JP6577168B2 - Thermoplastic elastomer composition and sheet thereof - Google Patents

Description

  The present invention relates to a resin composition comprising a thermoplastic elastomer and a sheet thereof.

In various applications such as food containers, automobile parts, building materials, and home appliance parts, molded bodies obtained by thermoforming resin sheets are widely used. Among these, those using a polypropylene resin as a base material are suitably used in applications that require high heat resistance, chemical resistance, and the like. On the other hand, compared to other resins, the decrease in viscosity at the time of melting is large and the melt tension is low, so the sheet is stretched locally at the time of shaping, the thickness becomes non-uniform, and the wrinkle pattern on the surface flows. There was a problem that it was easy to cause a malfunction.
Patent Document 1 discloses a sheet made of a composition comprising a specific low density polyethylene, a high density polyethylene, and talc with respect to a specific polypropylene. However, in this method, since a relatively large amount of polyethylene resin is added to the polypropylene resin, there is a problem that the heat resistance of the polypropylene resin is impaired and the appearance is inferior.
Patent Document 2 discloses electron beam cross-linking and reactive functional groups as a resin composition that can prevent wrinkle flow, has a small drawdown, and can achieve product thickness uniformity even during deep drawing in vacuum forming. A crosslinked resin composition is disclosed. However, the problem of electron beam irradiation is that the equipment cost is high and the manufacturing cost is high, the effect of reducing the local elongation during sheet molding due to main chain cutting may be reduced, and when reactive functional groups are cross-linked, After the introduction of the functional group, it is necessary to crosslink and a plurality of heat histories are applied, so that the resin may be deteriorated.

JP-A-5-262897 JP-A-8-73684

  An object of the present invention is to provide a non-foamed sheet resin composition and a non-foamed sheet comprising the resin composition for a non-foamed sheet that can reduce the local elongation of the sheet and suppress the flow of a texture pattern on the surface when the sheet is processed.

As a result of intensive studies, the present inventor has found that a non-foamed sheet composed of the modified polypropylene resin of the present invention and a thermoplastic elastomer can solve the above problems. That is, the present invention has the following contents.
[1] A resin composition for a non-foamed sheet comprising a thermoplastic elastomer (A) and a modified polypropylene resin (B), wherein the modified polypropylene resin (B) comprises a linear polypropylene resin (a). A resin composition for non-foamed sheets obtained by melt-kneading the conjugated diene compound (b) and the radical polymerization initiator (c).
[2] The resin composition for non-foamed sheets as described in 1 above, wherein the thermoplastic elastomer (A) satisfies the following 1) to 3).
1) MFR (230 ° C., 2.16 kg) is 0.1 to 10 g / 10 min 2) Density is 0.85 g / cm 3 or more and 0.88 g / cm 3 or less 3) Propylene content is 50% by weight or more [3] The resin composition for non-foamed sheets as described in any one of 1 to 2 above, wherein the porous polypropylene resin (B) satisfies the following 1) to 2).
1) MFR (230 ° C., 2.16 kg) is 0.1 to 10 g / 10 min. 2) Loss tangent (tan δ) at an angular frequency of 1 rad / s in dynamic viscoelasticity measurement at 200 ° C. is 2.0 or less. [4] The non-foamed sheet as described in any one of 1 to 3 above, wherein the MFR (230 ° C., 2.16 kg) of the linear polypropylene resin (a) is 0.1 to 10 g / 10 min. Resin composition.
[5] The total of the resin composition for non-foamed sheet (A) and (B) is 100 parts by weight, the thermoplastic elastomer (A) is 60 to 97 parts by weight, and the modified polypropylene resin (B) is 3 to 40 parts by weight. The resin composition for non-foamed sheets according to any one of 1 to 4 above, comprising a part.
[6] A non-foamed sheet obtained from the resin composition for non-foamed sheets according to any one of 1 to 5 above.
[7] A non-foamed sheet molded body obtained by heat-molding the non-foamed sheet as described in 6 above.
[8] The non-foamed sheet molded article according to 7, wherein the non-foamed sheet molded article is for automobile parts.

  The non-foamed sheet using the resin composition comprising the modified polypropylene resin and the thermoplastic elastomer of the present invention can reduce the local elongation of the sheet at the time of heat molding, and can suppress the flow of a texture pattern on the surface. It is possible to produce a molded body having a uniform thickness and excellent appearance. Furthermore, since the non-foamed sheet of the present invention can be composed of a polypropylene resin for the entire base material, it improves thermoformability without impairing its heat resistance, chemical resistance, and rigidity. It has the feature that it can.

As shown in Fig. 2, the non-foamed sheet was cut into a width of 40 mm and a length of 120 mm, a line was drawn at a position of 20 mm from the end in the length direction and the width direction, and the length direction was divided into 8 at 10 mm intervals. For stretching the non-foamed sheet, both ends of the sheet were fixed with clips, and heated in a furnace set at 130 ° C. for 3 minutes. Thereafter, the film was stretched to 150% at a stretching speed of 200 mm / min and held in a furnace for 1 minute. While being fixed to the clip, it was taken out from the furnace and cooled until it returned to room temperature to prepare a non-foamed sheet molded body.

  An embodiment of the present invention will be described as follows. The present invention is not limited to the following description.

<Resin composition for non-foamed sheet>
The resin composition for non-foamed sheets of the present invention comprises a thermoplastic elastomer (A) and a modified polypropylene resin (B). Moreover, a thermoplastic resin or rubber | gum (C) and an additive may be contained as needed.

  The composition ratio of the resin composition for a non-foamed sheet of the present invention is such that the total of (A), (B) and (C) is 100% by weight, (A) is 60 parts by weight or more and 97 parts by weight or less, (B) 3 parts by weight or more and 40 parts by weight or less, (C) preferably 0 part by weight or more and 25 parts by weight or less, (A) 70 parts by weight or more and 90 parts by weight or less, and (B) 10 parts by weight. It is particularly preferred that the composition comprises 30 parts by weight or less and 0 to 15 parts by weight of (C). When (B) is less than 3 parts by weight, the effect obtained in the present invention cannot be obtained, and when it is more than 40 parts by weight, the effect of modification is saturated.

<Thermoplastic elastomer (A)>
In the present invention, the thermoplastic elastomer refers to one that exhibits fluidity when heated and exhibits rubber elasticity at room temperature. Among them, specific examples of the thermoplastic elastomer (A) preferably used in the present invention include ethylene-α-olefin copolymers, propylene-α-olefin copolymers, ethylene-propylene-diene copolymers, and dynamics thereof. Olefin-based elastomers such as cross-linked products, ethylene-vinyl acetate copolymer, chlorinated polyethylene; styrene-isobutylene-styrene copolymer, styrene-isobutylene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene Examples thereof include styrene elastomers such as copolymers and hydrogenated products thereof; polyester elastomers; polyamide elastomers; polyurethane elastomers and the like. Moreover, you may use 2 or more types from these. A composition in which the elastomer described in the above-described preferred specific example is combined with another resin or additive by a method such as multistage polymerization or melt blending is known. As long as the requirements for the plastic elastomer are satisfied, these compositions can also be suitably used as the thermoplastic elastomer (A). Among these, from the viewpoint that the modified polypropylene resin (B) is easily dispersed and relatively inexpensive, an olefin elastomer is preferable, a propylene-α-olefin copolymer is more preferable, and ethylene-propylene is preferable. More preferred are copolymers

As the melt flow rate (hereinafter referred to as MFR) of (A), MFR (230 ° C., 2.16 kg) measured under conditions of 230 ° C. and 2.16 kg load is 0.1 g / 10 min or more and less than 10 g / 10 min. Is preferably 0.5 g / 10 min or more and less than 8 g / 10 min, and particularly preferably 0.5 g / 10 min or more and less than 5 g / 10 min. When the MFR (230 ° C., 2.16 kg) of (A) is less than 0.1 g / 10 min, the fluidity at the time of melting of the resin composition for non-foamed sheets tends to be insufficient, and the obtained non- There exists a tendency for the external appearance of a foam sheet to deteriorate. On the other hand, when MFR (230 degreeC, 2.16 kg) exceeds 10 g / 10min, it exists in the tendency for the local elongation of the non-foamed sheet obtained to become large.
The density of the thermoplastic elastomer (A) is preferably from 0.85 g / cm 3 to 0.90 g / cm 3, more preferably from 0.86 g / cm 3 to 0.89 g / cm 3, and from 0.87 g / cm 3 to 0.80. 88 g / cm 3 or less is particularly preferable. When the density of the thermoplastic elastomer (A) is within this range, the modified polypropylene resin (B) is easily dispersed, and the appearance of the non-foamed sheet is improved.

<Modified polypropylene resin (B)>
The modified polypropylene resin (B) of the present invention is obtained by reacting a linear polypropylene resin (a), a conjugated diene compound (b), and a radical polymerization initiator (c). Moreover, you may make the monomer copolymerizable with a conjugated diene compound react. The linear polypropylene resin (a) is a polypropylene resin having a linear molecular structure. Examples of the linear polypropylene resin (a) include a propylene homopolymer, a propylene block copolymer, and a propylene random copolymer. The linear polypropylene resin (a) preferably contains 75% by weight or more, more preferably 80% by weight or more, and more preferably 90% by weight or more from the viewpoint of crystallinity, rigidity, chemical resistance and the like. A propylene homocopolymer, preferably 100% by weight, is particularly preferred.

  The α-olefin copolymerizable with propylene includes ethylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3,4-dimethyl-1. Α-olefins having 2 or 4 to 12 carbon atoms such as butene, 1-heptene, 3-methyl-1-hexene, 1-octene and 1-decene, cyclopentene, norbornene, tetracyclo [6,2,11,8, Cyclic olefins such as 13,6] -4-dodecene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 1,4-hexadiene, methyl-1,4-hexadiene, 7-methyl-1,6 -Diene such as octadiene, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, maleic acid, acrylic Examples thereof include vinyl monomers such as ethyl luate, butyl acrylate, methyl methacrylate, maleic anhydride, styrene, methyl styrene, vinyl toluene, and divinyl benzene. These may be used alone or in combination of two or more. Of these, ethylene and 1-butene are preferable in terms of sheet formability, low cost, and the like.

  The MFR (230 ° C., 2.16 kg) of the linear polypropylene resin (a) is preferably 0.1 g / 10 min or more and less than 10 g / 10 min, more preferably 0.5 g / 10 min or more and less than 8 g / 10 min. 1.0 g / 10 min or more and less than 5.0 g / 10 min is more preferable. When the MFR (230 ° C., 2.16 kg) is less than 0.1 g / 10 min, the fluidity at the time of melting becomes insufficient, and the conjugated diene compound (b) and the radical polymerization initiator (c) melt. Kneading may become insufficient, and when the MFR (230 ° C., 2.16 kg) is 10 g / 10 min or more, the local elongation of the non-foamed sheet tends to increase.

The MFR (230 ° C., 2.16 kg) of the modified polypropylene resin (B) is preferably 0.1 g / 10 minutes or more and less than 10 g / 10 minutes, more preferably 0.5 g / 10 minutes or more and less than 8 g / 10 minutes. 1.0 g / 10 min or more and less than 5.0 g / 10 min is more preferable. If the MFR (230 ° C., 2.16 kg) is less than 0.1 g / 10 minutes, the fluidity at the time of melting may be insufficient, and the melt kneading with the thermoplastic elastomer (A) may be insufficient. If it is 10 g / 10 min or more, the local elongation of the non-foamed sheet tends to increase.
The tan δ of the modified polypropylene resin (B) is preferably 2.0 or less, particularly preferably 1.5 or less, and most preferably 1.3 or less. If tan δ is greater than 2.0, the effect of reducing the local elongation of the sheet tends to be small.

  Examples of the conjugated diene compound (b) include butadiene, isoprene, 1,3-heptadiene, 2,3-dimethylbutadiene, 2,5-dimethyl-2,4-hexadiene and the like. These may be used alone or in combination of two or more. Among these, butadiene and isoprene are preferable, and isoprene is more preferable from the viewpoint that the reaction is easily progressed uniformly in the reaction for modifying (a), is easy to handle, and is inexpensive.

  The amount of the conjugated diene compound (b) is preferably 0.01 parts by weight or more and 20 parts by weight or less, and 0.05 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the linear polypropylene resin (a). Further preferred. If the amount of (b) is less than 0.01 parts by weight, the reforming effect is small, and if it exceeds 20 parts by weight, the effect is small and the cost is high compared to the amount added.

  As the radical polymerization initiator (c), peroxides, azo compounds and the like are generally used, but those having a capability of extracting hydrogen from a polypropylene resin or the conjugated diene compound are preferable. Generally, ketone peroxides and peroxyketals are used. And organic peroxides such as hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and peroxyester. Of these, those having particularly high hydrogen abstraction ability are preferred, such as 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, Peroxyketals such as n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, dicumyl peroxide, 2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butylperoxide, 2,5-dimethyl Diacyl peroxides such as dialkyl peroxides such as -2,5-di (t-butylperoxy) -3-hexyne and benzoyl peroxides Xide, t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxyisopropyl carbonate Peroxyesters such as 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, and di-t-butylperoxyisophthalate. It is done. These may be used alone or in combination of two or more.

  The amount of the radical polymerization initiator (c) is preferably 0.01 parts by weight or more and 10 parts by weight or less, and 0.05 parts by weight or more and 4 parts by weight or less with respect to 100 parts by weight of the linear polypropylene resin (a). Is more preferable. If the addition amount of the radical polymerization initiator is less than 0.01 parts by weight, the modification effect may be difficult to obtain. If the addition amount exceeds 10 parts by weight, the decomposition reaction of the linear polypropylene resin proceeds extremely. There is a case.

  Monomers copolymerizable with the conjugated diene compound include vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, acrylic acid. Metal salts, metal methacrylate salts, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid esters such as 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid 2 -Methacrylic acid esters such as ethylhexyl and stearyl methacrylate may be used, and these may be used in combination with the conjugated diene compound.

Examples of the production method of (B) include a method in which the conjugated diene compound (b) and the radical polymerization initiator (c) are added to the linear polypropylene resin (a) and melt-kneaded.
It is considered that the main chain decomposition reaction of the linear polypropylene (a) does not easily occur due to the conjugated diene compound (b), and a reaction that causes a branched structure in the linear polypropylene (a) occurs.

  In the production method of (B), the order of addition when melt-kneading the linear polypropylene resin (a), the conjugated diene compound (b), and the radical polymerization initiator (c) is (a) (b) (c ) May be batch melt-kneaded, or (a) and one other may be mixed and then melt-kneaded, and the remaining raw materials may be added and further melt-kneaded. Further, (b) and (c) may be added simultaneously or separately to the molten state (a) and melt kneaded. Moreover, the amount to be added may be added all at once or in divided portions. However, it is preferable to avoid kneading for a long time in a state where only (b) is added to (a) in the molten state because the decomposition reaction described above may proceed extremely.

  (B) as a production apparatus, a roll, a kneader, a Banbury mixer, a brabender, a single-screw extruder, a kneader such as a twin-screw extruder, a biaxial surface renewal machine, a horizontal agitator such as a biaxial multi-disc apparatus; Vertical type stirrers such as a double helical ribbon stirrer can be mentioned. Among these, it is preferable to use a kneader such as a roll, a kneader, a Banbury mixer, a brabender, a single screw extruder, a twin screw extruder, etc., and an extruder such as a single screw extruder or a twin screw extruder is particularly produced. From the viewpoint of sex.

The melt kneading temperature may be selected from the viewpoint that the linear polypropylene resin (a) is sufficiently melted and does not thermally decompose. Further, the reaction proceeds in a short time by increasing the temperature, but if it is too high, the reaction may not be uniform, which is not preferable. Generally, it is 130 degreeC or more and 300 degrees C or less, More preferably, it is 160 degreeC or more and 250 degrees C or less.
The melt kneading time is 1 to 60 minutes.

  In order to remove the unreacted conjugated diene compound (b) and the radical polymerization initiator (c), it is preferable to vent.

  As the shape and size of the modified polypropylene-based resin (B), a granular material such as a pellet or flake is preferable from the viewpoint of handleability in a subsequent process.

<Thermoplastic resin (C)>
Moreover, the resin composition for non-foamed sheets of the present invention may contain a thermoplastic resin or rubber (C) that does not fall under (A) or (B), or an additive, as long as the effects of the present invention are not impaired. . Examples of the thermoplastic resin (C) include poly α-olefins such as polyethylene, polypropylene polybutene-1, polyisobutene, polypentene-1, polymethylpentene-1, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, Ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / maleic anhydride copolymer, ethylene / metal acrylate copolymer, ethylene / methacrylic acid Metal salt copolymer, ethylene / vinyl monomer copolymer such as ethylene / glycidyl methacrylate copolymer; polydiene copolymer such as polybutadiene, polyisoprene; acrylonitrile / butadiene / styrene graft copolymer, methacrylic acid Methyl / butadiene / styrene Vinyl monomer such as raft copolymer / diene monomer / vinyl monomer graft copolymer; polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, ethyl polyacrylate, polybutyl acrylate Vinyl polymers such as polymethyl methacrylate and polystyrene; vinyl copolymers such as vinyl chloride / acrylonitrile copolymer, vinyl chloride / vinyl acetate copolymer, acrylonitrile / styrene copolymer, methyl methacrylate / styrene copolymer Examples thereof include polymers.

  Examples of the additives include fluidity improvers such as lubricants and polyolefin waxes; antioxidants, metal deactivators, phosphorus processing stabilizers, ultraviolet absorbers, light stabilizers, fluorescent whitening agents, metal soaps, Stabilizers such as acid adsorbents; additives such as crosslinking agents, chain transfer agents, nucleating agents, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, antistatic agents; softening mineral oils, paraffin oils, etc. An agent may be used in combination. The amount to be added is 0 to 25 parts by weight with respect to 100 parts by weight of the resin composition for non-foamed sheet.

<Non-foamed sheet>
As a method for producing a non-foamed sheet of the present invention, when preparing a sheet, both pellets are dry blended using a blender, a mixer, etc., and then a sheet is formed, or once melt-kneaded before sheet forming Then, after preparing mixed pellets, a method of forming a sheet can be mentioned. In the present invention, a method of molding after dry blending is preferable because a heat history is small and deterioration of the resin can be suppressed.

  Examples of the method for producing a non-foamed sheet of the present invention include calender molding, T-die extrusion molding, inflation molding, press molding, injection molding, and the like. From the viewpoint of productivity, calender molding or T-die extrusion molding is preferable.

  The thickness of the non-foamed sheet is preferably from 0.1 to 5 mm, particularly preferably from 0.3 to 3 mm.

  The surface of the non-foamed sheet of the present invention may be subjected to printing or a texture pattern as necessary. The wrinkle pattern is preferably a wrinkle pattern such as a leather pattern, a geometric pattern, or a background pattern. Examples of how to apply a texture pattern include a method of pressing a texture roll when extruding a non-foamed sheet, and a method of using a textured mold for injection molding.

  The non-foamed sheet of the present invention may be used as it is. Further, it is further processed by a thermoforming method and suitably used as various molded products. Examples of the thermoforming method include a heat stretching method, a heat press method, a pressure forming method, and a vacuum forming method.

  Since the non-foamed sheet of the present invention is excellent in melt elongation, local elongation is suppressed in thermoforming including the thermoforming, and the thickness of the molded product can be made uniform. In addition, when the surface has a texture pattern, local deformation of the texture pattern (texture flow) can be suppressed. The degree of deformation of the wrinkle flow can be determined by visually observing the non-foamed sheet molded article and the variation in glossiness. When the wrinkle pattern is deformed, fine irregularities on the ridgeline of the wrinkle pattern are broken and the glossiness is increased.

  The non-foamed sheet and the molded body thereof of the present invention can be suitably used as automobile parts, particularly automobile interior materials. In addition to automobile parts, it can be used in a wide range of applications such as building materials and home appliance parts.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples. In the following examples and comparative examples, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively.

<MFR>
MFR is extruded from the die at a load of 230 ° C. and 2.16 kg for a certain time using a melt indexer S-01 (manufactured by Toyo Seiki Seisakusho) in accordance with the provisions of Method A described in JIS K 7210 (1999). It was set as the value converted into the amount extruded from a resin amount in 10 minutes.

<Loss tangent (tan δ)>
The modified polypropylene resin (B) is hot-pressed at 190 ° C. for 5 minutes using a 1.5 mm-thick spacer to produce a 1.5 mm-thick press plate, and punched from there with a 25 mmφ punch. A test piece was obtained. As a measuring device, a viscoelasticity measuring device ARES made by TA Instruments was used, and a parallel plate type jig of 25 mmφ was attached. A thermostat was set up to surround the jig, kept at 180 ° C., and after the jig was preheated, the thermostat was opened, a test piece of 25 mmφ was inserted between the parallel plates, the thermostat was closed, and preheated for 5 minutes. Later, the parallel plate spacing was compressed to 1 mm. After compression, the thermostat was opened again, the resin protruding from the parallel plate was scraped off with a brass spatula, the thermostat was closed and the temperature was kept again for 5 minutes, and then dynamic viscoelasticity measurement was started.

  The measurement was performed in the range of angular frequency from 0.1 rad / s to 100 rad / s, and storage elastic modulus and loss elastic modulus at each angular frequency and loss tangent tan δ were obtained as calculated values. Among these results, the value of loss tangent tan δ at an angular frequency of 1 rad / s was adopted. The amount of strain was 5%, and the measurement was performed in a nitrogen atmosphere.

<Length and thickness of each part after elongation of non-foamed sheet>
As shown in FIG. 1, the non-foamed sheet was cut into a width of 40 mm and a length of 120 mm, a line was drawn at a position of 20 mm from the end in the length direction and the width direction, and the length direction was divided into 8 at 10 mm intervals. For stretching the non-foamed sheet, both ends of the sheet were fixed with clips, and heated in a furnace set at 130 ° C. for 3 minutes. Thereafter, the film was stretched to 150% at a stretching speed of 200 mm / min and held in a furnace for 1 minute. While being fixed to the clip, it was taken out from the furnace and cooled until it returned to room temperature to prepare a non-foamed sheet molded body.

  After stretching by 150%, the length of each part W1 to W8 and the thickness of the center position of each part W1 to W8 were measured and the average value, standard deviation σ, and standard deviation / average value were calculated. The film thickness was measured using an upright gauge (digital type) manufactured by Mitutoyo Corporation (scale: 0.001 mm, probe: flat probe).

<Glossiness evaluation of non-foamed sheet>
For the glossiness, the portion between W1 to W2, W4 to W5, and W7 to W8 (A to C in the figure) among the eight divided portions was measured, and the average value, standard deviation σ, and standard deviation / average value were calculated. It was measured with a gloss meter (manufactured by Nippon Denka Co., Ltd., VG2000).

<Evaluation of the texture pattern of the non-foamed sheet> The texture pattern was confirmed visually. The evaluation criteria are shown below.
Unevenness on the edge of the wrinkle pattern is clear: ◎
There is a slightly unclear part on the ridgeline of the wrinkle pattern: ○
There is a part where the irregularities on the ridgeline of the wrinkle pattern are unclear:
There is an uneven part on the edge of the wrinkle pattern: ×
Next, resins used in Examples and Comparative Examples will be described.

<Thermoplastic elastomer (A)>
(A-1) Propylene-ethylene copolymer (propylene content 60% by weight):
MFR (230 ° C., 2.16 kg) 2 g / 10 min, density 0.88 g / cm ³
<Modified polypropylene resin (B)>
(B-1) Synthesized in Production Example 1. MFR (230 ° C., 2.16 kg) 3.2 g / 10 min, tan δ (200 ° C., 1 rad / s) = 1.2
<Linear polypropylene resin (a)>
(A-1) Propylene homopolymer:
MFR (230 ° C., 2.16 kg) 8 g / 10 min, density 0.90 g / cm ³
(A-2) Propylene homopolymer:
MFR (230 ° C., 2.16 kg) 3 g / 10 min, density 0.91 g / cm ³
<Production Example 1>
A mixture of 100 parts by weight of (a-1) as the linear polypropylene resin (a) and 0.65 parts by weight of t-butylperoxyisopropyl carbonate as a radical polymerization initiator at a cylinder temperature of 200 ° C. at 70 kg / hour from the hopper. , Melt-kneaded with a twin-screw extruder (46 mmφ, L / D = 63, manufactured by Kobe Steel) set at a screw speed of 230 rpm, and isoprene monomer as a conjugated diene compound from a press-fitting part provided in the middle using a metering pump 0.45 parts by weight was supplied. A modified polypropylene resin (B-1) was obtained by melt-kneading in a biaxial extruder and water-cooling and chopping the extruded strand (melt flow rate 3.2 g / 10 min, tan δ 1.2). .

<Example 1>
After dry blending the propylene-ethylene copolymer (A-1) and the modified polypropylene resin (B-1) obtained in Production Example 1 at a ratio of 80:20, an injection molding machine (Toyo Machine Metal Industries 100 ton) Molding was performed by a molding machine (electric type). As molding conditions, cylinder set temperature: 220/220/220/200/180 ° C., mold used: 150 mm square plate, wall thickness 2 mm, with three-sided texture, mold set temperature: 40 ° C., injection speed: 100 mm / sec Cooling time: 30 sec
The evaluation results of the obtained non-foamed sheet are shown in Table 1, Table 2, and Table 3.

<Example 2>
The same procedure as in Example 1 was performed except that the mixing ratio of (A-1) and (B-1) was 90:10. The evaluation results of the obtained non-foamed sheet are shown in Table 1, Table 2, and Table 3.

<Example 3>
The same procedure as in Example 1 was performed except that the mixing ratio of (A-1) and (B-1) was 95: 5. The evaluation results of the obtained non-foamed sheet are shown in Table 1, Table 2, and Table 3.

<Comparative Example 1>
The same procedure as in Example 1 was performed except that the mixing ratio of (A-1) and (a-2) was 80:20. The evaluation results of the obtained non-foamed sheet are shown in Table 1, Table 2, and Table 3.

<Comparative example 2>
The same procedure as in Example 1 was performed except that the mixing ratio of (A-1) and (a-2) was 90:10. The evaluation results of the obtained non-foamed sheet are shown in Table 1, Table 2, and Table 3.

<Comparative Example 3>
The same procedure as in Example 1 was performed except that the mixing ratio of (A-1) and (a-2) was 95: 5. The evaluation results of the obtained non-foamed sheet are shown in Table 1, Table 2, and Table 3.

<Comparative example 4>
(A-1) The same procedure as in Example 1 was conducted except that the content was changed to 100% by weight. The evaluation results of the obtained non-foamed sheet are shown in Table 1, Table 2, and Table 3.

Claims (6)

A resin composition for a non-foamed sheet comprising a thermoplastic elastomer (A) and a conjugated diene-modified polypropylene resin (B),
The thermoplastic elastomer (A) is an ethylene-propylene copolymer that exhibits rubber elasticity at room temperature,
The conjugated diene modified polypropylene resin (B) is a melt-kneaded product of the linear polypropylene resin (a), the conjugated diene compound (b) and the radical polymerization initiator (c),
MFR (230 ° C., 2.16 kg) of the conjugated diene-modified polypropylene resin (B) is 0.1 to 10 g / 10 minutes,
Loss tangent (tan δ) at an angular frequency of 1 rad / s in dynamic viscoelasticity measurement at 200 ° C. of the conjugated diene-modified polypropylene resin (B) is 2.0 or less ,
The total of (A) and (B) contained in the non-foamed sheet resin composition is 100 parts by weight, the thermoplastic elastomer (A) is 80 to 95 parts by weight, and the modified polypropylene resin (B) is 5 to 20 parts by weight. Part
The resin composition for non -foamed sheets, wherein the non-foamed sheet is further processed by a thermoforming method . The resin composition for non-foamed sheets according to claim 1, wherein the thermoplastic elastomer (A) satisfies the following 1) to 3).
1) MFR (230 ℃, 2.16kg ) is 0.1 to 10 g / 10 min 2) density of 0.85 g / cm ³ or more 0.88 g / cm ³ or less 3) propylene content is 50 wt% or more The total of (A) and (B) contained in the resin composition for non-foamed sheet is 100 parts by weight, 90 to 95 parts by weight of the thermoplastic elastomer (A), and 5 to 10 parts by weight of the modified polypropylene resin (B). The resin composition for non-foamed sheets according to claim 1, wherein the resin composition comprises a part. The non-foamed sheet obtained from the resin composition for non-foamed sheets in any one of Claims 1-3 . A non-foamed sheet molded body obtained by thermoforming the non-foamed sheet according to claim 4 . A non-foamed sheet molded article according to claim 5 , wherein the non-foamed sheet molded article is for automobile parts.

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