. These hydrophilic compounds can be used individually or in combination.

[0069] An amount of the hydrophilic compound contained in accordance with one or more embodiments of the present invention is preferably equal to or greater than 0.01 parts by weight and equal to or less than 5 parts by weight, and more preferably equal to or greater than 0.1 parts by weight and equal to or less than 2 parts by weight with respect to 100 parts by weight of the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C combined. If the amount of the hydrophilic compound contained is less than 0.01 parts by weight, then the effect of increasing an expansion ratio and the effect of enlarging a cell diameter are difficult to be obtained. If the amount of the hydrophilic compound contained is more than 5 parts by weight, then the hydrophilic compound becomes unlikely to be uniformly dispersed in a polypropylene resin.

[0070] Examples of the colorant for use in one or more embodiments of the present invention encompass carbon black, ultramarine blue, cyanine pigment, azo pigment, quinacridone pigment cadmium yellow, chrome oxide, iron oxide, perylene pigment, and Anthraquinone pigment. These colorants can be used individually or in combination.

[0071] An amount of the colorant contained in accordance with one or more embodiments of the present invention is preferably equal to or greater than 0.001 parts by weight and equal to or less than 10 parts by weight, and more preferably equal to or greater than 0.01 parts by weight and equal to or less than 8 parts by weight with respect to 100 parts by weight of the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C combined. In a case where blackening is intended with the use of carbon black, in particular, the carbon black is preferably equal to or greater than 1 part by weight and equal to or less than 10 parts by weight with respect to 100 parts by weight of the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C combined.

[0072] Note that, a melting point of a polypropylene resin (specifically, polypropylene resin A, polypropylene resin B, or polypropylene resin composition X) or a polyethylene resin (specifically, polyethylene resin

[0073] C) is a melting peak temperature in a second temperature rise in a DSC curve which is obtained when, in differential scanning calorimetry (DSC), 1 mg or more to 10 mg or less of polypropylene resin or polyethylene resin is (i) heated from 40° C. to 220° C. at a heating rate of 10° C./min., (ii) cooled from 220° C. to 40° C. at a cooling rate of 10° C./min., and then (iii) heated again from 40° C. to 220° C. at a heating rate of 10° C./min.

[0074] For the polypropylene resin composition X in accordance with one or more embodiments of the present invention, not only a single melting maximum peak Tm (PP) based on the polypropylene resin A and the polypropylene resin B but also a melting peak (or shoulder) Tm (PE) based on the polyethylene resin C appear around, for example, 130° C., as illustrated in 1. That is, the total of two melting peaks appear.

[0075] In one or more embodiments of the present invention, a melting point of the polypropylene resin composition X is obtained from (i) a melting point of approximately 135° C. or higher to 155° C. or lower, based on the respective melting points of the polypropylene resin A and the polypropylene resin B, and (ii) a melting point of approximately 120° C. or higher to 135° C. or lower, based on the melting point of the polyethylene resin C. In view of allowing a molding temperature during in-mold foaming molding to be easily made low and maintaining high compressive strength of an in-mold expanded molded product to be obtained without causing the compressive strength to decrease, the melting maximum peak point Tm (PP) based on the respective melting points of the polypropylene resin A and the polypropylene resin B is preferably 140° C. or higher to 150° C. or lower, more preferably 141° C. or higher to 149° C. or lower, and even more preferably 142° C. or higher to 148° C. or lower. Note that the “melting point of the polypropylene resin composition X” herein means the melting point Tm (PP).

[0076] In one or more embodiments of the present invention, examples of a method of mixing the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C to form the polypropylene resin composition X encompass (i) a method in which the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C are mixed with the use of, for example, a blender or an extruder and (ii) a method in which the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C are blended by multi-stage polymerization during polymerization.

[0077] Note that the method in which, for example, a blender or an extruder is used can also be used as a method of mixing the aforementioned additive in the polypropylene resin composition X. Note also that the aforementioned additive can be directly added.

[0078] Alternatively, it is possible to (i) prepare a masterbatch by including, at a high concentration, the additive in another resin and then (ii) add the masterbatch as a masterbatch resin.

[0079] In one or more embodiments, a resin to be used for production of the masterbatch resin is preferably a polyolefin resin, more preferably the polypropylene resin A and/or the polypropylene resin B, and most preferably a mixture of the polypropylene resin A and the polypropylene resin B.

[0080] In production of expanded polypropylene resin particles in accordance with one or more embodiments of the present invention, a method (granulation step) of producing polypropylene resin particles, which are made of a base material resin, can be first carried out.

[0081] Examples of the method of producing polypropylene resin particles encompass a method in which an extruder is used. Specifically, it is possible, for example, that (i) a polypropylene resin A, a polypropylene resin B, a polyethylene resin C, and, as necessary, an additive such as another resin, an expansion nucleating agent, a hydrophilic compound, and a colorant are blended, so that a blended product is obtained, (ii) the blended product is introduced into an extruder and is melted and kneaded, (iii) a resultant product is extruded through a die provided at a tip of the extruder, and is then allowed to pass through water so as to be cooled, and (iv) the resultant product is chopped with the use of a cutter, so that a desired particle shape such as a columnar shape, an ellipsoidal shape, a spherical shape, a cubic shape, and a rectangular parallelepiped shape can be obtained.

[0082] Alternatively, it is possible to (i) directly extrude the blended product through the die into water, and immediately cut the resultant product into a particle shape, so that particles are obtained, and then (ii) cool the particles. By thus melting and kneading the resins, the resins are made into a more uniform base material resin. Alternatively, it is possible to (i) introduce the polypropylene resin A, the polypropylene resin B, and the polyethylene resin C into an extruder, (ii) as necessary, feed an additive such as an expansion nucleating agent, a hydrophilic compound, and a colorant from a middle part of the extruder so as to be mixed in the extruder, and (iii) melt and knead a resultant mixture in the extruder.

[0083] In one or more embodiments, a weight of each of the polypropylene resin particles thus obtained is preferably 0.2 mg per particle or more to 10 mg per particle or less, and more preferably 0.5 mg per particle or more to 5 mg per particle or less. If the weight of each of the polypropylene resin particles is less than 0.2 mg per particle, then handleability tends to decrease. If the weight is more than 10 mg per particle, then a mold-filling property during an in-mold foaming molding step tends to decrease.

[0084] Expanded polypropylene resin particles in accordance with one or more embodiments of the present invention can be produced with the use of polypropylene resin particles thus obtained.

[0085] Preferable examples of a method of producing the expanded polypropylene resin particles in accordance with one or more embodiments of the present invention encompass a method of producing expanded polypropylene resin particles in an aqueous dispersion system by carrying out the following foaming step: (i) a dispersion liquid obtained by dispersing polypropylene resin particles along with a inorganic gas foaming agent such as carbon dioxide into an aqueous dispersion medium is placed in a pressure-resistant container, (ii) the dispersion liquid is heated to a temperature equal to or higher than a softening temperature of the polypropylene resin particles and is subjected to pressure, (iii) the temperature and the pressure are retained for a certain period of time, and (iv) the dispersion liquid is released to a region having a pressure lower than an internal pressure of the pressure-resistant container, so that the expanded polypropylene resin particles are obtained.

[0086] Specifically,

(1) Polypropylene resin particles, an aqueous dispersion medium, and, as necessary, a dispersing agent, for example, are placed into the pressure-resistant container. Then, while a resultant dispersion liquid is stirred, the inside of the pressure-resistant container is vacuumed as necessary. Then, a foaming agent having a pressure of 1 MPa (gage pressure) or more to 2 MPa (gage pressure) or less is introduced into the pressure-resistant container, and then the dispersion liquid is heated to a temperature equal to or higher than the softening temperature of the polypropylene resin. By the heating, the internal pressure of the pressure-resistant container rises to approximately 2 MPa (gage pressure) or more to 5 MPa (gage pressure) or less. If necessary, a foaming agent is further added to the inside of the pressure-resistant container around a foaming temperature to adjust a foaming pressure to a desired pressure. Then, a temperature is further adjusted. Thereafter, the adjusted temperature and the adjusted pressure are retained for a certain period of time. Subsequently, the dispersion liquid is released into a region having a pressure lower than the internal pressure of the pressure-resistant container, so that the expanded polypropylene resin particles are obtained.

[0087] As another aspect, the following aspect is possible:

(2) Polypropylene resin particles, an aqueous dispersion medium, and, as necessary, a dispersing agent, for example, are placed into the pressure-resistant container. Then, while a resultant dispersion liquid is stirred, the inside of the pressure-resistant container is vacuumed as necessary. Then, while the dispersion liquid is heated to a temperature equal to or higher than the softening temperature of the polypropylene resin particles, a foaming agent is introduced into the pressure-resistant container. Then, the temperature in the pressure-resistant container is adjusted to a foaming temperature, the foaming temperature is retained for a certain period of time, and the dispersion liquid is released into a region having a pressure lower than the internal pressure of the pressure-resistant container, so that expanded polyolefin resin particles are obtained.

[0088] As yet another aspect, the following aspect is possible:

(3) Polypropylene resin particles, an aqueous dispersion medium, and, as necessary, a dispersing agent, for example, are placed into the pressure-resistant container. Then, while a resultant dispersion liquid is stirred, the dispersion liquid is heated to a temperature around a foaming temperature. Then, a foaming agent is further introduced into the pressure-resistant container, and a temperature in the pressure-resistant container is adjusted to a foaming temperature. Then, the foaming temperature is retained for a certain period of time. Then, the dispersion liquid in the pressure-resistant container is released into a region having a pressure lower than an internal pressure of the pressure-resistant container, so that expanded polyolefin resin particles are obtained.

[0089] Note that the expansion ratio can be adjusted by (i) adjusting a pressure-releasing speed during foaming by increasing the internal pressure of the pressure-resistant container through injecting carbon dioxide, nitrogen, air, or a substance used as a foaming agent, into the pressure-resistant container before the dispersion liquid is released into the low-pressure region and (ii) controlling the pressure through introducing carbon dioxide, nitrogen, air, or a substance used as a foaming agent, into the pressure-resistant container also while the dispersion liquid is being released into the low-pressure region.

[0090] In one or more embodiments of the present invention, the pressure-resistant container into which the polypropylene resin particles are dispersed is not limited to any particular one, provided that the pressure-resistant container is capable of resisting a pressure inside the container and a temperature inside the container during production of the expanded particles. Examples of the pressure-resistant container encompass an autoclave-type pressure-resistant container.

[0091] An aqueous dispersion medium for use in one or more embodiments of the present invention is preferably water. Alternatively, the aqueous dispersion medium can also be an aqueous dispersion medium obtained by adding methanol, ethanol, ethylene glycol, glycerin, or the like to water. In a case where the base material resin contains a hydrophilic compound, water in the aqueous dispersion medium serves also as a foaming agent. This contributes to an increase in expansion ratio.

[0092] Examples of the foaming agent for use in one or more embodiments of the present invention encompass: saturated hydrocarbons such as propane, butane, and pentane; ethers such as dimethyl ether; alcohols such as methanol and ethanol; inorganic gas such as air, nitrogen, and carbon dioxide; and water. Among these foaming agents, inorganic gas and water have particularly small environmental impact and have no dangerous inflammability, and are therefore preferable. It is more preferable to use at least one foaming agent selected from the group consisting of carbon dioxide and water.

[0093] In one or more embodiments of the present invention, it is preferable to use a dispersing agent or/and a dispersion auxiliary agent in order to prevent polypropylene resin particles in an aqueous dispersion medium from adhering to each other.

[0094] Examples of the dispersing agent encompass inorganic dispersion agents such as tertiary calcium phosphate, tertiary magnesium phosphate, basic magnesium carbonate, calcium carbonate, barium sulfate, kaolin, talc, and clay. These inorganic dispersion agents can be used individually, or two or more of these inorganic dispersion agents can be used in combination.

[0095] Examples of the dispersion auxiliary agent encompass: (i) anionic surfactants of carboxylate type, (ii) anionic surfactants of sulfonate type such as alkylsulfonic acid salt, n-paraffin sulfonate salt, alkyl benzene sulfonate, alkyl naphthalene sulfonate, and sulfosuccinate, (iii) anionic surfactants of sulfate ester type such as sulfonated oil, alkyl sulfate salt, alkyl ether sulfate, and alkyl amide sulfate, and (iv) anionic surfactants of phosphate ester type such as alkyl phosphate, polyoxyethylene phosphate, and alkyl allyl ether sulfate. These dispersion auxiliary agents can be used individually or two or more of these dispersion auxiliary agents can be used in combination.

[0096] In one or more embodiments, the following are preferably used in combination: (i) at least one dispersing agent selected from the group consisting of tertiary calcium phosphate, tertiary magnesium phosphate, barium sulfate, and kaolin; and (ii) a dispersion auxiliary agent which is n-paraffin sulfonic acid soda.

[0097] In one or more embodiments of the present invention, it is ordinarily preferable to use an aqueous dispersion medium in an amount of equal to or greater than 100 parts by weight and equal to or less than 500 parts by weight with respect to 100 parts by weight of polypropylene resin particles so that dispensability of the polypropylene resin particles in the aqueous dispersion medium is good. The respective amounts of dispersing agent and dispersion auxiliary agent vary, depending on (i) the types of the dispersing agent and the dispersion auxiliary agent and (ii) the type of and amount of polypropylene resin particles used. Ordinarily, with respect to 100 parts by weight of polypropylene resin particles, the dispersing agent is preferably used in an amount of 0.2 parts by weight or more to 3 parts by weight or less, and the dispersion auxiliary agent is preferably used in an amount of 0.001 parts by weight or more to 0.1 parts by weight or less.

[0098] The step of thus obtaining expanded polypropylene resin particles from polypropylene resin particles may be referred to as “first-stage foaming step”, and the expanded polypropylene resin particles thus obtained may be referred to as “first-stage expanded particles”.

[0099] An expansion ratio of first-stage expanded particles may not reach a predetermined expansion ratio, depending on foaming conditions such as foaming temperature, foaming pressure, and the type of foaming agent. In such a case, expanded polypropylene resin particles whose expansion ratio is increased in comparison with that of first-stage expanded particles can be obtained by (i) applying an internal pressure to the first-stage expanded particles by impregnation of inorganic gas (e.g. air, nitrogen, carbon dioxide) and then (ii) causing the first-stage expanded particles to come into contact with steam having a certain pressure.

[0100] The step of thus further foaming the expanded polypropylene resin particles so as to obtain expanded polypropylene resin particles having a high expansion ratio may be referred to as “second-stage foaming step”. Expanded polypropylene resin particles thus obtained through the second-stage foaming step may be referred to as “second-stage expanded particles”.

[0101] In one or more embodiments of the present invention, a pressure of steam in the second-stage foaming step is adjusted preferably 0.04 MPa (gage pressure) or more to 0.25 MPa (gage pressure) or less, and more preferably 0.05 MPa (gage pressure) or more to 0.15 MPa (gage pressure) or less, in view of the expansion ratio of the second-stage expanded particles.

[0102] If the pressure of steam in the second-stage foaming step is less than 0.04 MPa (gage pressure), then the expansion ratio is less likely to increase. If the pressure is more than 0.25 MPa (gage pressure), then second-stage expanded particles to be obtained tend to adhere to each other, so that it becomes impossible to use the second-stage expanded particles for subsequent in-mold foaming molding.

[0103] In one or more embodiments, an internal pressure of air to be impregnated into the first-stage expanded particles is (i) desirably made to change as appropriate in view of (a) the expansion ratio of the second-stage expanded particles and (b) steam pressure in the second-stage foaming step and (ii) preferably 0.2 MPa or more (absolute pressure) to 0.6 MPa or less (absolute pressure).

[0104] If the internal pressure of air to be impregnated into the first-stage expanded particles is less than 0.2 MPa (absolute pressure), then steam having a high pressure is necessary to increase the expansion ratio, so that the second-stage expanded particles tend to adhere to each other. If the internal pressure of air to be impregnated into the first-stage expanded particles is more than 0.6 MPa (absolute pressure), then the second-stage expanded particles tend to become an open-cell foam. In such a case, rigidity, such as compressive strength, of an in-mold expanded molded product tends to decrease.

[0105] The expansion ratio of the expanded polypropylene resin particles in accordance with one or more embodiments of the present invention is not particularly limited, and is preferably 5 times or more to 60 times or less. If the expansion ratio of the expanded polypropylene resin particles is less than 5 times, then reductions in weight of a polypropylene resin in-mold expanded molded product tend to be insufficient. If the expansion ratio of the expanded polypropylene resin particles is more than 60 times, then mechanical strength of a polypropylene resin in-mold expanded molded product tend to be impractical.

[0106] An average cell diameter of the expanded polypropylene resin particles in accordance with one or more embodiments of the present invention is preferably 80 μm or more to 400 μm or less, and more preferably 85 μm or more to 360 μm or less, and even more preferably 90 μm or more to 330 μm or less. If the average cell diameter falls within these ranges, then the polypropylene resin in-mold expanded molded product tends to (i) have a good surface appearance and (ii) have a high compressive strength.

[0107] The average cell diameter of the expanded polypropylene resin particles can be controlled by adjusting the amount of an expansion nucleating agent to add. Alternatively, the average cell diameter can be controlled by, for example, adjusting a high-temperature heat quantity ratio described later. If the high-temperature heat quantity ratio is less than 15%, then the average cell diameter tends to become large. If the high-temperature heat quantity ratio is more than 50%, then the average cell diameter tends to become small.

[0108] In a DSC curve which is obtained by differential scanning calorimetry (DSC) in which a temperature of the expanded polypropylene resin particles is raised at a heating rate of 10° C./min., as illustrated in FIG. 2, expanded polypropylene resin particles in accordance with one or more embodiments of the present invention have (i) at least two melting peaks and (ii) at least two melting heat quantities of a low temperature-side melting heat quantity (Ql) and a high temperature-side melting heat quantity (Qh). As described earlier, not only the two melting peaks based on the polypropylene resins A and B but also a melting peak (or shoulder) based on the polyethylene resin C appear. That is, the total of three melting peaks appear (see FIG. 2).

[0109] Expanded polypropylene resin particles in accordance with one or more embodiments of the present invention can be easily obtained by, in the earlier-described method of producing expanded polypropylene resin particles in an aqueous dispersion system, (i) adjusting, as appropriate, a temperature in the pressure-resistant container during foaming to a proper value and (ii) retaining the temperature for a certain period of time. That is, in a case where a melting point of the polypropylene resin composition X based on melting points of the polypropylene resins A and B is Tm (PP) (° C.), the temperature in the pressure-resistant container during foaming is preferably Tm (PP)−8 (° C.) or higher, more preferably Tm (PP)−5 (° C.) or higher to Tm (PP)+4 (° C.) or lower, and even more preferably Tm (PP)−5 (° C.) or higher to Tm (PP)+3 (° C.) or lower. A period of time during which the polypropylene resin particles are retained at the temperature in the pressure-resistant container during foaming is preferably 1 min. or more to 120 min. or less, and more preferably 5 min. or more to 60 min. or less.

[0110] In one or more embodiments of the present invention, an entire melting heat quantity (Q), a low temperature-side melting heat quantity (Ql), and a high temperature-side melting heat quantity (Qh) of expanded polypropylene resin particles are defined as follows by use of FIG. 2. In the DSC curve obtained (FIG. 2), the entire melting heat quantity (Q=Ql+Qh), which is the sum of the low temperature-side melting heat quantity (Ql) and the high temperature-side melting heat quantity (Qh), is indicated by a part surrounded by a (i) line segment A-B which is drawn so as to connect a heat absorption quantity (point A) at a temperature of 80° C. and a heat absorption quantity (point B) at a temperature at which melting on a high temperature side ends and (ii) the DSC curve. The low temperature-side melting heat quantity (Ql) is indicated by a part surrounded by a line segment A-D, a line segment C-D, and the DSC curve, and the high temperature-side melting heat quantity (Qh) is indicated by a part surrounded by a line segment B-D, the line segment C-D, and the DSC curve where (i) a point C is a point at which a heat absorption quantity between two melting heat quantity regions in the DSC curve is the smallest, the two melting heat quantity regions being a region of the low temperature-side melting heat quantity and a region of the high temperature-side melting heat quantity and (ii) a point D is a point at which the line segment A-B intersects a line that is drawn so as to extend, parallel to a Y-axis, from the point C toward the line segment A-B.

[0111] The expanded polypropylene resin particles in accordance with one or more embodiments of the present invention has a ratio of the high temperature-side melting heat quantity (Qh) to the entire melting heat quantity [={Qh/(Ql+Qh)}×100(%)] (hereinafter also referred to as “high-temperature heat quantity ratio”), which ratio is preferably 15% or more to 50% or less, more preferably 17% or more to 40% or less, and even more preferably 20% or more to 35% or less. In a case where the high-temperature heat quantity ratio falls within these ranges, even if a molding temperature (steam pressure) during production of a polypropylene resin in-mold expanded molded product is low, it is still easy to obtain a polypropylene resin in-mold expanded molded product which (i) has a good surface appearance, (ii) has a high compressive strength, and (iii) has good fusibility.

[0112] The high-temperature heat quantity ratio of the expanded polypropylene resin particles can be adjusted as appropriate by, for example, (i) a retention time at the temperature in the pressure-resistant container (i.e. a retention time that (a) starts from a time point at which the polypropylene resin particles reach a desired temperature in the pressure-resistant container and (b) ends at time point at which the polypropylene resin particles foam, (ii) a foaming temperature (which is a temperature during foaming and which may or may not be identical to the temperature in the pressure-resistant container), and (iii) foaming pressure (pressure during foaming). In general, a high-temperature heat quantity ratio or a heat quantity at the high temperature-side melting peak tends to become large by extending a retention time, decreasing a foaming temperature, or/and decreasing foaming pressure. Because of these factors, conditions to obtain a desired high-temperature heat quantity ratio can be easily found by conducting several experiments in which a retention time, a foaming temperature, or/and a foaming pressure is systematically changed. Note that the foaming pressure can be adjusted by adjusting the amount of a foaming agent.

[0113] PCT International Publication No. WO2009/001626 discloses an expanded polypropylene resin particle which has such a crystal structure that a DSC curve, which is obtained in a first temperature rise when a temperature of an expanded polypropylene resin particle is raised from room temperature to 200° C. at a heating rate of 2° C./min. in heat flux differential scanning calorimetry, shows (i) a main endothermic peak of 100° C. to 140° C. endothermic peak apex temperature exhibiting 70% to 95% endothermic peak heat quantity with respect to an entire endothermic peak heat quantity and (ii) two or more endothermic peaks appearing on a high-temperature side with respect to the main endothermic peak.

[0114] In terms used in PCT International Publication No. WO2009/001626, the expanded polypropylene resin particles in accordance with one or more embodiments of the present invention are not limited to any number of endothermic peaks on a high-temperature side with respect to a main endothermic peak in heat flux differential scanning calorimetry at a heating rate of 2° C./min., but preferably has such a crystal structure that one endothermic peak appears.

[0115] The expanded polypropylene resin particles having such a crystal structure that one endothermic peak appears can be easily obtained by use of a base material resin including (i) a polypropylene resin A having a melting point of 140° C. or lower and (ii) a polypropylene resin B having a melting point higher than that of the polypropylene resin A by less than 25° C.

[0116] In one or more embodiments, the expanded polypropylene resin particles having such a crystal structure that one endothermic peak appears is preferable because, with such expanded polypropylene resin particles, (i) compatibility between both resins (specifically, polypropylene resin A and polypropylene resin B) when melted and kneaded is good, (ii) a variance in cell diameter of expanded polypropylene resin particles becomes small, and (iii) an in-mold expanded molded product has a good surface appearance.

[0117] The expanded polypropylene resin particles in accordance with one or more embodiments of the present invention can be made into a polypropylene resin in-mold expanded molded product by a conventionally known in-mold foaming molding method.

[0118] Examples of an in-mold foaming molding method in accordance with one or more embodiments of the present invention encompass:

[0119] i) a method of (a) subjecting expanded polypropylene resin particles to a pressure treatment with the use of inorganic gas (e.g. air, nitrogen, carbon dioxide) so that the expanded polypropylene resin particles, into which the inorganic gas is impregnated, has a certain internal pressure and (b) filling a mold with the expanded polypropylene resin particles, and (c) heating the mold by steam so that the expanded polypropylene resin particles are fused to each other.

[0120] ii) a method of (a) compressing expanded polypropylene resin particles by gas pressure, (b) filling a mold with the expanded polypropylene resin particles, and (c) heating the mold by steam so that the expanded polypropylene resin particles are fused to each other by the effect of resilience of the expanded polypropylene resin particles.

[0121] iii) a method of (a) filling a mold with expanded polypropylene resin particles without any particular pretreatment and (b) heating the mold by steam so that the expanded polypropylene resin particles are fused to each other.

[0122] A molded product density of the polypropylene resin in-mold expanded molded product in accordance with one or more embodiments of the present invention is not limited to any particular density. However, a polypropylene resin in-mold expanded molded product having a molded product density of 10 g/L or more to 100 g/L or less is suitably used.

[0123] The polypropylene resin in-mold expanded molded product in accordance with one or more embodiments of the present invention is obtained as a high-compressive-strength polypropylene resin in-mold expanded molded product by subjecting expanded polypropylene resin particles to in-mold foaming molding while a molding temperature (steam pressure) is reduced. In particular, the polypropylene resin in-mold expanded molded product is preferable in that a relationship between a molded product density and a 50%-strained compressive strength of the polypropylene resin in-mold expanded molded product satisfies the following Formula (1):

[50%-strained compressive strength(MPa)]≧0.0069×[Molded product density(g/L)]+0.018  (1)

[0124] Specifically, polypropylene resin in-mold expanded molded products satisfying Formula (1) have conventionally been used as highly strong polypropylene resin in-mold expanded molded products for automobile interior materials and automobile bumper core materials. However, such conventional polypropylene resin in-mold expanded molded products require a high molding temperature during in-mold foaming molding. For example, during in-mold foaming molding in which steam is used, such a high steam pressure as 0.24 MPa (gage pressure) or more was necessary. However, with one or more embodiments of the present invention, it is possible to produce a polypropylene resin in-mold expanded molded product satisfying Formula (1) even with such a low steam pressure as 0.22 MPa (gage pressure) or less.

[0125] A polypropylene resin in-mold expanded molded product thus obtained can be put to various applications such as heat insulating materials, shock-absorbing packing materials, and returnable containers in addition to automobile interior materials and automobile bumper core materials.

[0126] In particular, the polypropylene resin in-mold expanded molded product in accordance with one or more embodiments of the present invention is preferably used for automobile materials such as automobile interior materials and automobile bumper core materials because such automobile materials obtained from the polypropylene resin in-mold expanded molded product, which can be molded with a lower molding temperature (steam pressure), exhibit a compressive strength similar to those obtained from conventional molded products molded with a high molding temperature (steam pressure).

EXAMPLES

[0127] The following description will discuss one or more embodiments of the present invention in more detail with Examples and Comparative Examples. Note, however, that the present invention is not limited to these Examples and Comparative Examples.

[0128] Substances used in Examples and Comparative Examples are as provided below.

[0129] (Polypropylene Resin and Polyethylene Resin)

[0130] Table 1 shows polypropylene resins A-1 through A-3, polypropylene resins B-1 through B-3, and polyethylene resins C-1 through C-4 which were used.

TABLE-US-00001 TABLE 1 Comonomer content (weight %) Melting MFR Type of 1- point (g/10 catalyst butene Ethylene (° C.) min.) Polypropylene resin A-1 Ziegler 2.5 3.3 134 6.0 Polypropylene resin A-2 Ziegler 7.2 4.5 138 8.0 Polypropylene resin A-3 Ziegler 3.0 4.1 142 7.2 Polypropylene resin B-1 Ziegler — 2.8 153 8.5 Polypropylene resin B-2 Ziegler — 3.4 148 6.5 Polypropylene resin B-3 Ziegler 2.2 3.6 143 7.0 Polyethylene resin C-1 — — — 129 7.0 Polyethylene resin C-2 — — — 123 2.1 Polyethylene resin C-3 — — — 113 2.0 Polyethylene resin C-4 — — — 136 0.3
Polypropylene resins are random copolymers.

[0131] (Other Additives) [0132] Talc: manufactured by Hayashi-Kasei Co., Ltd., Talcan Powder PK-S [0133] Polyethylene glycol: manufactured by Lion Corporation, PEG#300 [0134] Carbon black: manufactured by Mitsubishi Chemical Corporation, MCF88 (average particle size: 18 nm)

[0135] In Examples and Comparative Examples, evaluations were made by the methods as below.

[0136] (Quantification of Copolymer Composition in Polypropylene Resin)

[0137] A polypropylene resin having a known comonomer content was hot pressed at 180° C., so that a film having a thickness of approximately 100 μm was produced. The film thus produced was subjected to IR spectrum measurement so that a propylene-derived absorbance (I810) at 810 cm.sup.−1, an ethylene comonomer-derived absorbance (I733) at 733 cm.sup.−1, and a butene comonomer-derived absorbance (I766) at 766 cm.sup.−1 were read. Then, an absorbance ratio (I733/I810) is shown in a horizontal axis, and an ethylene comonomer content is shown in a vertical axis, so that a calibration curve indicative of the ethylene comonomer content was obtained. Likewise, an absorbance ratio (I766/I810) is shown in a horizontal axis, and a butene comonomer content is shown in a vertical axis, so that a calibration curve indicative of the butene comonomer content was obtained. Then, as with the method of preparing a sample during production of the calibration curves, (i) a polypropylene resin having an unknown comonomer content was hot pressed, so that a film having a thickness of approximately 100 μm was produced, (ii) I810, I733, and I766 were read by IR spectrum measurement, and (iii) an ethylene comonomer content and a butene comonomer content were calculated according to the calibration curves produced earlier.

[0138] (Measurement of Melting Point of Polypropylene Resin, Polyethylene Resin, and Polypropylene Resin Composition)

[0139] A melting point tm of the polypropylene resin A, the polypropylene resin B, the polyethylene resin C, and the polypropylene resin composition X was measured with the use of a differential scanning calorimeter DSC (manufactured by Seiko Instruments Inc., model: DSC6200). Specifically, the melting point tm was found as a melting peak temperature in a second temperature rise on a DSC curve obtained by (i) raising a temperature of 5 mg to 6 mg of the polypropylene resin (polypropylene resin particles) from 40° C. to 220° C. at a heating rate of 10° C./min. so as to melt the polypropylene resin, (ii) lowering the temperature from 220° C. to 40° C. at a cooling rate of 10° C./min. so as to crystallize the polypropylene resin (polypropylene resin particles), and then (iii) raising the temperature again from 40° C. to 220° C. at a heating rate of 10° C./min.

[0140] (Expansion Ratio of Expanded Polypropylene Resin Particles)

[0141] Approximately 3 g or more to 10 g or less of the expanded polypropylene resin particles obtained was used. Then, the expanded polypropylene resin particles were dried at 60° C. for 6 hours, and were then subjected to conditioning indoors at 23° C. and at a humidity of 50%. Then, after a weight w(g) of the expanded polypropylene resin particles was measured, a volume v(cm.sup.3) of the expanded polypropylene resin particles was measured by an immersing the resultant particles, so that an absolute specific gravity (ρb=w/v) of the expanded particles was obtained. Then, based on a ratio of the absolute specific gravity to a density (pr) of the polypropylene resin particles before foaming, an expansion ratio (K=ρr/ρb) was calculated. Note that in each of Examples and Comparative Examples, the density (pr) of the polypropylene resin particles before foaming was 0.9 g/cm.sup.3.

[0142] (Average Cell Diameter of Expanded Polypropylene Resin Particle)

[0143] While caution was exercised so that a foam membrane (cell membrane) in an expanded polypropylene resin particle obtained would not be destroyed, the expanded particle was cut substantially through a center part, and then a cross section was observed with the use of a microscope (manufactured by Keyence Corporation: VHX digital microscope). A line segment, a length of which corresponds to 1000 μm, was drawn on an entire portion of a photograph captured by the microscope for observation except a portion of a surface layer of the expanded particle. Then, the number (n) of cells on which the line segment passes was counted, so that a cell diameter was calculated in 1000/n (μm). Such operations were carried out for 10 expanded particles, and an average value of respective cell diameters of cells calculated in the 10 operations was regarded as an average cell diameter of the expanded polypropylene resin particles.

[0144] (Calculation of High-Temperature Heat Quantity Ratio of Expanded Polypropylene Resin Particles)

[0145] A high-temperature heat quantity ratio [={Qh/(Ql+Qh)}×100(%)] was calculated based on a DSC curve in a first temperature rise (see FIG. 2) which was obtained with the use of a differential scanning calorimeter (manufactured by Seiko Instruments Inc., model: DSC6200) by raising a temperature of 5 mg to 6 mg of the expanded polypropylene resin particles from 40° C. to 220° C. at a heating rate of 10° C./min. In the DSC obtained illustrated in FIG. 2, an entire melting heat quantity (Q=Ql+Qh), which is the sum of a low temperature-side melting heat quantity (Ql) and a high temperature-side melting heat quantity (Qh), is indicated by a part surrounded by a (i) line segment A-B which is drawn so as to connect a heat absorption quantity (point A) at a temperature of 80° C. and a heat absorption quantity (point B) at a temperature at which melting on a high temperature side ends and (ii) the DSC curve. The low temperature-side melting heat quantity (Ql) is indicated by a part surrounded by a line segment A-D, a line segment C-D, and the DSC curve, and the high temperature-side melting heat quantity (Qh) is indicated by a part surrounded by a line segment B-D, the line segment C-D, and the DSC curve where (i) a point C is a point at which a heat absorption quantity between two melting heat quantity regions in the DSC curve is the smallest, the two melting heat quantity regions being a region of the low temperature-side melting heat quantity and a region of the high temperature-side melting heat quantity and (ii) a point D is a point at which the line segment A-B intersects a line that is drawn so as to extend, parallel to a Y-axis, from the point C toward the line segment A-B.

[0146] (DSC Measurement of Expanded Polypropylene Resin Particles at Heating Rate of 2° C./Min.)

[0147] DSC measurement was carried out with the use of a differential scanning calorimeter (manufactured by Seiko Instruments Inc., model: DSC6200) by raising a temperature of 1 mg to 3 mg of expanded polypropylene resin particles from 40° C. to 200° C. at a heating rate of 2° C./min.

[0148] (Moldability Evaluation)

[0149] With the use of a polyolefin molding machine (manufactured by DAISEN Co., Ltd., KD-345), (i) a mold, which allows a plate-like in-mold expanded molded product having a size of length 300 mm×width 400 mm×thickness 50 mm to be obtained, was filled with expanded particles while cracking was 5 mm, which expanded particles had been prepared in advance so that expanded polypropylene resin particles would have an internal air pressure as shown in Table 2 or 3 and (ii) the expanded particles were heat molded by being compressed by 10% in thicknesswise directions. This resulted in a plate-like polypropylene resin in-mold expanded molded product having a size of length 300 mm×width 400 mm×thickness 50 mm. In so doing, after the mold was filled with the expanded polypropylene resin particles and the mold was then completely closed, air in the mold was purged by use of steam having a pressure of 0.1 MPa (gage pressure) (preheating step), the expanded polypropylene resin particles were heat molded for 10 sec. by use of heating steam having a certain molding pressure (both-surface heating step). This resulted in an in-mold expanded molded product. The polypropylene resin in-mold expanded molded product obtained was (i) left at room temperature for 1 hour, (ii) cured and dried in a thermostatic chamber at 75° C. for 3 hours, and (iii) extracted again and left at room temperature for 24 hours. Then, fusibility and a surface property were evaluated. Note that during in-mold foaming molding, the in-mold expanded molded product was molded while the molding pressure (steam pressure) in the both-surface heating step was changed in increments of 0.01 MPa. The lowest molding pressure, at which an in-mold expanded molded product whose fusibility was evaluated as “good” or “excellent” in <Fusibility> evaluation (see below) was obtained, was regarded as a minimum molding pressure. An in-mold expanded molded product molded with the minimum molding pressure was subjected to (i) surface appearance evaluation, (ii) molded product density measurement, and (iii) 50%-strained compressive strength measurement.

[0150] <Fusibility>

[0151] The in-mold expanded molded product thus obtained was (i) notched by 5 mm in a thickness-wise direction with the use of a cutter and (ii) cleaved by hand. A cleaved surface was observed by visual inspection, and a percentage of clefts in expanded particles and not clefts in the interfaces of the expanded particles was obtained. Then, fusibility was judged by the following criteria:

Excellent: The percentage of clefts in the expanded particles was 80% or more.
Good: The percentage of clefts in the expanded particles was 60% or more to less than 80%.
Failed: The percentage of clefts in the expanded particles was less than 60% (fusibility was so low that the percentage of clefts appearing in the interfaces of the expanded particles on the cleaved surface was more than 40%).

[0152] <Surface appearance (Surface part)>

[0153] A surface having a length of 300 mm and a width of 400 mm of the in-mold expanded molded product obtained was observed by visual inspection, and a surface property was judged by the criteria as below. For the judgment of the surface property, inter-particle spaces (spaces between expanded polypropylene resin particles), which serves as one of indices for evaluating the surface property, were counted, by visual inspection, in a surface of 50 mm per side in a center part of the molded product.

EE (Extraordinarily excellent): There is no inter-particle space or one inter-particle space; there is no noticeable surface unevenness; there is no wrinkle or shrinkage and the surface is therefore beautiful.
VE (Very excellent): There are two or three inter-particle spaces; there is no noticeable surface unevenness; there is no wrinkle or shrinkage and the surface is therefore beautiful.
E (Excellent): There are four or five inter-particle spaces; there is no noticeable surface unevenness; there is no wrinkle or shrinkage and the surface is therefore beautiful.
G (Good): Six or more inter-particle spaces are observed, or some surface unevenness, shrinkage, or wrinkles are observed.
F (Failed): Inter-particle spaces, surface unevenness, shrinkage, or wrinkles are noticeable throughout the surface observed.

[0154] <Surface Appearance (Edge Part)>

E (Excellent): An edge part (ridge part), at which two surfaces of the in-mold expanded molded product obtained intersect, had no unevenness resulting from the expanded polypropylene resin particles and had a clear ridge formed; mold transferability is good. Even if the edge part was rubbed with a finger, the expanded particles were not peeled off.
F (Failed): Unevenness resulting from the expanded polypropylene resin particles was noticeable at an edge part (ridge part); a clear ridge was not formed; mold transferability was poor. If the edge part was rubbed with a finger, then the expanded particles were easily peeled off.

[0155] (Molded Product Density)

[0156] A test piece, which had a size of length 50 mm×width 50 mm x thickness 25 mm, was cut out from substantially a center part of the in-mold expanded molded product obtained. Note that the test piece had a thickness of 25 mm by cutting off, by approximately 12.5 mm, each of parts containing respective surface layers of the in-mold expanded molded product. A weight W(g) of the test piece was measured, and the length, width, and thickness of the test piece were measured with the use of a caliper, so that a volume V(cm.sup.3) of the test piece was calculated. Then, a molded product density was obtained by W/V. Note that a unit conversion to g/L was made on a calculated value thus obtained.

[0157] (50%-Strained Compressive Strength and Evaluation)

[0158] The test piece, whose molded product density was measured, was subjected to a compressive strength test. Specifically, a compressive stress of the test piece when the test piece was compressed by 50% at a rate of 10 mm/min. was measured with the use of a tension and compression testing machine (manufactured by Minebea Co., Ltd., TG series) in conformity with NDZ-Z0504. In addition, the 50%-strained compressive strength was evaluated as follows.

[0159] The following Formula (1) is satisfied: A The following Formula (1) is not satisfied: B

[50%-strained compressive strength(MPa)]≧0.0069×[Molded product density(g/L)]+0.018  (1)

Examples 1 through 16 and Comparative Examples 1 through 11

[0160] [Production of Polypropylene Resin Particles]

[0161] The polypropylene resin A, the polypropylene resin B, the polyethylene resin C, and additives were mixed in amounts shown in Tables 2 and 3 with the use of a blender. Each of the mixtures obtained was melted and kneaded at a resin temperature of 220° C. and extruded in a strand shape with the use of a twin-screw extruder (manufactured by O. N. Machinery Co., Ltd., TEK45). The strand thus extruded was water-cooled in a water tank having a length of 2 m, and was then cut. This resulted in polypropylene resin particles (1.2 mg per particle).

[0162] [Production of First-Stage Expanded Particles and Second-Stage Expanded Particles]

[0163] 100 parts by weight of the polypropylene resin particles obtained, 300 parts by weight of water, 1.5 parts by weight of powdered basic tribasic calcium phosphate as a dispersing agent, 0.06 parts by weight of n-paraffin sulfonic acid soda as a dispersion auxiliary agent, and 5.8 parts by weight of carbon dioxide as a foaming agent were placed in a 10 L-pressure-resistant container. While a resultant dispersion liquid was stirred, a temperature of the dispersion liquid was raised to a foaming temperature shown in a corresponding part in Table 2 or 3, and the dispersion liquid was retained at the foaming temperature for 10 min. Then, carbon dioxide was additionally injected into the pressure-resistant container so that a foaming pressure was adjusted to a value shown in a corresponding part in Table 2 or 3. Then, the foaming pressure was retained for 30 min. Then, a valve at a lower part of the pressure-resistant container was opened while carbon dioxide was injected into the pressure-resistant container such that the temperature and pressure in the pressure-resistant container were retained. An aqueous dispersion medium was released from the valve into air under atmospheric pressure through an orifice plate having an opening diameter of 3.6 mm, so that expanded polypropylene resin particles (first-stage expanded particles) were obtained. A high-temperature heat quantity ratio, a cell diameter, and an expansion ratio of the first-stage expanded particles thus obtained were measured. The results are shown in a corresponding part of Table 2 or 3. Note that expanded polypropylene resin particles were subjected to DSC measurement at a heating rate of 2° C./min. In each of Examples 1 through 16 and Comparative Examples 1 through 11, the DSC curve showed the total of three endothermic peaks which are (i) one main endothermic peak in a range of 130° C. to 145° C., (ii) one high temperature peak on a high temperature-side of the main endothermic peak, and (iii) one peak based on the polyethylene resin C in a range of 110° C. to 137° C. In each of Example 16 and Comparative Example 9, second-stage expanded particles were obtained by introducing the first-stage expanded particles obtained into a pressure-resistant container, applying a predetermined internal pressure to the first-stage expanded particles by impregnation of air, and then heating the first-stage expanded particles with use of steam.

[0164] [Production of in-Mold Expanded Molded Product]

[0165] The first-stage expanded particles obtained or the second-stage expanded particles obtained were introduced into a pressure-resistant container. Then, pressurized air was impregnated so that internal pressure of the expanded particles was adjusted in advance as shown in a corresponding part of Table 2 or 3. Then, (i) a mold, which allows a plate-like in-mold expanded molded product having a size of length 300 mm×width 400 mm×thickness 50 mm to be obtained, was filled with the expanded polypropylene resin particles while cracking was 5 mm, which expanded polypropylene resin particles had the adjusted internal pressure and (ii) the expanded particles were heat molded by being compressed by 10% in thicknesswise directions. This resulted in a plate-like in-mold expanded molded product having a size of length 300 mm×width 400 mm×thickness 50 mm. In so doing, after the mold was filled with the expanded polypropylene resin particles having the adjusted internal pressure and the mold was then completely closed, air in the mold was purged by use of steam (preheating step), and a one-surface heating step and an other-surface heating step were then carried out. Thereafter, the expanded polypropylene resin particles were heat molded for 10 sec. by use of heating steam having a certain molding pressure (both-surface heating step). This resulted in an in-mold expanded molded product. Note that (i) the preheating step was carried out for 10 sec., (ii) the one-surface heating step was carried out for 2 sec., (iii) the other-surface heating step was carried out for 2 sec., and (iv) the both-surface heating step was carried out for 10 sec. as described above. Note also that the in-mold expanded molded product was prepared while a molding pressure (steam pressure) was changed in 0.01 MPa increments in the both-surface heating step. Tables 2 and 3 show the results of moldability evaluation, molded product density measurement, and 50%-strained compressive strength measurement.

TABLE-US-00002 TABLE 2 (“PBW” stands for “Part by weight”.) Examples 1 2 3 4 5 6 7 8 Base Polypropylene Polypropylene resin A-1 PBW 60 50 70 65 50 74 60 50 material resin A Polypropylene resin A-2 PBW resin X Polypropylene resin A-3 PBW Polypropylene Polypropylene resin B-1 PBW 35 45 25 34 49 25 30 40 resin B Polypropylene resin B-2 PBW Polypropylene resin B-3 PBW Polyethylene Polyethylene resin C-1 PBW 5 5 5 1 1 1 10 10 resin C Polyethylene resin C-2 PBW Polyethylene resin C-3 PBW Polyethylene resin C-4 PBW Additive Talc PBW 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Polyethylene glycol PBW 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Carbon black PBW Physical Melting point based on ° C. 146 147 145 146 147 144 145 146 property polypropylene resins Melting point based on ° C. 130 130 130 130 130 130 130 130 polyethylene resin First- Foaming Amount of carbon dioxide PBW 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 stage conditions Foaming temperature ° C. 149 150 147 149 150 147 149 150 foaming Foaming pressure (gage MPa 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 pressure) Physical High-temperature % 21 20 22 21 21 23 20 20 property heat quantity ratio Average cell diameter μm 130 120 130 140 130 140 110 100 Expansion ratio Times 20 21 19 21 20 19 21 21 Second- Foaming Expanded particle internal MPa — — — — — — — — stage conditions pressure (Absolute pressure) foaming Heating pressure MPa — — — — — — — — (gage pressure) Physical High-temperature % — — — — — — — — property heat quantity ratio Average cell diameter μm — — — — — — — Expansion ratio Times — — — — — — — In-mold Moldability Expanded particle internal MPa 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 expanded pressure (Absolute pressure) molded Minimum molding pressure MPa 0.19 0.19 0.18 0.19 0.20 0.19 0.18 0.18 product (gage pressure) Surface Surface part — EE EE EE VE VE VE VE VE appearance Edge part — E E E E E E E E Physical Molded product density g/L 30 30 30 30 30 30 30 30 property 50%-strained compressive MPa 0.232 0.234 0.230 0.233 0.235 0.230 0.227 0.230 strength 50%-strained compressive MPa A A A A A A A A strength evaluation Examples 9 10 11 12 13 14 15 16 Base Polypropylene Polypropylene resin A-1 PBW 65 60 60 60 60 60 material resin A Polypropylene resin A-2 PBW 60 60 resin X Polypropylene resin A-3 PBW Polypropylene Polypropylene resin B-1 PBW 25 35 35 35 35 35 resin B Polypropylene resin B-2 PBW 35 35 Polypropylene resin B-3 PBW Polyethylene Polyethylene resin C-1 PBW 10 5 5 5 5 5 resin C Polyethylene resin C-2 PBW 5 5 Polyethylene resin C-3 PBW Polyethylene resin C-4 PBW Additive Talc PBW 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Polyethylene glycol PBW 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Carbon black PBW 6 Physical Melting point based on ° C. 145 148 145 146 146 146 146 146 property polypropylene resins Melting point based on ° C. 130 130 130 124 124 130 130 130 polyethylene resin First- Foaming Amount of carbon dioxide PBW 5.8 5.8 5.8 5.8 5.8 5.8 5.0 5.2 stage conditions Foaming temperature ° C. 147 151 148 149 149 149 152 151 foaming Foaming pressure (gage MPa 3.3 3.3 3.3 3.3 3.3 3.3 2.6 2.8 pressure) Physical High-temperature % 21 21 21 21 20 21 22 20 property heat quantity ratio Average cell diameter μm 110 140 130 120 120 110 160 140 Expansion ratio Times 20 21 20 20 20 21 10 13 Second- Foaming Expanded particle internal MPa — — — — — — — 0.35 stage conditions pressure (Absolute pressure) foaming Heating pressure MPa — — — — — — — 0.06 (gage pressure) Physical High-temperature % — — — — — — — 19 property heat quantity ratio Average cell diameter μm — — — — — — — 150 Expansion ratio Times — — — — — — — 30 In-mold Moldability Expanded particle internal MPa 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 expanded pressure (Absolute pressure) molded Minimum molding pressure MPa 0.17 0.20 0.19 0.19 0.19 0.19 0.20 0.18 product (gage pressure) Surface Surface part — VE EE EE EE EE EE EE EE appearance Edge part — E E E E E E E E Physical Molded product density g/L 30 30 30 30 30 30 60 20 property 50%-strained compressive MPa 0.226 0.233 0.231 0.225 0.225 0.232 0.520 0.190 strength 50%-strained compressive MPa A A A A A A A A strength evaluation

TABLE-US-00003 TABLE 3 (“PBW” stands for “Part by weight”.) Comparative Examples 1 2 3 4 5 6 Base Polypropylene Polypropylene resin A-1 PBW 80 40 60 55 60 material resin A Polypropylene resin A-2 PBW resin X Polypropylene resin A-3 PBW 60 Polypropylene Polypropylene resin B-1 PBW 15 55 40 30 35 resin B Polypropylene resin B-2 PBW Polypropylene resin B-3 PBW 35 Polyethylene Polyethylene resin C-1 PBW 5 5 15 5 5 resin C Polyethylene resin C-2 PBW Polyethylene resin C-3 PBW Polyethylene resin C-4 PBW Additive Talc PBW 0.05 0.05 0.05 0.05 0.05 0.05 Polyethylene glycol PBW 0.5 0.5 0.5 0.5 0.5 0.5 Physical Melting point based on ° C. 141 148 146 145 148 141 property polypropylene resins Melting point based on ° C. 130 130 130 130 130 polyethylene resin First- Foaming Amount of carbon dioxide PBW 5.8 5.8 5.8 5.8 5.8 5.8 stage conditions Foaming temperature ° C. 145 151 149 149 149 145 foaming Foaming pressure (gage MPa 3.4 3.2 3.3 3.3 3.3 3.4 pressure) Physical High-temperature % 21 20 22 18 23 22 property heat quantity ratio Average cell diameter μm 100 120 140 100 130 120 Expansion ratio Times 18 22 19 18 20 18 Second- Foaming Expanded particle internal MPa — — — — — — stage conditions pressure (Absolute pressure) foaming Heating pressure MPa — — — — — — (gage pressure) Physical High-temperature % — — — — — — property heat quantity ratio Average cell diameter μm — — — — — — Expansion ratio Times — — — — — — In-mold Moldability Expanded particle internal MPa 0.2 0.2 0.2 0.2 0.2 0.2 expanded pressure (Absolute pressure) molded Minimum molding pressure MPa 0.18 0.24 0.20 0.17 0.24 0.19 product (gage pressure) Surface Surface part — EE EE E E EE EE appearance Edge part — E E E E E E Physical Molded product density g/L 30 30 30 30 30 30 property 50%-strained compressive MPa 0.200 0.237 0.232 0.175 0.235 0.210 strength 50%-strained compressive — B A A B A B strength evaluation Comparative Examples 7 8 9 10 11 Base Polypropylene Polypropylene resin A-1 PBW 60 60 100 material resin A Polypropylene resin A-2 PBW resin X Polypropylene resin A-3 PBW Polypropylene Polypropylene resin B-1 PBW 35 35 100 95 resin B Polypropylene resin B-2 PBW Polypropylene resin B-3 PBW Polyethylene Polyethylene resin C-1 PBW 5 resin C Polyethylene resin C-2 PBW Polyethylene resin C-3 PBW 5 Polyethylene resin C-4 PBW 5 Additive Talc PBW 0.05 0.05 0.05 0.05 0.05 Polyethylene glycol PBW 0.5 0.5 0.5 0.5 0.5 Physical Melting point based on ° C. 146 146 134 153 152 property polypropylene resins Melting point based on ° C. 114 137 130 polyethylene resin First- Foaming Amount of carbon dioxide PBW 5.8 5.8 6.5 5.8 5.8 stage conditions Foaming temperature ° C. 149 149 135 154 153 foaming Foaming pressure (gage MPa 3.3 3.3 3.4 3.0 3.0 pressure) Physical High-temperature % 21 22 20 22 21 property heat quantity ratio Average cell diameter μm 100 110 100 130 120 Expansion ratio Times 21 20 14 21 20 Second- Foaming Expanded particle internal MPa — — 0.35 — — stage conditions pressure (Absolute pressure) foaming Heating pressure MPa — — 0.05 — — (gage pressure) Physical High-temperature % — — 19 — — property heat quantity ratio Average cell diameter μm — 110 — — Expansion ratio Times — 21 — — In-mold Moldability Expanded particle internal MPa 0.2 0.2 0.2 0.2 0.2 expanded pressure (Absolute pressure) molded Minimum molding pressure MPa 0.18 0.20 0.17 0.28 0.27 product (gage pressure) Surface Surface part — VE G E E E appearance Edge part — E E E E E Physical Molded product density g/L 30 30 30 30 30 property 50%-strained compressive MPa 0.180 0.232 0.195 0.270 0.260 strength 50%-strained compressive — B A B A A strength evaluation

[0166] Comparisons between the molded products having substantially identical molded product densities indicate that (i) those in Examples can be molded with a low molding pressure and exhibit higher 50%-strained compressive strength and (ii) those in Comparative Examples exhibit decreased 50%-strained compressive strength with a low molding pressure and demand a higher molding pressure for high 50%-strained compressive strength.

[0167] The present invention can be used for production of, for example, automobile interior materials, automobile bumper core materials, heat insulating materials, shock-absorbing packing materials, and returnable containers.

[0168] Although the disclosure has been described with respect to only a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that various other embodiments may be devised without departing from the scope of the present invention. Accordingly, the scope of the present invention should be limited only by the attached claims.

REFERENCE SIGNS LIST

[0169] Tm (pp): Melting maximum peak point of polypropylene resin composition X based on respective melting points of polypropylene resin A and polypropylene resin B in DSC curve of second temperature rise

[0170] Tm (pe): Peak melting point of polypropylene resin composition X based on melting point of polyethylene resin C in DSC curve of second temperature rise

[0171] Point A: Heat absorption quantity of expanded polypropylene resin particles at 80° C. in DSC curve of first temperature rise

[0172] Point B: Heat absorption quantity of expanded polypropylene resin particles at temperature at which melting on high temperature side ends in DSC curve of first temperature rise

[0173] Point C: Point at which heat absorption quantity of expanded polypropylene resin particles becomes smallest between two melting heat quantity regions in DSC curve of first temperature rise, the two melting heat quantity regions being region of low temperature-side melting heat quantity and region of high temperature-side melting heat quantity

[0174] Point D: Point at which line segment A-B intersects line that is drawn so as to extend, parallel to Y-axis, from point C toward line segment A-B in DSC curve of first temperature rise of expanded polypropylene resin particles

[0175] Qh: High temperature-side melting heat quantity of expanded polypropylene resin particles in DSC curve of first temperature rise

[0176] Ql: Low temperature-side melting heat quantity of expanded polypropylene resin particles in DSC curve of first temperature rise