TECHNICAL FIELD

One or more embodiments of the present invention relate to an injection molded body of a polypropylene resin composition.

BACKGROUND

A polypropylene resin has good physical properties and moldability, and its use range has been expanding rapidly as an environmentally friendly material. Particularly, in automobile parts and the like, polypropylene resin products that are light in weight and excellent in rigidity are provided. One such product is an injection molded body of a polypropylene resin.

In the injection molding materials, from the viewpoint of productivity, higher fluidity is required, and in many cases, such requirement is dealt with by changing prescription or changing molding conditions.

When making the injection molding material to have a high fluidity by changing the prescription, the material intrudes into the gaps of the mold splitting surface, and burrs are likely to occur in the molded product. Since it is common to increase the material injection pressure or to increase the injection speed when dealing with changes in the molding conditions, a gap is generated on the mold splitting surface due to the injection pressure, and burrs are likely to occur in the molded product. Such a tendency becomes prominent in the case of a large injection molded body, for example, an injection molded body for automobiles. For this reason, there is a demand for injection molding materials with little generation of burrs, in which burrs are practically absent or negligible, so that deburring work after injection molding is unnecessary or simplified.

As such a material, for example, in a propylene resin composition containing a propylene resin, an elastomer, and an inorganic filler, or a propylene resin and an inorganic filler as main components, respectively, there has been proposed a propylene resin composition in which characteristics of the propylene resin satisfy one or both of a specific infrared absorbance ratio and a specific Mw/Mn ratio and in which a characteristic value of the resin composition is within a range satisfying a specified inequality (Patent Literature 1). Specifically, ethylene-α-olefin copolymers and styrene thermoplastic elastomers are proposed as elastomers, and talc has been proposed as an inorganic filler. However, since compatibility between the propylene type resin and the elastomer is low, deterioration of physical properties and poor appearance may occur. There is a statement on the effect only when the elastomer is blended in an amount of 25% by weight or more (Example 4) and for example, in the case where the amount of the elastomer is 20% by weight (Comparative Example 2), no burr prevention effect is recognized. In addition, when an inorganic filler such as talc cannot be blended, such a propylene resin composition cannot be applied.

Further, there has been proposed a polypropylene resin composition containing a crystalline polypropylene satisfying a specific MFR value range and a specific Mw/Mn ratio range; a propylene polymer satisfying a specific MFR value range, a specific Mw/Mn ratio range, and a ratio of components having a molecular weight of 2,000,000 or more; a thermoplastic elastomer as an optional component; an inorganic filler as an optional component; and a crystal nucleating agent (Patent Literature 2). The propylene polymer proposed in this literature is a long-chain branched propylene polymer in which a macromer produced from an active species derived from a catalyst component is incorporated in the main chain to form a branched structure. However, when a thermoplastic elastomer and an inorganic filler are not used in combination, the effect only when 30% by weight (Example 1) or more of the propylene polymer is blended is described, and when a thermoplastic elastomer and an inorganic filler are used in combination, the effect only when the total amount of the propylene polymer and the thermoplastic elastomer is blended in 35% by weight (Example 4) or more is described, but the burr prevention effect at a blending amount less than the above amount was unknown. In addition, a special metal catalyst and a dedicated polymerization apparatus are required for synthesizing the above propylene polymer.

As described above, in a polypropylene resin, it was difficult to suppress or prevent the formation of burrs by using a small amount of modifier, that is, to obtain an injection molded body of a polypropylene resin composition compatible with fluidity and burr prevention performance.

CITATION LIST
Patent Literature

PTL 1: JP 2005-194297 A

PTL 2: JP 2011-88955 A

SUMMARY

One or more embodiments of the present invention provide an injection molded body of a polypropylene resin composition, which has excellent in fluidity and burr prevention performance.

One or more embodiments of the present invention include the following:

[1] An injection molded body of a polypropylene resin composition, which contains a conjugated diene-modified polypropylene resin (A) that has a melt flow rate of 1-150 g/10 min as measured at 230° C. under a load of 2.16 kg and a polypropylene resin (B) that has a melt flow rate of 7-100 g/10 min as measured at 230° C. under a load of 2.16 kg, wherein a content of the conjugated diene-modified polypropylene resin (A) is 0.1-50 parts by weight and a content of the polypropylene resin (B) is 99.9-50 parts by weight, relative to 100 parts by weight of a total of the conjugated diene-modified polypropylene resin (A) and the polypropylene resin (B), and the polypropylene resin composition has a melt flow rate of 10-80 g/10 min as measured at 230° C. under a load of 2.16 kg, while having a melt tension of 0.7-30 gf as measured at 200° C. at 10 m/min.

[2] The injection molded body according to the above [1], wherein the melt flow rate of the conjugated diene-modified polypropylene resin (A) is 10-100 g/10 min.

[3] The injection molded body according to the above [1] or [2], wherein the content of the conjugated diene-modified polypropylene resin (A) is 1-35 parts by weight and the content of the polypropylene resin (B) is 99-65 parts by weight, relative to 100 parts by weight of the total of the conjugated diene-modified polypropylene resin (A) and the polypropylene resin (B).

[4] The injection molded body according to any one of the above [1] to [3], wherein the conjugated diene-modified polypropylene resin (A) is a molten mixture of (a) a polypropylene resin, (b) a radical polymerization initiator, and (c) a conjugated diene compound.

[5] A method for producing the injection molded body according to any one of the above [1] to [4], including a step of injection molding the polypropylene resin composition at a temperature of 170-300° C.

The injection molded body of the polypropylene resin composition according to one or more embodiments of the present invention has excellent fluidity and burr prevention performances. Therefore, it is possible to perform continuous and stable injection molding, and it is possible to omit or simplify the operation of removing the burr of the injection molded body. The injection molded body according to one or more embodiments of the present invention is particularly suitable for a large-sized injection molded body produced by using a large mold. Furthermore, the injection molded body of the polypropylene resin composition according to one or more embodiments of the present invention can be adjusted to a desired fluidity, and as compared with a conventionally known injection molded body of a polypropylene resin, a desired injection molded body can be obtained.

DETAILED DESCRIPTION OF EMBODIMENTS

Hereinafter, one or more embodiments of the present invention will be described.

The injection molded body according to one or more embodiments of the present invention is an injection molded body composed of a polypropylene resin composition. The polypropylene resin composition contains a conjugated diene-modified polypropylene resin (A) that has a melt flow rate of 1-150 g/10 min as measured at 230° C. under a load of 2.16 kg and a polypropylene resin (B) that has a melt flow rate of 7-100 g/10 min as measured at 230° C. under a load of 2.16 kg, in which the content of the conjugated diene-modified polypropylene resin (A) is 0.1-50 parts by weight and the content of the polypropylene resin (B) is 99.9-50 parts by weight, relative to 100 parts by weight of the total of the conjugated dien-modified polypropylene resin (A) and the polypropylene resin (B), and the polypropylene resin composition has a melt flow rate of 10-80 g/10 min as measured at 230° C. under a load of 2.16 kg, while having a melt tension of 0.7-30 gf as measured at 200° C. at 10 m/min. The injection molded body according to one or more embodiments of the present invention refers to an injection molded body that is not foamed. A foam produced by blending a foaming agent in a resin composition and foaming during molding is not included in the scope of the injection molded body according to one or more embodiments of the present invention.

The conjugated diene-modified polypropylene resin (A) according to one or more embodiments of the present invention is a resin obtained by introducing a branched structure into a polypropylene resin by reacting a conjugated diene compound with a polypropylene resin and increasing the molecular weight thereof.

The conjugated diene-modified polypropylene resin (A) according to one or more embodiments of the present invention has a melt flow rate of 1-150 g/10 min as measured at 230° C. under a load of 2.16 kg. When the melt flow rate of the component (A) is less than 1 g/10 min, there is no problem from the viewpoint of suppressing burrs, but the fluidity of the resin composition is insufficient and there are cases where troubles such as short-shot etc. may occur in injection molding in a large mold. When the melt flow rate of the component (A) exceeds 150 g/10 min, mixing with the component (B) becomes insufficient, or the metering process in injection molding in the dry blend may become unstable in some cases. If the melt flow rate of the component (A) exceeds 150 g/10 minutes, it becomes difficult to adjust the melt flow rate of the composition within the range described later, and if mixing with the component (B) becomes insufficient, the composition becomes nonuniform and the effect of suppressing burrs is reduced. The melt flow rate of the component (A) may be 10-100 g/10 minutes.

Here, the melt flow rate (hereinafter sometimes abbreviated as “MFR” in some cases) refers to the value calculated as follows: using a Melt Indexer F-F01 (manufactured by Tovo Seiki Seisaku-sho, Ltd.) in accordance with JIS K 7210: 1999, the amount of resin extruded from a die for a predetermined period of time at 230° C. under a load of 2.16 kg is measured and used to calculate an amount of resin extruded for 10 minutes. This converted value was calculated by MFR automatic calculation processing (Method B). The calculation formulas are as follows. Even when the melt flow rate exceeds 50 (g/10 min), this method was applied.

MFR (g/10 min)=(427×L×ρ)/t

L (interval of test conditions): 3 (cm)

ρ (melt density at test temperature): A value (g/cm³) calculated according to the following formula by cutting method, provided that p is set to 0.75 (g/cm³) when the cutting method is impossible.

ρ=m/(0.711×L)

m: mass (g) of the sample flowing out as the piston moves through the interval L, measured by the cutting method.

L: same as above interval

t (interval movement time): actual measured value (seconds)

That is, when the cutting method can be applied, MFR may be calculated by the following calculation formula

MFR (g/10 min)=(600×m)/t

The conjugated diene-modified polypropylene resin (A) according to one or more embodiments of the present invention may be obtained by melt-mixing (a) a polypropylene resin, (b) a radical polymerization initiator, and (c) a conjugated diene compound. This molten mixture is excellent in that it does not require expensive equipment and can be manufactured at low cost.

The polypropylene resin (a) used for obtaining the conjugated diene-modified polypropylene resin (A) is a polypropylene resin having crystallinity. A homopolymer of propylene, a copolymer of propylene and a monomer copolymerizable with propylene may be used. It may also be a mixture of a propylene homopolymer and a propylene copolymer. As the copolymer, either a block copolymer or a random copolymer may be used. As the copolymer, a copolymer containing 51% by weight or more of propylene may be used, and from the viewpoint of maintaining crystallinity, rigidity, chemical resistance, and the like which are the features of the polypropylene resin, a copolymer containing propylene in an amount of 75% by weight or more may be used.

Examples of the monomer copolymerizable with propylene include an α-olefin having 2 or 4 to 12 carbon atoms, such as ethylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3,4-dimethyl-1-butene, 1-heptene, 3-methyl-1-hexene, 1-octene, and 1-decene; cyclic olefins, such as cyclopentene, norbomene, and tetracyclo[6,2,11,8,13,6]-4-dodecene; dienes, such as 5-methylene-2-norbomene, 5-ethylidene-2-norbomene, 1,4-hexadiene, methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene; vinyl monomers, such as vinyl chloride, vinylidene chloride, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, maleic acid, ethyl acrylate, butyl acrylate, methyl methacrylate, maleic anhydride, styrene, methylstyrene, vinyl toluene, and divinylbenzene; and the like. These may be used singly or in combination of two or more kinds thereof of these, α-olefins may be used from the viewpoint of improvement in cold resistance, low cost, etc., and ethylene and 1-butene may be used.

Examples of polypropylene resin (a) include homopolymers of propylene, random copolymers of propylene-ethylene, block copolymers of propylene-ethylene, and other propylene-ethylene copolymers. These may be mixed and used.

The propylene-ethylene copolymer may be a propylene polymer in which a polymer containing ethylene as a main component and an ethylene-propylene rubber-like copolymer are dispersed in a linear polymer containing propylene as a main component to form a sea-island structure. Such a propylene polymer is referred to as impact-resistant polypropylene, conventionally as block polypropylene in Japan, but it is not a block copolymer in a chemical sense.

As the radical polymerization initiator (b) used for obtaining the conjugated diene-modified polypropylene resin (A), generally a peroxide, an azo compound or the like can be mentioned, but those having a hydrogen abstraction ability from the polypropylene resin (a) or the conjugated diene compound (c) may be used. Although not particularly limited, examples thereof include organic peroxides such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and peroxyester.

Among these, in particular, those having a high hydrogen abstraction ability may be used, and examples thereof include peroxyketals, such as 1,1-bis(t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, n-butyl 4,4-bis(t-butylperoxy)valerate, and 2,2-bis(t-butylperoxy)butane; dialkyl peroxides, such as dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxv)hexane, α,α′-bis(t-butylperoxy-m-isoproropyl)benzene, t-butyl cumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne; diacyl peroxides such as benzoyl peroxide; and peroxy esters, such as t-butyl peroxy octate, t-butyl peroxy isobutyrate, t-butyl peroxy laurate, t-butyl peroxy 3,5,5-trimethyl hexanoate t-butyl peroxy isopropyl carbonate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxy acetate, t-butyl peroxy benzoate, and di-t-butyl peroxy isophthalate, etc. These may be used singly or in combination of two or more kinds thereof.

The addition amount of the radical polymerization initiator (b) used for obtaining the conjugated diene-modified polypropylene resin (A) may be 0.05 parts by weight or more and 10 parts by weight or less, or 0.2 parts by weight or more and 5 parts by weight or less, relative to 100 parts by weight of the polypropylene resin (a). When the addition amount of the radical polymerization initiator is less than 0.05 parts by weight, modification may be insufficient in some cases, when the addition amount of the radical polymerization initiator exceeds 10 parts by weight, molecular chain breakage may take place over such modification, and the desired modification effect may not be obtained in some cases.

Examples of the conjugated diene compound (c) used for obtaining the conjugated diene-modified polypropylene resin (A) include butadiene, isoprene, 1,3-heptadiene, 2,3-dimethylbutadiene, 2,5-dimethyl-2,4-hexadiene, and the like. These may be used singly or in combination. Among them, butadiene and isoprene may be used because they are inexpensive, easy to handle, and reactions are easy to proceed uniformly.

The addition amount of the conjugated diene compound (c) may be 0.01 parts by weight or more and 5 parts by weight or less, or 0.05 parts by weight or more and 2 parts by weight or less, relative to 100 parts by weight of the polypropylene resin (a). If the addition amount of the conjugated diene compound is less than 0.01 parts by weight, modification may be insufficient in some cases, and if it exceeds 5 parts by weight, fluidity may be insufficient in some cases.

In producing the conjugated diene-modified polypropylene resin (A), a monomer copolymerizable with the conjugated diene compound may be used in combination with the conjugated diene compound. Examples of such copolymerizable monomers include vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, an acrylic acid metal salt, a methacrylic acid metal salt, an acrylic acid esters, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, etc, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, and the like.

In the production of the conjugated diene-modified polypropylene resin (A), it is possible to relatively easily adjust the melt flow rate of the conjugated diene-modified polypropylene resin (A) within the range of 1 or more and 150 or less when the addition amount of the radical polymerization initiator (b) is 0.1 times or more and 10 times or less (weight basis) the addition amount of the conjugated diene compound (c). The addition amount of the radical polymerization initiator (b) may be 0.5 times or more and 7.5 times or less, or 0.75 times or more and 5 times or less the addition amount of the conjugated diene compound (c).

Examples of an apparatus for reacting the polypropylene resin (a), the radical polymerization initiator (b), and the conjugated diene compound (c) in order to obtain the conjugated diene-modified polypropylene resin (A) include kneaders such as roll, co-kneader, Banbury mixer, Brabender mixer single-screw extruder, and twin-screw extruder, horizontal stirrers such as twin-screw surface renewal devices and twin-screw multi-disk equipment; vertical stirrers such as double helical ribbon stirrer. Among those, kneaders may be used, and extruders may be used from the viewpoint of productivity.

The order and method for mixing and kneading (stirring) the polypropylene resin (a), the radical polymerization initiator (b), and the conjugated diene compound (c) to obtain the conjugated diene-modified polypropylene resin (A) are not particularly limited. After mixing the polypropylene resin (a), the radical polymerization initiator (b), and the conjugated diene compound (c), melt kneading (stirring) may be carried out. Alternatively, the polypropylene resin (a) may be melt kneaded (stirred), and then the radical polymerization initiator (b) and the conjugated diene compound (c) may be simultaneously or separately mixed, either all at once or in portions. The temperature in the kneader (stirrer) may be 130 to 300° C. because the polypropylene resin (a) is molten but not thermally decomposed. In addition, the kneading (stirring) time may be 1 to 60 minutes.

In this manner, the conjugated diene-modified polypropylene resin (A) can be produced. The shape and size of the conjugated diene-modified polypropylene resin (A) to be produced are not limited, and the resin (A) may be in the form of pellets.

The polypropylene resin (B) refers to a polypropylene resin having crystallinity. The polypropylene resin modified with the conjugated diene is not included in the concept of the polypropylene resin (B). The polypropylene resin (B) may be either a homopolymer of propylene or a copolymer of propylene and a monomer copolymerizable with propylene. The polypropylene resin (B) may also be a mixture of propylene homopolymer and copolymer. The copolymer may be a so-called block copolymer or a random copolymer. As the copolymer, a copolymer containing 51% by weight or more of propylene may be used, and from the viewpoint of maintaining crystallinity, rigidity, chemical resistance, and the like which are the features of the polypropylene resin, a copolymer containing 75% parts by weight or more of propylene may be used. As the monomer copolymerizable with propylene, the above-mentioned monomers can be used.

Examples of polypropylene resin (B) include a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-ethylene block copolymer, and other propylene-ethylene copolymers. These may be mixed and used.

The propylene-ethylene copolymer may be a propylene polymer in which a polymer containing ethylene as a main component and an ethylene-propylene rubber-like copolymer are dispersed in a linear polymer containing propylene as a main component to form a sea-island structure. Such a propylene polymer is referred to as an impact-resistant polypropylene, conventionally as a block polypropylene in Japan, but it is not a block copolymer in a chemical sense.

The polypropylene resin (B) may have a melt flow rate of 7-100 g/10 minutes, 10-70 g/10 minutes, or 20-50 g/10 minutes, as measured under the above-mentioned conditions. When the melt flow rate of the polypropylene resin (B) is within the above range, in the production of the injection molded body, the molten resin can be filled into a mold at a relatively low pressure during molding using a mold whose cavity includes a thin portion with a clearance of approximately 1 to 2 mm, and stable injection molding tends to be continuously carried out. If the melt flow rate of the component (B) exceeds 100 g/10 minutes, it becomes difficult to adjust the melt flow rate of the composition within the range described later, and when the mixing with the component (A) becomes insufficient, the composition becomes nonuniform and the effect of suppressing burrs is diminished. When the melt flow rate of the component (B) is less than 7 g/10 min, there is no problem from the viewpoint of suppressing burrs, but molding defects such as short shots are likely to be occurred or excessive injection pressure is required, so that another molding defect may occur.

The polypropylene resin composition constituting the injection molded body according to one or more embodiments of the present invention may have a melt flow rate of 10-80 g/10 min, 20-80 g/10 min, 30-80 g/10 min, 40-80 g/10 min, or 60-80 g/10 min, as measured under the above-mentioned conditions.

In the case where a relatively compact molded body is to be obtained and not so much fluidity is required or when it is desired to increase the mold transferability or the like by applying a certain amount of resin pressure during molding, the melt flow rate of the polypropylene resin composition may be 10-60 g/10 min, 10-50 g/10 min, or 10-40 g/10 min.

In the case where a relatively medium-sized molded body is to be obtained and it is necessary to achieve a balance between flowability and resin pressure during molding to some extent, the melt flow rate of the polypropylene resin composition may be 20-75 g/10 min, from 25-70 g/10 min, or 30-65 g/10 min.

When the melt flow rate of the polypropylene resin composition is within the above range, in the production of the injection molded body, the molten resin can be filled into a mold at a relatively low pressure during molding using a mold whose cavity includes a thin portion with a clearance of approximately 1 to 2 mm, and stable injection molding tends to be continuously carried out. If the melt flow rate of the composition exceeds 80 g/10 min, the effect of suppressing burrs of the component (A) is reduced. When the melt flow rate of the composition is less than 10 g/10 min, the effect of suppressing burrs is not affected, but molding defects such as short shots are likely to be occurred or excessive injection pressure is required, so that another molding defect may occur.

The melt flow rate of the resin composition is a numerical value measured after sufficient melt-kneading of each component, and can be easily adjusted on the basis of the melt flow rate of each of the conjugated diene-modified polypropylene resin (A) and the polypropylene resin (B), the blending amount of each component, and the like.

The polypropylene resin composition may have a melt tension of 0.7-30 gf, 1.0-20 gf, 1.5-10 gf, or 2.0-5.0 gf, as measured at 200° C. and 10 m/min. When the melt tension of the polypropylene resin composition is within the above range, the injection molded body can achieve an excellent effect of suppressing burrs. The melt tension of the resin composition is a numerical value measured after sufficient melt-kneading of each component and can be easily adjusted based on the melt flow rate of each of the conjugated diene-modified polypropylene resin (A) and the polypropylene resin (B), as well as on the basis of the type, the combination, the blending amount, etc. of each component.

In the present application, the melt tension (hereinafter occasionally abbreviated as “MT”) is measured as follows. Using a CAPILOGRAPH (manufactured by Toyo Seiki Seisaku-sho, Ltd.) which includes a 10 mm cylinder having an end with a 1 mm orifice having a length of 10 mm and is equipped with an attachment for melt tension measurement, a strand discharged from a die when a piston is fallen at 200° C. and a piston fall speed of 10 mm/min, is connected to a pulley with a load cell located 520 mm below, and taken up at a speed of 10 m/min by the pulley, and a load applied to the pulley with a load cell is measured with time. The maximum value and the minimum value of the load obtained after the load shake was stabilized roughly were measured, and the average value of them was regarded as the melt tension. Note that in the case where the strand is broken, measurement is regarded as unmeasurable and in the case where the load applied to the load cell pulley is low enough to be undetectable, the melt tension is regarded as 0.

The melt tension indicates the tension required for deforming the molten resin, whereas the melt flow rate is a measure showing the fluidity of the molten resin, so that both are different concepts. As shown in a later comparative example, even when the melt flow rate of the resin composition is within the range specified in the present disclosure and when the melt tension of the resin composition is not within the range specified in the present disclosure, a desired effect of suppressing burrs cannot be achieved. Focusing attention on the melt tension of the resin composition, it is not known at all in the past that burrs of the injection molded body can be reduced by adjusting the melt tension, and such a reduction of burrs is the finding that is found for the first time by the present inventors. In one or more embodiments of the present invention, a mechanism of suppressing burrs of the injection molded body by using the predetermined components (A) and (B) and adjusting both the melt flow rate and the melt tension of the resin composition within a predetermined range is unknown at present. However, one of the reasons is thought to be that the molten resin hardly intrudes into the gaps of the mold due to the increased elasticity of the molten resin, resulting in less generation of burrs. In addition, it is considered that the crystallization promoting effect achieved by the addition of the component (A) as described below also contributes to the reduction in generation of burrs.

In the polypropylene resin composition, the content of the conjugated diene-modified polypropylene resin (A) is 0.1-50 parts by weight and the content of the polypropylene resin (B) is 99.9-50 parts by weight, relative to 100 parts by weight of the total of the conjugated diene-modified polypropylene resin (A) and the polypropylene resin (B). When the blending ratio is within the above range, an injection molded body satisfying both fluidity and burr prevention effect can be provided at low cost. If the blending ratio is out of the above range, for example, when the content of the conjugated diene-modified polypropylene resin (A) is less than 0.1 parts by weight, sufficient burr prevention effect tends to be not obtained. If the content of the conjugated diene-modified polypropylene resin (A) exceeds 50 parts by weight, the fluidity tends to be lowered and the appearance of the molded product tends to deteriorate. From the viewpoint of fluidity and burr prevention effect, the content of (A) may be 0.5-45 parts by weight and the content of (B) may be 99.5-55 parts by weight; the content of (A) may be 1-35 parts by weight and the content of (B) may be 99-65 parts by weight; the content of (A) may be 2-25 parts by weight and the content of (B) may be 98-75 parts by weight; and the content of (A) may be 3-15 parts by weight and the content of (B) may be 97-85 parts by weight.

The polypropylene resin composition constituting the injection molded body according to one or more embodiments of the present invention may further contain a polypropylene resin different from any of the above-mentioned components (A) and (B), a high-density polyethylene resin, a high pressure method low density polyethylene resin, a linear low density polyethylene resin, an ethylene-α-olefin copolymer, an olefin elastomer, a styrene elastomer, and other thermoplastic resins.

The polypropylene resin composition may further contain stabilizers such as an antioxidant, a metal deactivator, a phosphorus processing stabilizer, an ultraviolet absorber, an ultraviolet stabilizer, a fluorescent whitening agent, a metal soap, and an antacid adsorbent; and additives such as a crosslinking agent, a chain transfer agent, a nucleating agent, a plasticizer, a lubricant, a filler, a reinforcing material, a pigment, a dye, a flame retardant, and an antistatic agent. However, the polypropylene resin composition does not contain a foaming agent.

One or more embodiments of the present invention relate to an injection molded body of the polypropylene resin composition. The injection molded body according to one or more embodiments of the present invention is excellent in fluidity and burr prevention performance. Therefore, it is particularly suitable for large-size injection molded bodies manufactured using a large mold. Furthermore, the injection molded body according to one or more embodiments of the present invention can be adjusted to a desired fluidity and can suppress burrs, so that a desired injection molded body can be obtained as compared with the conventionally known injection molded body of a polypropylene resin.

The injection molding method that can be used for manufacturing the injection molded body according to one or more embodiments of the present invention is not particularly limited, and a known method can be applied. Specific molding conditions can be appropriately determined in consideration of the melt flow rate and melt tension indicated by the polypropylene resin composition, the type of molding machine, the shape of mold, and the like.

Specifically, the resin temperature may be 170 to 300° C., 180 to 280° C., or 190 to 270° C., and the mold temperature may be 10 to 100° C., or 20 to 80° C. It may also be possible to carry out the molding under the conditions of molding cycle 1 to 120 minutes, injection speed 10 to 300 mm/sec, injection pressure 10 to 200 MPa. and the like.

The injection molded body according to one or more embodiments of the present invention can be used for various purposes. Particularly, as a large-sized injection molded body in which burrs are suppressed, it can be used as an automobile part, an exterior part for household electric appliances, an exterior part for industrial machinery, an exterior member for building, an interior member for building, a protective member for absorbing an impact, a casing of an electronic component, and the like.

EXAMPLES

Hereinafter, one or more embodiments of the present invention will be explained in more detail by way of examples, but the present invention is not limited to these examples at all.

In examples and comparative examples, test methods and determination criteria used in various evaluations are as follows.

(1) Melt Flow Rate (MFR)

The melt flow rate refers to the value calculated as follows. Using a Melt Indexer F-F01 (manufactured by Toyo Seiki Seisaku-sho, Ltd.) in accordance with JIS K 7210: 1999, the amount of resin extruded from a die for a predetermined period of time at 230° C. under a load of 2.16 kg is measured and used to calculate an amount of resin extruded for 10 minutes as the melt flow rate. Such value was obtained by MFR automatic calculation processing (Method B). The calculation formulas are as follows. Even when the melt flow rate exceeds 50 (g/10 min), this method was applied.

MFR (g/10 min)=(427×L×ρp)/t

L (interval of test conditions): 3 (cm)

ρ (melt density at test temperature): it is a value (g/cm³) calculated according to the following formula by a cutting method, provided that p is set to 0.75 (g/cm³) when the cutting method is impossible.

ρ=m/(0.711×L)

m: mass (g) of the sample flowing out as a piston moves through the interval L, measured by the cutting method.

L: same as above interval

t (interval movement time): actual measured value (seconds)

That is, when the cutting method can be applied, calculation may be performed by the following calculation formula

MFR (g/10 min)=(600×m)/t

(2) Melt Tension (MT)

Using a CAPILOGRAPH (manufactured by Toyo Seiki Seisaku-sho. Ltd.) which includes a ϕ 10 mm cylinder having an end with a ϕ 1 mm orifice having a length of 10 mm and was equipped with an attachment for melt tension measurement, a strand discharged from a die when a piston was fallen at 200° C. and a piston fall speed of 10 mm/min, was connected to a pulley with a load cell located 370 mm or 520 mm below, and taken up at a speed of 10 m/min by the pulley, and a load applied to the pulley with a load cell was measured with time. The maximum value and the minimum value of the load obtained after the load shake was stabilized roughly were measured, and the average value of them was regarded as the melt tension. In addition, in the case where the strand was broken, measurement was regarded as unmeasurable and in the case where the load applied to the load cell pulley was low enough to be undetectable, the melt tension was regarded as 0.

(3) Crystallization Temperature

According to the measurement method in accordance with the JIS K 7121 (1987), using a differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Inc., 4 to 10 mg of a measurement sample was heated from room temperature to 230° C. at a rate of 20° C./min, held at 230° C. for 5 minutes to melt, then cooled down from 230° C. to 0° C. at a rate of 10° C./min, thereby to obtain a DSC curve of crystallization behavior. In the obtained DSC curve, the temperature at the point where the calorific value becomes the maximum at the main crystallization peak was regarded as the crystallization temperature.

(4) Burr Evaluation Described in Tables 3 to 5

Using an injection molding machine (IS-100 manufactured by Toyo Machinery & Metal Co., Ltd.), injection molding was carried out in a burr evaluation mold having a disk-shaped cavity with a diameter of 50 mm and a thickness of 2 mm at the minimum filling pressure capable of completely filling the resin composition.

The length of burr (burr length) generated in the injection molded body by the slit having a thickness (clearance) of 0.01 mm, 0.02 mm, 0.03 mm or 0.04 mm×width of 4 mm provided in the circumferential portion of the cavity was measured using a magnifying lens. The shorter the burr length, the better the effect (burr characteristics) of suppressing burr generation is. The burr characteristics were evaluated according to the following criteria.

(Tables 3 and 4)

ο: Burr was not observed, or burr length was less than 0.1 mm

ΔA: Burr length was 0.1 mm to 0.3 mm.

χ: Burr length was 0.4 mm or more.

—: Not evaluated.

(Table 5)

⊚: Burr was not observed.

οΔ: Burr was observed, and burr length was less than 0.1 mm.

Δ: Burr length was 0.1 mm to 0.3 mm

χ: Burr length was 0.4 mm or more.

—: Not evaluated

(5) Burr Evaluation Described in Tables 6 to 8

Using an injection molding machine (IS-100 IV manufactured by Toyo Machinery & Metal Co., Ltd.), injection molding was carried out in a burr evaluation mold having a disk-shaped cavity with a diameter of 50 mm and a thickness of 2.5 mm at a filling pressure of 100 MPa. When the resin composition could not be filled completely into the cavity at the pressure, such a case was judged to be unevaluable due to poor molding.

The length of burr (burr length) generated in the injection molded body by the slit having a thickness (clearance) of 0.02 mm or 0.03 mm×width of 4 mm provided on the circumferential portion of the cavity was measured using a magnifying lens. The shorter the burr length, the better the effect (burr characteristics) of suppressing burr generation is. The burr characteristics were evaluated according to the following criteria in Tables 6 to 7. In Table 8, concrete numbers of the burr length are described.

(Tables 6 to 7)

OK: Burr was not observed, or burr length was less than 0.2 mm

NG: Burr length was 0.2 mm or more.

Production of Conjugated Diene-Modified Polypropylene Resin (A)
Production Example 1

A mixture of 100 parts by weight of a propylene homopolymer (for blowing and extrusion) having a melt flow rate of 2 g/10 min as a (a) polypropylene resin and 0.45 parts by weight oft-butylperoxy isopropyl carbonate as a (b) radical polymerization initiator was fed to a 46 mm twin-screw extruder (L/D=62) at a rate of 70 kg/hour from the hopper and melt-kneaded at a cylinder temperature of 200° C. Then, from the press-in part provided in the middle, 0.55 parts by weight of isoprene as a (c) conjugated diene compound was fed at a rate of 0.385 kg hour using a metering pump and melt-kneaded in the twin-screw extruder to obtain pellets of a conjugated diene-modified polypropylene resin (A-1). The MFR was 1 g/10 min. The obtained conjugated diene-modified polypropylene resin (A-1) is shown in Table 1.

Production Example 2

A conjugated diene-modified polypropylene resin (A-2) was obtained in the same manner as in Production Example 1 except that a propylene homopolymer (for injection molding) having a melt flow rate of 8 g/10 min was used as a (a) polypropylene resin, the blending amount of t-butylperoxy isopropyl carbonate as a (b) radical polymerization initiator was changed to 0.75 parts by weight, and the supply amount of isoprene as a (c) conjugated diene compound was changed to 0.65 parts by weight. The MFR was 3 g/10 min.

Production Example 3

A conjugated diene-modified polypropylene resin (A-3) was obtained in the same manner as in Production Example 1 except that a propylene homopolymer (for injection molding) having a melt flow rate of 8 g/10 min was used as a (a) polypropylene resin, the blending amount of t-butylperoxy isopropyl carbonate as a (b) radical polymerization initiator was changed to 0.75 parts by weight, and the supply amount of isoprene as a (c) conjugated diene compound was changed to 0.6 parts by weight. The MFR was 7 g/10 min.

Production Example 4

A conjugated diene-modified polypropylene resin (A-4) was obtained in the same manner as in Production Example 1 except that a propylene homopolymer (for injection molding) having a melt flow rate of 45 g/10 min was used as a (a) polypropylene resin, the blending amount of t-butylperoxy isopropyl carbonate as a (b) radical polymerization initiator was changed to 1.1 parts by weight, and the supply amount of isoprene as a (c) conjugated diene compound was changed to 0.5 parts by weight. The MFR was 60 g/10 min.

Production Example 5

A conjugated diene-modified polypropylene resin (A-5) was obtained in the same manner as in Production Example 1 except that a propylene homopolymer (for injection molding) having a melt flow rate of 45 g/10 min was used as a (a) polypropylene resin, the blending amount of t-butylperoxy isopropyl carbonate as a (b) radical polymerization initiator was changed to 1.1 parts by weight, and the supply amount of isoprene as a (c) conjugated diene compound was changed to 0.2 parts by weight. The MFR was 150 g/10 min.

Production Example 6

A conjugated diene-modified polypropylene resin (A-6) was obtained in the same manner as in Production Example 1 except that a propylene homopolymer (for injection molding) having a melt flow rate of 45 g/10 min was used as a (a) polypropylene resin, the blending amount of t-butylperoxy isopropyl carbonate as a (b) radical polymerization initiator was changed to 1.1 parts by weight, and the supply amount of isoprene as a (c) conjugated diene compound was changed to 0.55 parts by weight. The MFR was 43 g/10 min.

TABLE 1

Production
Production
Production
Production
Production
Production

Example
Example
Example
Example
Example
Example

1
2
3
4
5
6

(a) Linear
Melt flow rate (MFR)
g/10 min
2
8
8
45
45
45

polypropylene resin

Parts by weight
100
100
100
100
100
100

(b) Radical initiator

Parts by weight
0.45
0.75
0.75
1.1
1.1
1.1

(c) Conjugated

Parts by weight
0.55
0.65
0.6
0.5
0.2
0.55

diem compound

(A) Conjugated
Number

A-1
A-2
A-3
A-4
A-5
A-6

diene-modified
Melt flow rate(MFR)
g/10 min
1
3
7
60
150
43

polypropylene resin
Melt tension (MT)
Gram-force
Unmeasurable
Unmeasurable
Unmeasurable
3.39
1.38
4.45

200° C. 10 m/min

(broken)
(broken)
(broken)

Polypropylene Resin (B)

As the polypropylene resin (B), the following materials were used.

(B-1) Propylene homopolymer having a melt flow rate of 0.9 g/10 min (E-100GPL, manufactured by Prime Polymer Co., Ltd.),

(B-2) Propylene homopolymer having a melt flow rate of 3 g/10 min (F113G, manufactured by Prime Polymer Co., Ltd.),

(B-3) Propylene homopolymer having a melt flow rate of 7 g/10 min (J-700GP, manufactured by Prime Polymer Co., Ltd.),

(B-4) Propylene-ethylene copolymer having a melt flow rate of 30 g/10 min (J830HV manufactured by Prime Polymer Co., Ltd.),

(B-5) Propylene-ethylene copolymer having a melt flow rate of 45 g/10 min (J708UG, manufactured by Prime Polymer Co., Ltd.),

(B-6) Propylene-ethylene copolymer having a melt flow rate of 55 g/10 min (J709QG, manufactured by Prime Polymer Co., Ltd.),

(B-7) Propylene-ethylene copolymer having a melt flow rate of 60 g/10 min (YS559N, manufactured by SanAllomer Ltd.),

(B-8) Propylene-ethylene copolymer having a melt flow rate of 5 g/10 min (J704UG, manufactured by Prime Polymer Co., Ltd.),

(B-9) Propylene-ethylene copolymer having a melt flow rate of 100 g/10 min (VMD81M, manufactured by SanAllomer Ltd.),

(B-10) Propylene homopolymer having a melt flow rate of 60 g/10 min (S119, manufactured by Prime Polymer Co., Ltd.), and

(B-11) Propylene homopolymer having a melt flow rate of 30 g/10 min (J107G, manufactured by Prime Polymer Co., Ltd.).

The propylene-ethylene copolymers described in (B-4), (B-5), (B-6), (B-7). (B-8), and (B-9) refer to propylene polymers in which a polymer containing ethylene as a main component and an ethylene-propylene rubber-like copolymer are dispersed in a linear polymer containing propylene as a main component to form a sea-island structure. Such a propylene polymer is referred to conventionally as a block polypropylene and the like in Japan.

With respect to (B-4), (B-6), (B-8), (B-9), (B-10), and (B-11), each melt tension of the resins alone was also measured.

TABLE 2

MFR
MFR (gf)

(g/10
200° C.

Number
Product name
Manufacturer
Composition
min)
10m/min

B-1
E-100GPL
Manufactured by Prime Polymer
Propylene homopolymer
0.9
—

Co., Ltd.

B-2
F113G
Manufactured by Prime Polymer
Propylene homopolymer
3
—

Co., Ltd.

B-3
J-700GP
Manufactured by Prime Polymer
Propylene homopolymer
7
—

Co., Ltd.

B-4
J830HV
Manufactured by Prime Polymer
Propylene-ethylene
30
0.9

Co., Ltd.
copolymer

B-5
J708UG
Manufactured by Prime Polymer
Propylene-ethylene
45
—

Co., Ltd.
copolymer

B-6
J709QG
Manufactured by Prime Polymer
Propylene-ethylene
55
0.6

Co., Ltd.
copolymer

B-7
YS559N
Manufactured by SunAllomer Ltd.
Propylene-ethylene
60
—

copolymer

B-8
J704UG
Manufactured by Prime Polymer
Propylene-ethylene
5
2.3

Co., Ltd.
copolymer

B-9
VMD81M
Manufactured by SunAllomer Ltd.
Propylene-ethylene
100
0.6

copolymer

B-10
S119
Manufactured by Prime Polymer
Propylene homopolymer
60
Unmeasurable

Co., Ltd.

B-11
J107G
Manufactured by Prime Polymer
Propylene homopolymer
30
0.3

Co., Ltd.

Examples 1-1 to 1-4
<Production of Injection Molded Body>

A conjugated diene-modified polypropylene resin (A), a polypropylene resin (B), and a color masterbatch as a colorant [Dye color PP-M77255, Black, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., Black, 3 parts by weight (relative to 100 parts by weight of the total of (A) and (B))] were dry-blended using the type and composition ratio shown in Table 3. From the obtained dry-blended product, an injection molded body was produced under the temperature conditions shown in Table 3, and the degree of burr formation was evaluated in accordance with the items of the above-described burr evaluation. The obtained results are shown in Table 3.

Comparative Example 1-1

An injection molded body was produced using the type and composition ratio of the materials shown in Table 3 in the same manner as in Example 1 except that the conjugated diene-modified polypropylene resin (A) was not used and the degree of burr formation was evaluated. The obtained results are shown in Table 3.

TABLE 3

Temperature
Conjugated diene-modified
Polypropylene

condition (° C.)
polypropylene resin (A)
resin (B)
Colorant
Evaluation of burrs (clearance mm)

Number
Nozzle tip
Mold
Number
Parts
Number
Parts
Parts
0.01 mm
0.02 mm
0.03 mm
0.04 mm

Example 1-1B
220
40
A-3
3
B-4
97
3
∘
Δ
Δ
Δ

Example 1-2B
220
40
A-3
5
B-4
95
3
∘
∘
Δ
Δ

Example 1-3B
220
40
A-3
10
B-4
90
3
∘
∘
∘
Δ

Example 1-4A
200
40
A-3
20
B-4
80
3
∘
∘
∘
∘

Example 1-4B
220
40
A-3
20
B-4
80
3
∘
∘
∘
Δ

Example 1-4C
240
40
A-3
20
B-4
80
3
∘
∘
∘
Δ

Example 1-4D
260
40
A-3
20
B-4
80
3
∘
∘
∘
Δ

Comparative
200
40
—
—
B-4
100
3
Δ
Δ
Δ
Δ

Example 1-1A

Comparative
220
40
—
—
B-4
100
3
Δ
Δ
Δ
Δ

Example 1-1B

Comparative
240
40
—
—
B-4
100
3
Δ
Δ
Δ
x

Example 1-1C

Comparative
760
40
—
—
B-4
100
3
Δ
Δ
x
x

Example 1-1D

From Comparative Examples 1-1A to 1-1D, it can be seen that the polypropylene resin (B-4) is a resin that easily generates burrs, but as seen in Example 1-1B, by blending 3 parts by weight of the conjugated diene-modified polypropylene resin (A) (provided that the total of the components (A) and (B) is 100 parts by weight, and the same applies hereinafter) with the (B-4), it was recognized that the effect of suppressing burrs was exhibited. Further, as seen in Examples 1-2 B and 1-3 B, it was recognized that such effect was increased by increasing the blending amount of the component (A) to 5 parts by weight and 10 parts by weight, respectively. Further, from Examples 1-4A to 1-4D, the effect of suppressing burrs was remarkable at any molding temperature of from 200° C. to 260° C. when 20 parts by weight of the component (A) was blended. Especially, as seen in Examples 1-4D, it was recognized that even when the molding temperature was changed to a condition such as 260° C. at which burrs extremely easily generates, the effect of suppressing burrs was exhibited.

Since the compositions of Examples 14A to 1-4D correspond to the composition of Example 4-11 in Table 6 which will be described later, Examples 1-4A to 1-4D satisfy the requirements of MFR value and MT value of the resin composition specified in the present application. In addition, since the compositions of Example 1-1B to Example 1-3B were intermediate between the composition of Comparative Example 4-10 and the composition of Example 4-11 in Table 6, and Comparative Examples 4-10 and Examples 4-11 all satisfy the requirements of the MFR value and the MT value of the resin composition of the present application, it is estimated that Examples 1-1B to 1-3B also satisfy the requirements of the MFR value and the MT value of the resin composition of the present application.

Example 2-1 and Comparative Example 2-1
<Production of Injection Molded Body>

A dry-blended product was obtained in the same manner as in Example 1 using the type and composition ratio of the resins shown in Table 4, and an injection molded body was produced under the temperature conditions shown in Table 4, and the degree of burrs was evaluated in accordance with the items of the above-described burr evaluation. The obtained results are shown in Table 4.

TABLE 4

Temperature
Conjugated diene-modified
Polypropylene

condition (° C.)
polypropylene resin (A)
resin (B)
Burr evaluation (clearance mm)

Number
Nozzle tip
Mold
Number
Parts
Number
Parts
0.01 mm
0.02 mm
0.03 mm
0.04 mm

Example 2-1A
200
40
A-4
20
B-6
80
∘
Δ
Δ
Δ

Comparative
200
40
—
—
B-6
100
Δ
x
x
x

Example 2-1A

Example 2-1B
220
40
A-4
20
B-6
80
∘
Δ
Δ
Δ

Comparative
220
40
—
—
B-6
100
Δ
x
x
x

Example 2-1B

Example 2-1C
240
40
A-4
20
B-6
80
∘
Δ
Δ
Δ

Comparative
240
40
—
—
B-6
100
Δ
x
x
x

Example 2-1C

Example 2-1D
260
40
A-4
20
B-6
80
∘
Δ
Δ
Δ

Comparative
260
40
—
—
B-6
100
—
—
—
—

Example 2-1D

From Comparative Examples 2-1A to 2-1D, it is understood that the polypropylene resin (B-6) is a resin that easily generates burrs. However, as shown in Examples 2-1A to 2-1D, it was confirmed that the resin (B-6) blended with the component (A) exhibits the effect of suppressing burrs without sacrificing the fluidity (MFR) of the composition. Furthermore, as shown in Example 2-1D, it was recognized that even when the molding temperature was changed to a condition such as 260° C. at which burrs extremely easily generate, the effect of suppressing burrs was exhibited.

Since the compositions of Examples 2-1A to 2-1D correspond to the composition of Example 4-33 in Table 6 described later. Examples 2-1A to 2-1D satisfy the requirements of MFR value and MT value of the resin composition specified in one or more embodiments of the present invention.

Examples 3-1 to 3-18 and Comparative Examples 3-1 to 3-7
<Production of Injection Molded Body>

A dry-blended product was obtained in the same manner as in Example 1 using the type and composition ratio of the resins shown in Table 5, and an injection molded body was produced under the temperature conditions shown in Table 5, and the degree of burr formation was evaluated in accordance with the items of the above-described burr evaluation. The obtained results are shown in Table 5.

TABLE 5

Conjugated

diene-modified

Burr evaluation

Temperature
polypropylene

(clearance mm)

condition ° C.
resin (A)
Polypropylene resin(B)
0.01
0.02
0.03
0.04

Number
Nozzle tip
Mold
Number
Parts
Number
Parts
Number
Parts
mm
mm
mm
mm

Comparative
220
40
—
—
B-5
100
—
—
Δ
X
X
X

Example 3-1B

Example 3-1B
220
40
A-1
3
B-5
97
—
—
◯Δ
Δ
Δ
X

Example 3-2B
220
40
A-1
5
B-5
95
—
—
⊚
Δ
Δ
X

Example 3-3B
220
40
A-1
7
B-5
93
—
—
⊚
Δ
Δ
X

Example 3-4B
220
40
A-1
10
B-5
90
—
—
⊚
Δ
Δ
Δ

Example 3-5B
220
40
A-1
15
B-5
85
—
—
⊚
Δ
Δ
Δ

Example 3-6B
220
40
A-1
20
B-5
80
—
—
⊚
◯Δ
Δ
Δ

Example 3-7B
220
40
A-2
3
B-5
97
—
—
◯Δ
Δ
Δ
X

Example 3-8B
220
40
A-2
5
B-5
95
—
—
⊚
Δ
Δ
X

Example 3-9B
220
40
A-2
7
B-5
93
—
—
⊚
Δ
Δ
X

Example 3-10B
220
40
A-2
10
B-5
90
—
—
⊚
Δ
Δ
Δ

Example 3-11B
220
40
A-2
15
B-5
85
—
—
⊚
Δ
Δ
Δ

Example 3-12B
220
40
A-2
20
B-5
80
—
—
⊚
◯Δ
Δ
Δ

Example 3-13B
220
40
A-3
3
B-5
97
—
—
◯Δ
Δ
Δ
X

Example 3-14B
220
40
A-3
5
B-5
95
—
—
⊚
Δ
Δ
X

Example 3-15B
220
40
A-3
7
B-5
93
—
—
⊚
Δ
Δ
X

Example 3-16B
220
40
A-3
10
B-5
90
—
—
⊚
Δ
Δ
X

Example 3-17B
220
40
A-3
15
B-5
85
—
—
⊚
Δ
Δ
Δ

Example 3-18B
220
40
A-3
20
B-5
80
—
—
⊚
◯Δ
Δ
Δ

Comparative
220
40
—
—
B-5
95
B-1
5
◯Δ
X
X
X

Example 3-2B

Comparative
220
40
—
—
B-5
90
B-1
10
◯Δ
X
X
X

Example 3-3B

Comparative
220
40
—
—
B-5
80
B-1
20
◯Δ
X
X
X

Example 3-4B

Comparative
220
40
—
—
B-5
95
B-7
5
◯Δ
X
X
X

Example 3-5B

Comparative
220
40
—
—
B-5
90
B-2
10
◯Δ
X
X
X

Example 3-6B

Comparative
220
40
—
—
B-5
80
B-2
20
◯Δ
X
X
X

Example 3-7B

Comparative
240
40
—
—
B-5
100
—
—
Δ
X
X
X

Example 3-1C

Example 3-1C
240
40
A-1
3
B-5
97
—
—
◯Δ
Δ
Δ
X

Example 3-2C
240
40
A-1
5
B-5
95
—
—
◯Δ
Δ
Δ
X

Example 3-3C
240
40
A-1
7
B-5
93
—
—
⊚
Δ
Δ
X

Example 3-4C
240
40
A-1
10
B-5
90
—
—
⊚
Δ
Δ
X

Example 3-5C
240
40
A-1
15
B-5
85
—
—
⊚
Δ
Δ
Δ

Example 3-6C
240
40
A-1
20
B-5
80
—
—
⊚
◯Δ
Δ
Δ

Example 3-7C
240
40
A-2
3
B-5
97
—
—
◯Δ
Δ
Δ
X

Example 3-8C
240
40
A-2
5
B-5
95
—
—
◯Δ
Δ
Δ
X

Example 3-9C
240
40
A-2
7
B-5
93
—
—
⊚
Δ
Δ
X

Example 3-10C
240
40
A-2
10
B-5
90
—
—
⊚
Δ
Δ
X

Example 3-11C
240
40
A-2
15
B-5
85
—
—
⊚
Δ
Δ
Δ

Example 3-12C
240
40
A-2
20
B-5
80
—
—
⊚
◯Δ
Δ
Δ

Example 3-13C
240
40
A-3
3
B-5
97
—
—
◯Δ
Δ
Δ
X

Example 3-14C
240
40
A-3
5
B-5
95
—
—
⊚
Δ
Δ
X

Example 3-15C
240
40
A-3
7
B-5
93
—
—
⊚
Δ
Δ
X

Example 3-16C
240
40
A-3
10
B-5
90
—
—
⊚
Δ
Δ
X

Example 3-17C
240
40
A-3
15
B-5
85
—
—
⊚
Δ
Δ
Δ

Example 3-18C
240
40
A-3
20
B-5
80
—
—
⊚
◯Δ
Δ
Δ

Comparative
240
40
—
—
B-5
95
B-1
—
—
—
—

Example 3-2C

Comparative
240
40
—
—
B-5
90
B-1
10
—
—
—
—

Example 3-3C

Comparative
240
40
—
—
B-5
80
B-1
20
◯Δ
X
X
X

Example 3-4C

Comparative
240
40
—
—
B-5
95
B-2
5
—
—
—
—

Example 3-5C

Comparative
240
40
—
—
B-5
90
B-2
10
—
—
—
—

Example 3-6C

Comparative
240
40
—
—
B-5
80
B-2
20
◯Δ
X
X
X

Example 3-7C

From Comparative Example 3-1B or 3-1C, it can be seen that the polypropylene resin (B-5) is a resin that easily generates burrs. However, as can be seen from Example 3-1B or 3-1C to 3-18B or 3-18C, it has been found that the resin (B-5) blended with the component (A) exhibits an effect of suppressing the generation of burrs. Furthermore, as can be seen from Comparative Example 3-2B or 3-2C to 3-7B or 3-7C, in the case where in place of the component (A), a polypropylene resin (B-1) or (B-2) having an MFR value similar to that of the component (A) but not modified was added to the (B-5), almost no effect of suppressing burrs was found. Specifically, the MFRs of (A-1) and (B-1) are approximately the same with each other, and the MFR of (A-2) is approximately the same with that of (B-2). For example, when comparing Example 3-2B in which 5 parts by weight of (A-1) is added to (B-5) and Comparative Example 3-2B in which 5 parts by weight of (B-1) is added to (B-5), and comparing Example 3-8B in which 5 parts by weight of (A-2) is added to (B-5) and Comparative Example 3-5B n which 5 parts by weight of (B-2) is added to (B-5), it is understood that the effect of suppressing burrs in the examples is more excellent than that of in the comparative examples.

Furthermore, in Example 3-1B or 3-1C to 3-18B or 3-18C, the burr suppressing effect also increases as the added amount of the component (A) increases to 3, 5, 10, and 20 parts by weight. On the other hand, in Comparative Examples 3-2 to 3-7, even when the addition amount of the non-modified polypropylene resin (B-1) or (B-2) was increased to 5, 10, and 20 parts by weight, there was no increase in the burr suppressing effect

In addition, in each example, a burr suppressing effect was observed at both molding temperatures of 220° C. and 240° C.

Since the compositions of Examples 3-4B and 3-4C correspond to the composition of Example 4-13 in Table 6 described later, Example 3-4B and Example 3-4C satisfy the requirements of MFR value and MT value of the resin composition specified in the present application. In addition, the other examples in Table 5 also satisfy the requirements of MFR value and MT value of the resin composition of the present application.

Examples or Comparative Examples 4-1 to 4-51
<Production of Injection Molded Body>

A conjugated diene-modified polypropylene resin (A), a polypropylene resin (B), and a color masterbatch as a colorant [Dye color PP-M77255, Black, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., 3 parts by weight (relative to 100 parts by weight of the total of (A) and (B))] were dry-blended. This dry blended pellet mixture was fed from a hopper to a 32 mmϕ twin-screw extruder (L/D=25) at 9 kg/hour and melt-kneaded at a cylinder temperature of 200° C. to obtain pellets of the composition. From the obtained composition pellets, injection molded bodies were produced under the temperature conditions shown in Table 6 and the degree of formation of burrs was evaluated in accordance with the items of the above-described burr evaluation, provided that the clearance as 0.02 mm. The obtained results are shown in Table 6.

In addition, the composition pellet was subjected to a measurement of physical properties including a melt flow rate (MFR), a melt tension (MT), and a cystallization temperature.

TABLE 6

Conjugated diene-

Resin composition

modified polypropylene
Polypropylene resin(B)
MFR
MT

Burr

resin (A)

Parts
230° C.
200° C.
Crystallization
evaluation

Parts

Parts by
2.16 kgf
10 m/min
temperature
Clearance

Number
Parts by weight
Number
weight
g/10 min
gf
° C.
0.02 mm

Comparative

0
B-8
100
5.9
0.7

Unevaluable

Example 4-1

Comparative
A-3
5
B-8
95
5.1
3.1

Unevaluable

Example 4-2

Comparative
A-3
10
B-8
90
5.0
3.6

Unevaluable

Example 4-3

Comparative
A-6
5
B-8
95
5.6
31

Unevaluable

Example 4-4

Comparative
A-6
10
B-8
90
6.0
3.3

Unevaluable

Example 4-5

Comparative
A-4
5
B-8
95
5.5
2.7

Unevaluable

Example 4-6

Comparative
A-4
10
B-8
90
6.1
3.3

Unevaluable

Example 4-7

Comparative
A-5
10
B-8
90
6.5
2.7

Unevaluable

Example 4-8

Comparative
A-5
20
B-8
80
8.7
2.8
126.0
Unevaluable

Example 4-9

Comparative

0
B-4
100
32.7
0.2
129.5
NG

Example 4-10

Example 4-11
A-3
20
B-4
80
23.3
2.0

OK

Example 4-12
A-3
50
B-4
50
18.0
3.5

OK

Example 4-13
A-1
10
B-5
90
30.2
1.3

OK

Example 4-14
A-6
3
B-4
97
28.8
1.1

OK

Example 4-15
A-6
10
B-4
90
29.4
2.0

OK

Example 4-16
A-6
20
B-4
80
30.6
2.8
128.5
OK

Example 4-17
A-6
50
B-4
50
40.9
2.0

OK

Example 4-18
A-4
3
B-4
97
28.8
1.1

OK

Example 4-19
A-4
5
B-4
95
28.8
1.2

OK

Example 4-20
A-4
10
B-4
90
29.6
1.7

OK

Example 4-21
A-4
20
B-4
80
31.2
2.3
128.8
OK

Example 4-22
A-4
50
B-4
50
46.3
1.7

OK

Comparative
A-5
20
B-4
80
41.8
0.5

NG

Example 4-23

Comparative

0
B-6
100
53.6
0.0

NG

Example 4-24

Example 4-25
A-3
5
B-6
95
43.0
1.3

OK

Example 4-26
A-3
10
B-6
90
38.5
2.0

OK

Example 4-27
A-3
20
B-6
80
31.1
2.7
130.1
OK

Example 4-28
A-3
50
B-6
50
22.5
3.1

OK

Example 4-29
A-6
5
B-6
95
45.9
1.1
126.2
OK

Example 4-30
A-6
10
B-6
90
46.3
1.7
126.7
OK

Example 4-31
A-6
20
B-6
80
44.4
2.2
127.3
OK

Example 4-32
A-6
50
B-6
50
53.8
1.8

OK

Example 4-33
A-4
20
B-6
80
50.6
0.9

OK

Example 4-34
A-4
50
B-6
50
60.2
1.6

OK

Comparative

0
B-9
100
105.0
0.0
130.7
NG

Example 4-35

Comparative
A-3
5
B-9
95
83.3
1.1

NG

Example 4-36

Comparative
A-6
5
B-9
95
88.4
0.8

NG

Example 4-37

Comparative
A-4
5
B-9
95
90.1
0.8

NG

Example 4-40

Comparative
A-4
10
B-9
90
89.8
1.2

NG

Example 4-41

Comparative
A-5
10
B-9
90
98.0
0.6

NG

Example 4-42

Comparative
A-5
20
B-9
80
106.5
0.8
129.0
NG

Example 4-43

Comparative

0
B-10
100
52.1
0.0
113.2
NG

Example 4-44

Example 4-45
A-3
20
B-10
80
43.3
1.3
126.7
OK

Example 4-46
A-6
20
B-10
80
54.7
0.8
126.3
OK

Example 4-47
A-4
20
B-10
80
57.1
0.7
126.3
OK

Comparative

0
B-11
100
32.7
0.0
112.2
NG

Example 4-48

Example 4-49
A-3
20
B-11
80
24.2
1.9
128.9
OK

Example 4-50
A-6
20
B-11
80
32.9
1.2
126.7
OK

Example 4-51
A-4
20
B-11
80
33.7
1.0
126.5
OK

Temperature conditions for injection molding: nozzle tip 80° C., mold 40° C.

In the case of using the component (B) having an MFR value of less than 7 of the resin alone as in the resin (B-8), it is understood that satisfactory molding cannot be achieved from Comparative Examples 4-1 to 4-9 under the present molding condition even if the component (A) is added. Therefore, in one or more embodiments of the present invention, it may not be preferable to use the component (B) having an MFR value of less than 7 of the resin alone.

As can be seen from Examples 4-11 to 4-22; Examples 4-25 to 4-34; Examples 4-45 to 4-47; and Examples 4-49 to 4-51, when a conjugated diene-modified polypropylene resin (A) having an MFR in the range of 1 to 150 and a polypropylene resin (B) having an MFR in the range of 7 to 100 are blended so that the MFR of the resin composition is in the range of 10 to 80 g/10 min and the MT was in the range of 0.7 to 30 gf it was recognized that a remarkable effect of suppressing burrs was exhibited in the burr evaluation at a clearance of 0.02 mm. Also, such effect was observed as in Examples 4-14 and 4-18, even when only 3 parts by weight of component (A) was added.

From Comparative Example 4-23, it can be understood that a sufficient effect of suppressing burrs cannot be achieved when the MT of the resin composition is less than 0.7 gf even if the requirements of respective MFR values of the component (A), the component (B), and the resin composition are satisfied. From Comparative Examples 4-36 to 4-43, even if the requirements for MFR values of the component (A) and component (B) are satisfied, it is understood that a sufficient effect of suppressing burrs cannot be achieved if the MFR of the resin composition exceeds 80 g/10 min.

Furthermore, as can be seen by comparing Examples 4-45 to 4-47 and Comparative Example 4-44, it was confirmed that when 20 parts by weight of the component (A) is added to the component (B) whose crystallization temperature (Tc) of the resin itself is generally 113° C., the Tc value of the resin composition becomes 126 to 127° C. That is, it was recognized that the addition of the component (A) increased the crystallization rate during cooling. The same can be understood from comparison between Examples 4-49 to 4-51 and Comparative Example 4-48. The effect of promoting crystallization by addition of such a conjugated diene-modified polypropylene resin (A) has not been known hitherto and has been found independently by the present inventors.

Comparative Examples 5-1 to 5-16

Using the type and composition ratio of the resins shown in Table 7, a conjugated diene-modified polypropylene resin (A), a polypropylene resin (B), and a color masterbatch as a colorant [Dye color PP-M77255, Black, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., 3 parts by weight (relative to 100 parts by weight of the total of (A) and (B))] were dry-blended. The resulting pellet mixture was fed from a hopper to a 32 mm twin-screw extruder (L/D=25) at 9 kg/hour and melt-kneaded at a cylinder temperature of 200° C. to obtain pellets of the composition. Three parts by weight of a chemical foaming agent (POLYTHLENE EE 65 C, manufactured by Eiwn Chemical Ind. Co., Ltd.) was dry-blended with 100 parts by weight of the pellets obtained as described above, and injection molded bodies were produced under the same temperature conditions as in Table 6 and the degree of burr formation was evaluated in accordance with the items of the above-described burr evaluation, provided that the clearance was 0.02 mm.

TABLE 7

Conjugated diene-modified

polypropylene resin (A)
Polypropylene resin(B)
Burr evaluation

Parts

Parts
Clearance

Number
Parts by weight
Number
Parts by weight
0.02 mm

Comparative

0
B-4
100
NG

Example 5-1

Comparative
A-6
20
B-4
80
NG

Example 5-2

Comparative
A-4
20
B-4
80
NG

Example 5-3

Comparative

0
B-6
100
NG

Example 5-4

Comparative
A-3
20
B-6
80
NG

Example 5-5

Comparative
A-6
3
B-6
97
NG

Example 5-6

Comparative
A-6
5
B-6
95
NG

Example 5-7

Comparative
A-6
10
B-6
90
NG

Example 5-8

Comparative
A-6
20
B-6
80
NG

Example 5-9

Comparative
A-4
20
B-6
80
NG

Example 5-10

Comparative

0
B-9
100
NG

Example 5-11

Comparative
A-5
20
B-9
80
NG

Example 5-12

Comparative

0
B-10
100
NG

Example 5-13

Comparative
A-3
20
B-10
80
NG

Example 5-14

Comparative
A-6
20
B-10
80
NG

Example 5-15

Comparative
A-4
20
B-10
80
NG

Example 5-16

Temperature conditions for injection molding: nozzle tip 180° C., mold 40° C.

As can be seen from Comparative Examples 5-1 to 5-16, in each of comparative examples in which a foaming agent was added, an effect of suppressing burrs was not recognized in the burr evaluation at a clearance of 0.02 mm. In particular, in Comparative Examples 5-2, 5-3, 5-5 to 5-10, and 5-14 to 5-16, the composition itself of each of the resin compositions is the same as the composition of the resin composition in each example. These comparative examples are not directed to injection molded bodies that are not added with a foaming agent, but they are different from examples in that a foaming agent was added. From this, even if each requirement of the resin composition in the present application is satisfied, the effect of suppressing burrs is not exhibited when a foaming agent is added, and it is understood that the effect of suppressing burrs according to one or more embodiments of the present invention can be exerted only in an injection molded body to which no foaming agent is added.

Examples 6-1 to 6-6
<Production of Injection Molded Body>

Using the type and composition ratio of the resins shown in Table 8, a conjugated diene-modified polypropylene resin (A), a polypropylene resin (B), and a color masterbatch as a colorant [Dye color. PP-M77255, Black, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., 3 parts by weight (relative to 100 parts by weight of the total of (A) and (B))] were dry-blended. The resulting dry-blended pellet mixture was fed from a hopper to a 32 mmϕ twin-screw extruder (L/D=25) at 9 kg/hour and melt-kneaded at a cylinder temperature of 200° C. to obtain pellets of the composition. Injection molded bodies were produced under the same temperature conditions as in Table 8, and the degree of burr formation was evaluated in accordance with the items of the above-described burr evaluation, provided that the clearance was 0.03 mm. The obtained results are shown in Table 8.

In addition, the composition pellets were subjected to a measurement of physical properties including melt flow rate (MFR) and melt tension (MT).

TABLE 8

Conjugated diene-

Resin composition

modified polypropylene
Polypropylene resin(B)
MFR
MT

resin (A)

Parts
230° C.
200° C.
Burr length

Parts

Parts by
2.16 kgf
10 m/min
Clearance

Number
Parts by weight
Number
weight
g/10 min
gf
0.03 mm

Example 6-1
A-3
10
B-4
90
26.4
1.1
0.3

Example 6-2
A-6
5
B-4
95
28.8
1.5
0.3

Example 6-3
A-3
3
B-6
97
42.7
1.1
0.3

Example 6-4
A-6
3
B-6
97
47.0
0.9
0.3

Example 6-5
A-5
20
B-6
80
57.5
1.3
0.3

Example 6-6
A-3
10
B-9
90
71.1
1.7
0.2

Temperature conditions for injection molding: nozzle tip 180° C., mold 40° C.

From Examples 6-1 to 6-3, an effect of suppressing burrs % as observed by the burr evaluation at the clearance of 0.03 mm when a conjugated diene-modified polypropylene resin (A) having an MFR in the range of 1 to 150 and a polypropylene resin (B) having an MFR in the range of 7 to 100 were blended so that the MFR of the resin composition was in the range of 10 to 80 g/10 min and the MT was in the range of 0.7 to 30 gf. Particularly, in Example 6-6 in which the MFR of the resin composition was in the range of 60 to 80 g/10 min, it was found that the burr length was shorter than in other examples and an effect of suppressing burrs was excellent.

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.