JP2019065276A - Polypropylene resin composition - Google Patents

Abstract

To provide a polypropylene resin composition capable of providing an extrusion sheet for heat molding, excellent in transparency and excellent in drawdown resistance or stretchability at good moldability.SOLUTION: There is provided a polypropylene resin composition (X) containing 100 pts.mass of a resin composition (A) containing a polypropylene resin (A-1) and 1 to 40 pts.mass of an alicyclic hydrocarbon resin (B) having softening temperature of 70°C to 160°C, in which the resin composition (A) satisfies following requirements (a1) and (a2), the polypropylene resin composition (X) satisfies a following requirement (x1). (a1) melt flow rate (230°C, 2.16 kg load) (MFR(A)) is 40 g/10 min or less. (a2) strain hardening index λ is 1.1 or more. (x1) isothermal crystallization time of the polypropylene resin composition (X) (t(X)) (sec.) calculated by a differential thermal scanning type calorimeter (DSC) satisfies a following Formula (x-1). t(X)/t(A)>1.00 Formula (x-1).SELECTED DRAWING: None

Description

  The present invention relates to a polypropylene-based resin composition, and more particularly, to a polypropylene-based resin composition which can obtain a thermoforming sheet which is excellent in transparency and excellent in drawdown resistance and spreadability.

  Thermoforming sheets are representative of packaging containers such as food containers, transport containers for semiconductors and electronic parts, housing members, insert molding and in-mold molding by thermoforming represented by vacuum forming, pressure forming, and vacuum pressure forming. It is secondarily processed into a molded article suitable for each application such as a decorative member.

  As a resin for forming the sheet, non-crystalline resin such as polystyrene, ABS or acrylic excellent in thermoforming property is used, but polypropylene resin is used for applications requiring heat resistance, solvent resistance and electrical insulation. Often.

  As the polypropylene resin used for the thermoforming sheet, a propylene homopolymer or a propylene-α-olefin random copolymer is often used from the viewpoint of heat resistance, rigidity and the like. However, since these resins have a low melt tension, they tend to cause a so-called draw-down phenomenon in which the sheet sags greatly at the time of preheating in the secondary forming of the sheet. When the drawdown is large, defects such as generation of wrinkles in the secondary molded product and ignition in contact with a heat medium for heating the sheet occur. In general, since drawdowns increase in proportion to the size of a sheet, improvement of drawdown resistance is particularly important when forming large sized secondary products.

  In order to improve the drawdown resistance, generally, a method using polypropylene having a low melt flow rate (MFR) is known. However, if the MFR is too low, although the drawdown resistance is improved, sharkskin and screw marks tend to be generated during sheet formation, and sheet formability is deteriorated. In addition, as the sheet size increases, there is a limit in improving the drawdown resistance.

  Also, as another method of improving drawdown resistance, a method of blending low density polyethylene having a high melt viscosity or polyethylene of high molecular weight with a polypropylene resin is known, but heat resistance and transparency are significantly deteriorated. , There is a limit to the use.

  In order to eliminate these disadvantages, for example, a method of improving the drawdown resistance by extending the molecular weight distribution by two-stage polymerization of polypropylene having different molecular weights (see, for example, Patent Document 1) or polypropylene having a wide molecular weight distribution A method to be used (see, for example, Patent Document 2) has been proposed, but since the molecular weight difference between the low molecular weight component and the high molecular weight component is large, the high molecular weight component tends to be poorly dispersed and fish eyes are generated during sheet formation , Was of low commercial value.

  A thermoforming sheet (see, for example, Patent Document 3) in which a polypropylene resin is incorporated with a polypropylene resin having a long-chain branched structure as a method for improving drawdown resistance without occurrence of fish eyes has been proposed. . Since this sheet is excellent in drawdown resistance and spreadability, the uneven thickness of the molded product obtained by secondarily processing the sheet is uniform, and the buckling strength is excellent.

JP-A-55-123637 Unexamined-Japanese-Patent No. 6-93034 Unexamined-Japanese-Patent No. 2017-2229

However, a resin composition containing a polypropylene resin having a long-chain branched structure such as a polypropylene-based resin composition described in Patent Document 3 has a problem of moldability such that it is difficult to form a film, and an obtained thermoformed extrusion sheet The problem is that the transparency of the
In view of the above situation, according to the present invention, a polypropylene-based resin composition which is excellent in transparency and is excellent in drawdown resistance and spreadability can be obtained with a moldability with a resin composition containing a specific polypropylene resin. It aims at providing a resin composition.

  As a result of intensive researches to solve the above-mentioned problems, the present inventors have found that a polypropylene-based resin composition containing a specific resin composition containing a polypropylene-based resin and a specific alicyclic hydrocarbon resin is crystallized. It has been found that the sheet is excellent in sheet formability, the obtained sheet is excellent in transparency, and excellent in drawdown resistance and spreadability at the time of thermoforming.

The polypropylene resin composition of the present invention is an alicyclic hydrocarbon resin having a softening temperature of 70 ° C. to 160 ° C. with respect to 100 parts by mass of the resin composition (A) containing a polypropylene resin (A-1) B) A polypropylene resin composition (X) containing 1 to 40 parts by mass, which is
The resin composition (A) satisfies the following requirements (a1) and (a2),
The polypropylene resin composition (X) is characterized by satisfying the following requirement (x1).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) is 40 g / 10 min or less.
(A2) The degree of strain hardening λ is 1.1 or more.
(X1) The isothermal crystallization time (t (X)) (seconds) of the polypropylene resin composition (X) determined by a differential scanning calorimeter (DSC) satisfies the following formula (x-1).
t (X) / t (A)> 1.00 ... Formula (x-1)
(In the above formula, t (A) is the isothermal crystallization time (seconds) of the resin composition (A) measured at a temperature 10 ° C. higher than the crystallization start temperature (Tc (A)) of the resin composition (A) T (X) is the isothermal crystallization time (seconds) of the polypropylene resin composition (X) measured at a temperature 10 ° C. higher than the crystallization start temperature (Tc (A)) of the resin composition (A) is there.)

In the polypropylene resin composition of the present invention, the resin composition (A) may satisfy the following requirements (a1 ′) to (a2 ′).
(A1 ') MFR (A) is 30 g / 10 minutes or less.
(A2 ') The strain hardening degree λ is 1.3 or more.

In the polypropylene resin composition of the present invention, the resin composition (A) may satisfy the following requirements (a1 ′ ′) to (a2 ′ ′).
(A1 ′ ′) MFR (A) is 20 g / 10 min or less.
(A2 ′ ′) The strain hardening degree λ is 1.5 or more.

  In the polypropylene resin composition of the present invention, the polypropylene resin (A-1) may be a polypropylene resin (A-1-1) having a long chain branched structure.

  In the polypropylene resin composition of the present invention, the polypropylene resin (A-1-1) may be a polypropylene resin produced by a method other than the crosslinking method.

  The extruded sheet for thermoforming of the present invention has the above-mentioned polypropylene resin composition.

  The method for producing a thermoformed extruded sheet according to the present invention is a step of extruding the polypropylene resin composition in a molten state and cooling and solidifying it into a sheet shape in the production of the thermoformed extruded sheet, one side or both sides of the sheet, It is characterized in that it is pressed and solidified by cooling with a metal belt or an elastic metal roll.

  The molded article of the present invention is a thermoformed article of the extruded sheet for thermoforming.

  The polypropylene resin composition of the present invention is easy to form into a sheet because crystallization is suppressed. In addition, because oriented crystallization of the polypropylene resin is suppressed, a sheet excellent in transparency can be obtained while maintaining the heat resistance, the solvent resistance, and the electrical insulation characteristic of the polypropylene resin. Furthermore, since it is excellent in drawdown resistance and spreadability in secondary forming of a sheet, a large-sized molded object excellent in uneven thickness and shaping property can be manufactured.

The polypropylene resin composition of the present invention is an alicyclic hydrocarbon resin having a softening temperature of 70 ° C. to 160 ° C. with respect to 100 parts by mass of the resin composition (A) containing a polypropylene resin (A-1) B) A polypropylene resin composition (X) containing 1 to 40 parts by mass, which is
The resin composition (A) satisfies the following requirements (a1) and (a2),
The polypropylene resin composition (X) is characterized by satisfying the following requirement (x1).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) is 40 g / 10 min or less.
(A2) The degree of strain hardening λ is 1.1 or more.
(X1) The isothermal crystallization time (t (X)) (seconds) of the polypropylene resin composition (X) determined by a differential scanning calorimeter (DSC) satisfies the following formula (x-1).
t (X) / t (A)> 1.00 ... Formula (x-1)
(In the above formula, t (A) is the isothermal crystallization time (seconds) of the resin composition (A) measured at a temperature 10 ° C. higher than the crystallization start temperature (Tc (A)) of the resin composition (A) T (X) is the isothermal crystallization time (seconds) of the polypropylene resin composition (X) measured at a temperature 10 ° C. higher than the crystallization start temperature (Tc (A)) of the resin composition (A) is there.)

Hereinafter, modes for carrying out the present invention will be described in detail.
The polypropylene-based resin composition (X) of the present invention is a resin composition in which a specific amount of an alicyclic hydrocarbon resin (B) is blended with a resin composition (A) containing a polypropylene-based resin (A-1). is there.

[Resin composition (A)]
The resin composition (A) contains at least a polypropylene resin (A-1), and optionally contains another polypropylene resin (C).
When the resin composition (A) is composed only of the polypropylene resin (A-1), the polypropylene resin (A-1) satisfies the requirements (a1) and (a2) described later.
When the resin composition (A) is composed of a blend of a polypropylene resin (A-1) and another polypropylene resin (C), it is added to the resin composition (A) and at least a polypropylene resin (A-). It is preferable that 1) satisfy requirements (a1) and (a2) described later.
The blend of the polypropylene-based resin (A-1) and the other polypropylene-based resin (C) is not particularly limited, and may be a mixture of pellets and / or powder, a melt blend, or a solution blend, It may be a combination.

(A1) MFR (A)
Even if the resin composition has the strain hardening property described later, the resin composition (A) needs to have a certain viscosity because sufficient molding stability can not be obtained if the viscosity is too low, and in the present specification, The MFR (230 ° C., 2.16 kg load) is defined as an index of this viscosity.

In the present specification, MFR (230 ° C., 2.16 kg load) of the resin composition (A) is referred to as MFR (A). MFR (A) fulfills the following requirement (a1), preferably fulfills requirement (a1 ′), more preferably fulfills requirement (a1 ′ ′) MFR (A) of resin composition (A) By making the value or less, a sheet with a good appearance can be obtained.
(A1) MFR (A) is 40 g / 10 min or less (a1 ') MFR (A) is 30 g / 10 min or less (a1'') MFR (A) is 20 g / 10 min or less

  The lower limit of the MFR (A) of the resin composition (A) is not particularly limited, but is preferably 0.1 g / 10 minutes or more, and more preferably 0.3 g / 10 minutes or more. By making MFR (A) more than said value, the moldability at the time of sheet manufacture can be improved, and it can suppress that the appearance defect called a shark skin or a screw mark generate | occur | produces on the sheet surface.

  In this specification, measurement of MFR of polypropylene resin (A-1), other polypropylene resin (C), and resin composition (A) conforms to ISO 1133: 1997 Conditions M, 230 ° C., 2. Measure under the condition of 16 kg load. The unit is g / 10 minutes.

(A2) Strain hardening degree λ
The strain hardening degree of the resin composition (A) satisfies the following requirement (a2), preferably satisfies the requirement (a2 ′), and more preferably satisfies the requirement (a2 ′ ′) Strain of the resin composition (A) By setting the degree of curing to a value within the following range, a sheet having good drawdown resistance and spreadability can be obtained.
(A2) Strain hardening degree λ is 1.1 or more (a2 ′) Strain hardening degree λ is 1.3 or more (a2 ′ ′) Strain hardening degree λ is 1.5 or more

  The upper limit of the degree of strain hardening of the resin composition (A) is not particularly limited, but is preferably 50 or less, more preferably 20 or less. By setting the degree of strain hardening to a value in the above range, the appearance of a molded product obtained by thermoforming can be improved.

The strain hardening degree of a resin composition (A) is calculated | required based on the measurement of the strain hardening in extension viscosity measurement. For strain hardening (non-linearity) of elongational viscosity, see Lecture & Rheology, The Society of Rheology, edited by Polymer Society of Japan, 1992, pp. 221-222, and in the present specification, the strain hardening degree is calculated as a shear viscosity value by a method according to the determination method illustrated in FIGS. As 値^* (0.01), ηe (3.5) is adopted as the value of elongation viscosity, and the strain hardening degree λ is defined by the following formula (1).
λ = ηe (3.5) / {3 × η ^* (0.01)} Formula (1)
In the above equation (1), η ^* (0.01) is measured by a dynamic frequency sweep experiment, and the complex viscosity at a measurement temperature of 180 ° C. and an angular frequency ω = 0.01 rad / s [unit: Pa · s The complex viscosity η ^* is calculated from the complex elastic modulus G ^* [unit: Pa] and the angular frequency ω according to ^** = G ^* / ω. Further, η e (3.5) is the elongation viscosity at a measurement temperature of 180 ° C., a strain rate of 1.0 s ⁻¹ and a strain amount of 3.5 measured by elongation viscosity measurement.

Usually, data obtained by these visco-elasticity measurement is a collection of numerical values such as elastic modulus and viscosity at discrete frequencies or measurement time intervals.
Therefore, when the measurement is carried out using an apparatus or condition different from that used in the present invention, the complex viscosity η ^* (0.01) at an angular frequency ω = 0.01 and the elongation at a strain 3.5 are not necessarily required. There may be cases where data of viscosity 粘度 e (3.5) does not exist, in which case it is possible to estimate the corresponding value by performing interpolation such as linear interpolation and spline interpolation using data before and after that forgiven. When performing interpolation, it is the usual practice to use stress and time scales as logarithmic scales.

  At this time, the strain hardening degree λ shows a value of about 1 (for example, 0.9 or more and less than 1.1) or less than 1 if the sample has no strain hardening (nonlinearity) in the extension viscosity, and the strain hardening ( As the nonlinearity increases, the value of the strain hardening degree λ increases.

[Polypropylene-based resin (A-1)]
When the resin composition (A) is composed of only the polypropylene resin (A-1), the polypropylene resin (A-1) satisfies the requirements (a1) and (a2) described above.
When the resin composition (A) is composed of a blend of a polypropylene resin (A-1) and another polypropylene resin (C), at least a polypropylene resin (in addition to the resin composition (A) A-1) satisfies the requirements (a1) and (a2) described above.

(A3) Long-Chain Branched Structure Generally, crystalline polypropylene is a linear polymer and generally does not have strain hardening.
On the other hand, the polypropylene-based resin (A-1) used in the present invention is preferably a polypropylene-based resin (A-1-1) having a long chain branched structure, whereby the resin composition (A) It is possible to develop strain hardening.

  The long chain branched structure in the present invention refers to branching by a molecular chain consisting of several tens carbon atoms or more and several hundreds carbon atoms or more in molecular weight in the carbon skeleton (branch main chain) constituting the branch in order to exhibit strain hardening. Say the structure. This long chain branching structure is distinguished from short chain branching formed by copolymerization with an α-olefin such as 1-butene.

  As a method for introducing a long chain branched structure into a polypropylene-based resin, a method using high energy ionizing radiation (for example, JP-A-62-121704) or a method using an organic peroxide (for example, JP-A-2001-2001- Macromonomer copolymerization method (for example, JP-A-2001-525460) in which a long chain branched structure is formed by producing a macromonomer having a terminal unsaturated bond, and copolymerizing it with propylene. And the like, and the strain hardening degree of the polypropylene-based resin can be greatly improved even when manufactured using any method.

  The polypropylene-based resin (A-1-1) having a long chain branched structure is not particularly limited as long as it has a long chain branched structure, but has a comb-like chain structure and long chain branching during polymerization Those obtained by the macromonomer copolymerization method in which a structure is formed are preferable. Examples of such methods include, for example, JP-A-2001-525460, JP-A-10-338717, JP-A-2002-523575, JP-A-2009-57542, JP-A-05027353, and the like. The method disclosed in Japanese Patent Application Laid-Open No. 10-338717 can be mentioned. In particular, the macromonomer copolymerization method disclosed in JP 2009-57542 A is suitable for the present invention because it can produce a long chain branch-containing polypropylene resin without generating a gel.

Having a long chain branched structure in polypropylene is defined by a method based on the rheological properties of a resin, a method of calculating a branching index g 'using a relationship between molecular weight and viscosity, a method using ¹³ C-NMR, and the like. In the present invention, the presence or absence of a long chain branched structure is determined by a branching index g ′ and / or ¹³ C-NMR as described below.

(A4) Branching index g '
The branching index g 'is known as a direct indicator for long chain branching structures. Although a detailed description is given in "Developments in Polymer Characterization-4" (J. V. Dawkins ed. Applied Science Publishers, 1983), the definition of the branching index g 'is as follows.
Branching index g '= [η] br / []] lin
[Η] br: Intrinsic viscosity of polymer (br) having a long chain branched structure [η] lin: Intrinsic viscosity of linear polymer having the same molecular weight as the polymer (br) As apparent from the above definition, the branching index g 'is If the value is smaller than 1, it is judged that a long chain branched structure exists, and the value of the branching index g 'becomes smaller as the long chain branched structure increases.

The branching index g 'can be obtained as a function of the absolute molecular weight Mabs by using GPC with a light scatterometer and viscometer on the detector. About the measuring method of branching index g 'in this invention, although details are described in Unexamined-Japanese-Patent No. 2015-40213, it is as follows.
[Measuring method]
GPC: Alliance GPCV 2000 (manufactured by Waters)
Detector: described in the order of connection Multi-angle laser light scattering detector (MALLS): DAWN-E (manufactured by Wyatt Technology)
Differential Refractometer (RI): attached to GPC Viscosity detector (Viscometer): attached to GPC Mobile phase solvent: 1,2,4-trichlorobenzene (Irganox 1076 added at a concentration of 0.5 mg / mL)
Mobile phase flow rate: 1 mL / min Column: Tosoh GMHHR-H (S) Two HTs connected Sample injection temperature: 140 ° C
Column temperature: 140 ° C
Detector temperature: All 140 ° C
Sample concentration: 1 mg / mL
Injection volume (sample loop volume): 0.2175 mL

[analysis method]
Data processing included with MALLS to determine absolute molecular weight (Mabs), root mean square radius of inertia (Rg) obtained from multi-angle laser light scattering detector (MALLS), and intrinsic viscosity ([η]) obtained from Viscometer The software ASTRA (version 4.73.04) is used, and calculations are performed with reference to the following documents.
References:
1. "Developments in Polymer Characterization-4" (J.V. Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004)
3. Macromolecules, 33, 2424-2436 (2000)
4. Macromolecules, 33, 6945-6952 (2000)

  In the polypropylene-based resin composition (X) of the present invention, when the polypropylene-based resin (A-1) contains a gel, the sheet appearance is deteriorated, so a resin composition (A) containing no gel It is preferable to use That is, the polypropylene resin (A-1-1) having a long chain branched structure is preferably a polypropylene resin produced by a method other than the crosslinking method, and more preferably a polypropylene resin having a small amount of gel. In particular, a method of producing a macromonomer having a terminal unsaturated bond and forming a long chain branched structure by copolymerizing with propylene as the polypropylene resin (A-1-1) having a long chain branched structure described above The one manufactured using is preferred. In particular, those described below and having a branching index g ′ at an absolute molecular weight Mabs of 1,000,000 and satisfying 0.3 or more and less than 1.0 are preferable, more preferably 0.55 or more and 0.98 or less, further preferably 75 or more and 0.96 or less, and most preferably 0.78 or more and 0.95 or less. When the branching index g 'is in this range, the appearance of the sheet is not deteriorated because highly crosslinked components are not formed and there is no or very little gel formation.

[ ¹³ C-NMR]
As described above, ¹³ C-NMR can distinguish short chain branched structures from long chain branched structures. Macromol. Chem. Phys. 2003, vol. The detailed description is given in 204 and 1738, but the outline is as follows.

The propylene-based polymer having a long chain branched structure has a specific branched structure as shown in the following structural formula (1). In structural formula (1), Ca, Cb, and Cc represent methylene carbon adjacent to a branched carbon, Cbr represents methine carbon at the base of branched chain, P ¹ , P ² , and P ³ represent propylene-based heavy chain The combined residue is shown.

The propylene-based polymer residues P ¹ , P ² and P ³ may contain, in themselves, another branched carbon (Cbr) other than Cbr described in the structural formula (1).

Such branched structures are identified by ¹³ C-NMR analysis. Assignment of each peak is described in Macromolecules, Vol. 35, no. 10. 2002, pages 3839-3842 can be referred to. That is, a total of three methylene carbons (Ca, Cb, Cc) are observed at 43.9 to 44.1 ppm, 44.5 to 44.7 ppm and 44.7 to 44.9 ppm, respectively, 31.5 Methine carbon (Cbr) is observed at ̃31.7 ppm. The methine carbon observed in the above 31.5 to 31.7 ppm may be abbreviated as branched methine carbon (Cbr) hereinafter.

  It is characterized in that three methylene carbons adjacent to the branched methine carbon Cbr are observed as being divided into three nonequivalently to the diastereotopic.

Such a branched chain assigned by ¹³ C-NMR indicates a propylene-based polymer residue having 5 or more carbon atoms branched from the main chain of the propylene-based polymer, and the branch having 4 or less carbon atoms is branched The presence of a long chain branched structure can be determined by identifying the peak of the branched methine carbon in the present invention, since the carbon can be distinguished by the difference in the peak position of carbon.
The measurement method of ¹³ C-NMR in the present invention is as follows.

[ ¹³ C-NMR measurement method]
An NMR sample with an inner diameter of 10 mmφ with 200 mg of sample together with 2.4 ml of o-dichlorobenzene / deuterated brominated benzene (C ₆ D ₅ Br) = 4/1 (volume ratio) and hexamethyldisiloxane which is a standard substance of chemical shift It was placed in a tube and dissolved, and ¹³ C-NMR measurement was performed.
^{The 13} C-NMR measurement was performed using an AV400M NMR apparatus manufactured by Bruker Biospin Ltd. equipped with a 10 mmφ cryoprobe.
The measurement was carried out by the proton complete decoupling method at a temperature of 120 ° C. of the sample. Other conditions are as follows.
Pulse angle: 90 °
Pulse interval: 4 seconds Integration number: 20000 The chemical shift was set with the methyl carbon peak of hexamethyldisiloxane as 1.98 ppm, and the chemical shifts of the peaks due to other carbons were based on this.
The peak around 44 ppm can be used to calculate the amount of long chain branching.

The ¹³ C-NMR spectrum of the polypropylene resin (A-1-1) having a long chain branching structure has a long chain branching quantity quantified from a peak at around 44 ppm being at least 0.01 / 1000 total propylene Preferably, it is more preferably 0.03 pieces / 1000 total propylene or more, still more preferably 0.05 pieces / 1000 total propylene or more. If this value is too large, it may cause appearance defects such as gel and fish eye, so it is preferably 1.00 / 1000 total propylene or less, more preferably 0.50 / 1000 total propylene or less, more preferably 0. .30 pieces / 1000 total propylene or less.

  The polypropylene resin (A-1-1) having such a long chain branched structure is sufficient to impart strain curability to the resin composition (A) containing the polypropylene resin (A-1). It is good if the amount is included. The polypropylene resin (A-1-1) is contained in preferably 100% by mass, more preferably 5% by mass or more, in 100% by mass of the resin composition (A).

  The polypropylene resin (A-1) used in the present invention is various types such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene block copolymer (block polypropylene), etc. The propylene-based polymer of (1) or a combination thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of a propylene monomer.

(A5) Melting point The polypropylene resin (A-1) used in the present invention preferably has high crystallinity from the viewpoint of heat resistance and solvent resistance. The melting point (DSC melting peak temperature) of the polypropylene resin (A-1) is preferably 140 ° C. or more, more preferably 145 to 170 ° C., and further preferably 150 to 168 ° C. The polypropylene resin (A-1) is preferably a propylene homopolymer or a propylene-α-olefin copolymer having such a melting point.

[Other polypropylene-based resin (C)]
In the present invention, the other polypropylene resin (C) has a feature different from the polypropylene resin (A-1) by satisfying at least the following (c1). Moreover, the other polypropylene resin (C) may further satisfy at least any one of the following requirements (c2) to (c5).
(C1) The strain hardening degree λ is less than 1.1.
(C2) does not have a long chain branched structure.
(C3) The branching index g 'is 0.95 or more.
(C4) MFR (C) is 0.1 g / 10 minutes or more and 100 g / 10 minutes or less.
(C5) The melting point is 115 ° C. or more and 175 ° C. or less.
In addition, since the measuring method of the said requirements is the same as the method as described in the resin composition (A) and polypropylene resin (A-1) mentioned above, description here is abbreviate | omitted.

When the resin composition (A) is a blend of a polypropylene resin (A-1) and another polypropylene resin (C), the polypropylene resin (A-1) and the other polypropylene resin (C) The mass ratio of polypropylene resin (A-1): other polypropylene resin (C) = 1 to 99: 99 to 1 is preferable, and polypropylene resin (A-1): other polypropylene resin (C) = 2 to 88: 98 to 12 is more preferable.
The degree of strain hardening λ of the other polypropylene resin (C) may be less than 1.1, preferably 0.8 or more and less than 1.1.
Other polypropylene-based resins (C) include various types of propylene-based polymers such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), and propylene block copolymer (block polypropylene). Coalescence or a combination thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of a propylene monomer.

[Alicyclic hydrocarbon resin (B)]
The alicyclic hydrocarbon resin (B) is considered to be a component having a function of delaying the crystallization of the resin composition (A) by containing the resin composition (A). By delaying the crystallization rate of the resin composition (A), it is considered that solidification at the time of sheet formation can be delayed to facilitate film formation.
In addition, the alicyclic hydrocarbon resin (B), when contained in the resin composition (A), has the effect of delaying the orientational crystallization of the resin composition (A) caused by shear deformation or extension deformation during extrusion molding. Since it is considered to be present, it is considered that the increase in the degree of crystallinity of the sheet is suppressed and the effect of improving the transparency of the sheet is high. About the effect which delays crystallization of a resin composition (A), it evaluated by the isothermal crystallization time of the polypropylene resin composition (X) mentioned later.

  The softening temperature of the alicyclic hydrocarbon resin (B) is preferably 70 ° C. or more and 160 ° C. or less, more preferably 75 ° C. or more and 155 ° C. or less, and still more preferably 80 ° C. or more and 150 ° C. or less. When the softening temperature is in the above range, a polypropylene resin composition (X) having good moldability and transparency can be obtained. The softening temperature is measured by JIS K2207: 1996 (ring and ball method).

  The alicyclic hydrocarbon resin (B) is obtained, for example, by polymerizing a mixture of one or two or more kinds of dicyclopentadiene derivatives such as dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene or the like as a main raw material Hydrocarbon resins, hydrogenated coumarone / indene resin, hydrogenated C9 petroleum resin, hydrogenated C5 petroleum resin, C5 / C9 copolymer petroleum resin, hydrogenated terpene resin, hydrogenated rosin resin, etc., and Commercially available products can be used, and specific examples include Alcon series manufactured by Arakawa Chemical Co., Ltd.

[Polypropylene resin composition (X)]
The polypropylene resin composition (X) in the present invention comprises the resin composition (A) and the alicyclic hydrocarbon resin (B) as main components, and the resin composition (A) and the alicyclic hydrocarbon It may be a mixture with the resin (B) or may be a melt-kneaded product.
In the present invention, "main component" means a component that occupies 50% by mass or more of the entire material. When the entire polypropylene resin composition (X) is 100% by mass, the total of the resin composition (A) and the alicyclic hydrocarbon resin (B) may be 50% by mass or more.

  In the polypropylene resin composition (X), 1 to 40 parts by mass of the alicyclic hydrocarbon resin (B) needs to be contained with respect to 100 parts by mass of the resin composition (A), and preferably 3 to 35 mass It is a department. When it is in the above range, sheet formation becomes easy and orientation crystallization of the resin composition (A) is suppressed, so that the transparency of the sheet is improved.

(X1) Isothermal crystallization time (t (X))
In the polypropylene resin composition (X), the isothermal crystallization time (t (X)) (seconds) of the polypropylene resin composition (X) determined by differential scanning calorimetry (DSC) is represented by the following formula (x- It is necessary to satisfy 1).
t (X) / t (A)> 1.00 ... Formula (x-1)
(In the above formula (x-1), t (A) is measured at a temperature 10 ° C. higher than the crystallization initiation temperature (Tc (A)) of the resin composition (A). Isothermal crystallization of the resin composition (A) Is time (second), and t (X) is the isothermal crystallization of polypropylene resin composition (X) measured at a temperature 10 ° C. higher than the crystallization initiation temperature (Tc (A)) of resin composition (A) Time (seconds)
When the isothermal crystallization time (t (X)) of the polypropylene resin composition (X) is in the above range, sheet formation becomes easy, and the effect of suppressing the orientation crystallization of the resin composition (A) is high. , Improve the transparency of the sheet.
The upper limit of the isothermal crystallization time (t (X)) is not particularly limited, but from the viewpoint of sheet formability, t (X) / t (A) is preferably 30 or less, more preferably 15 or less, and 10 or less More preferably, 5 or less is particularly preferred.

(Measurement of isothermal crystallization time by differential scanning calorimeter (DSC))
The isothermal crystallization time in the present invention is a value measured using a differential scanning calorimeter (DSC), and is based on JIS-K 7121 "Method for measuring transition temperature of plastic".

  Specifically, 5 mg of the sample is placed in an aluminum holder and the temperature is raised from 40 ° C. to 200 ° C. at a rate of 10 ° C./min in a nitrogen atmosphere. After holding at 200 ° C. for 10 minutes, crystallization is performed at a temperature decrease rate of 10 ° C./minute up to 40 ° C., and the crystallization initiation temperature (Tc (A)) is measured and calculated from the DSC curve at this time.

  Next, 5 mg of a sample of the resin composition (A) or the polypropylene resin composition (X) is placed in an aluminum holder, and the temperature is raised from 40 ° C. to 200 ° C. at a rate of 10 ° C./min. After holding for 10 minutes, the temperature is raised to 40 ° C. up to a temperature 10 ° C. higher than the crystallization initiation temperature (Tc (A)) of the resin composition (A) determined by the method described above (hereinafter sometimes referred to as “measurement temperature”). The sample is cooled at a rate of / min and then kept at the measurement temperature to measure the behavior of crystallization and heat generation of the sample. The time from when the temperature of the sample reaches the measurement temperature until the exothermic peak top time is taken as isothermal crystallization time. When there are two or more exothermic peaks in the isothermal crystallization measurement, the time until the top of the first exothermic peak is taken as isothermal crystallization time.

  Additives, fillers, colorants, and other resin components may be added to the polypropylene resin composition (X) as long as the effects of the present invention are not impaired. However, the total amount of additives, fillers, colorants and other resin components is preferably 50% by mass or less with respect to the polypropylene resin composition (X).

  Additives can be used for polypropylene resins such as antioxidants, neutralizing agents, light stabilizers, ultraviolet light absorbers, crystal nucleating agents, antiblocking agents, lubricants, antistatic agents, metal deactivators, etc. Various known additives can be blended.

Examples of the antioxidant include phenol-based antioxidants, phosphite-based antioxidants, and thio-based antioxidants.
As a neutralizing agent, higher fatty acid salts such as calcium stearate and zinc stearate can be exemplified.
Examples of light stabilizers and ultraviolet light absorbers include hindered amines, benzotriazoles, benzophenones and the like.

  Examples of crystal nucleating agents include metal amides of aromatic carboxylic acids, metal salts of aromatic phosphates, sorbitol derivatives, metal salts of rosin, and amide nucleating agents. Among these crystal nucleating agents, aluminum p-t-butylbenzoate, phosphoric acid 2,2'-methylenebis (4,6-di-t-butylphenyl) sodium, phosphoric acid 2,2'-methylenebis (4) , 6-di-t-butylphenyl) aluminum, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphospho A complex of aluminum (6-hydroxyl) hydroxide and an organic compound, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis- [ Examples include (4-propylphenyl) methylene] -nonitol, sodium salts of rosin and the like.

As the lubricant, higher fatty acid amides such as stearic acid amide can be exemplified.
As an antistatic agent, fatty acid partial esters, such as glycerol fatty acid monoester, etc. can be illustrated.
Examples of metal deactivators include triazines, phosphones, epoxies, triazoles, hydrazides, oxamides and the like.

As the filler, various known fillers that can be used for polypropylene resins, such as inorganic fillers and organic fillers, can be blended.
Examples of the inorganic filler include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, carbon fiber and the like.
Further, as the organic filler, crosslinked rubber fine particles, thermosetting resin fine particles, thermosetting resin hollow fine particles and the like can be exemplified.

  As other resin components, modifiers, such as an elastomer which can be added to propylene resin, polyethylene resin, etc. can be added suitably.

Among the above other resin components, as an elastomer, an ethylene-α-olefin copolymer, a binary random copolymer resin of propylene and an α-olefin having 4 to 12 carbon atoms, propylene and ethylene and 4 to 4 carbon atoms Mention may be made of ternary random copolymer resins with 12 alpha-olefins.
Furthermore, styrenic elastomers can also be added, and as styrenic elastomers, they can be appropriately selected from commercially available ones and used, for example, Kraton as a hydrogenated substance of styrene-butadiene block copolymer Polymer Japan Co., Ltd. under the trade name "Kraton G" and Asahi Chemicals Co., Ltd. under the trade name "Tuftec" as a hydrogenated product of styrene-isoprene block copolymer from Kuraray Co., Ltd. "Septon Under the trade name “Hybrid” from Kuraray Co., Ltd. as a hydrogenated substance of styrene-vinylated polyisoprene block copolymer, and JSR Co., Ltd. as a hydrogenated substance of styrene-butadiene random copolymer under the trade name “Hybuller” from Kuraray Co., Ltd. The product is sold under the trade name of “Dynaron” and is selected appropriately from these product groups. It may be used.

Further, among the above-mentioned other resin components, as the polyethylene resin, ethylene-α-olefin copolymers such as low density polyethylene and linear low density polyethylene can be mentioned, and the density thereof is 0.860 to 0.910 g / it is preferably in the range of cm ^3, more preferably 0.870~0.905g / cm ^3, further preferably 0.875~0.895g / cm ^3. If the above range is exceeded, the transparency may be reduced.
The density is a value measured at 23 ° C. in accordance with JIS K7112.

The α-olefin used for the ethylene-α-olefin copolymer is preferably an α-olefin having 3 to 18 carbon atoms. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1,4,4-dimethylpentene- 1 mag can be mentioned. Moreover, as an alpha-olefin, 1 type, or 2 or more types of combinations may be sufficient.
Examples of the ethylene-α-olefin copolymer include ethylene-based elastomers and ethylene-propylene-based rubbers. In particular, an ethylene-α-olefin copolymer called metallocene-type polyethylene, which is produced using a metallocene-based catalyst with less reduction in transparency, is suitable.

  Moreover, it is also possible to color in order to provide design property, and various coloring agents, such as an inorganic pigment, an organic pigment, dye, can be used for coloring. In addition, bright materials such as aluminum flakes, titanium oxide flakes and (synthetic) mica can also be used.

  The method for producing a polypropylene-based resin composition (X) comprises melt-kneading the resin composition (A), an alicyclic hydrocarbon resin (B), an additive, a filler, a colorant, other resin components and the like Method of dry blending or melt-kneading an alicyclic hydrocarbon resin (B) in a resin composition (A) and an additive, a filler, a coloring agent, and other resin components melt-kneaded, resin composition A method of dry blending or melt-kneading a masterbatch in which (A) is added to an alicyclic hydrocarbon resin (B), and additives, fillers, colorants, other resin compositions, etc. are dispersed in a carrier resin at a high concentration. And so on.

[Sheet]
The sheet having the polypropylene resin composition (X) of the present invention is a sheet comprising the main layer using at least the polypropylene resin composition (X) of the present invention, and even if it is a single layer sheet, two or more layers It may be a multilayer structure of
In the multilayer sheet, in addition to the main layer using the polypropylene resin composition (X), a surface layer, a surface decoration layer, a printing layer, a light shielding layer, a colored layer, a barrier layer, and a tie layer which can be provided between these layers Layers can be included.
In addition, a surface treatment agent such as an antifogging agent, an antistatic agent, or a lubricant may be applied to one side or both sides of the sheet.

  The thickness of the sheet having the polypropylene resin composition (X) of the present invention is preferably 0.02 mm to 4 mm, more preferably 0.04 mm to 3.5 mm, and particularly preferably 0.05 mm to 3 mm. When the thickness of the sheet is in this range, sheet formation is easy, and a sheet having excellent transparency can be obtained.

  The sheet having the polypropylene resin composition (X) of the present invention can be produced by various known molding methods. Examples of known methods include T-die, extrusion using a circular die, and the like.

As a method of cooling a molten sheet extruded from a die, a metal roll such as an air knife, an air chamber, a rubber roll, a stainless steel belt, a steel roll, etc. on the surface of a metal roll in which cooling water or oil circulates. There is a method of pressing by a flexible elastic metal roll or the like while having a metal roll or a metal surface to cool and solidify it, and a method of cooling and solidify by sandwiching it with a metal belt such as a pair of stainless steel belts.
In the production of the sheet by extrusion molding, in the step of extruding the polypropylene resin composition (X) of the present invention in a molten state and cooling and solidifying it into a sheet, a mirror-like elastic metal roll or metal belt is applied to the sheet surface It is possible to improve the transparency of the sheet by transferring and mirror-finishing, or by bringing an elastic metal roll or metal belt having high heat exchange properties into contact and rapidly solidifying it, so one side or both sides of the sheet can be obtained. Is preferably pressed with a metal belt or an elastic metal roll to cool and solidify.

[Molded body]
The formed body of the present invention can be obtained as a thermoformed body by forming the above-mentioned sheet by thermoforming such as vacuum forming, pressure forming, vacuum pressure forming, or plug-assisted vacuum pressure forming. As a heating method in such thermoforming, indirect heating, hot plate heating, hot roll heating, etc. may be mentioned.

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.

1. Measurement method of various physical properties (i) Melt flow rate (MFR)
In accordance with ISO 1133: 1997 Conditions M, it was measured at 230 ° C. under a 2.16 kg load. The unit is g / 10 minutes.

(Ii) melting peak temperature (melting point: Tm)
The melting peak temperature is raised to 200 ° C. and held for 10 minutes using a differential scanning calorimeter (DSC), and then the temperature is dropped to 40 ° C. at a temperature lowering rate of 10 ° C./min. The temperature of the endothermic peak top when measured in ° C./min was taken as the melting peak temperature. The unit is ° C.

(Iii) Isothermal crystallization time The isothermal crystallization time was measured by the above-mentioned method using a differential scanning calorimeter (DSC).
When the isothermal crystallization time of the polypropylene resin composition (X) is to be measured, the resin composition (A) and the alicyclic hydrocarbon resin (B) are melt-kneaded with a twin-screw extruder, Pellets of the resin composition (X) were obtained and used to measure the isothermal crystallization time.

(Iv) Strain hardening degree λ
The strain hardening degree λ was determined by the method described above.
At this time, η ^* (0.01) used as the shear viscosity value and ηe (3.5) used as the extension viscosity value were measured by the following method.
Moreover, the sample used for measurement at this time was formed into a flat plate of 0.7 mm and 2 mm in thickness by pressing for 1 hour under conditions of a temperature of 180 ° C. and a pressure of 10 MPa, and a sample of 0.7 mm in thickness A 2 mm sample was used for dynamic frequency sweep experiments for elongational viscosity measurement.

(Iv-1) Shear viscosity ^** (0.01)
Dynamic frequency sweep experiments were performed using ARES manufactured by Rheometric Scientific.
A 25 mm diameter parallel disk was used for the measurement geometry.
The measurement was performed in the measurement mode Dynamic Frequency Sweep Test using the device control software TA Orchestrator.
The sample used the press-formed body of thickness 2 mm created by said method.
The measurement temperature was 180 ° C.
The angular frequency ω was measured at five points per digit so as to be equally spaced on a logarithmic scale between 0.01 and 100 rad / s.
The complex viscosity 粘度^* (0.01) [unit: Pa · s] at ω = 0.01 rad / s was adopted as an index indicating the viscosity at a low shear rate of the sample. The complex viscosity η ^* is calculated from the complex elastic modulus G ^* [unit: Pa] and ω by η ^* = G ^* / ω.

(Iv-2) extensional viscosity η e (3.5)
Elongation viscosity measurement was performed using a measurement instrument of ARES manufactured by Rheometric Scientific, using an Extensional Viscosity Fixture manufactured by TA Instruments.
The measurement was performed in the measurement mode Extensional Viscosity Test using the device control software TA Orchestrator.
The sample used the test piece of thickness 0.7mm shape | molded by said method.
The test piece had a width of 10 mm and a length of 18 mm.
The strain rate was 1.0 s ⁻¹ and the measurement temperature was 180 ° C.
Other measurement parameters were set as follows.
Sampling Mode: log
Points Per Zone: 200
Solid Density: 0.9
Melt Density: 0.8
Prestretch Rate: 0.05 s ⁻¹
Relaxation after Prestretch: 30 sec
Under this condition, collect data at least up to 3.7 seconds from the start of measurement. The software provides time dependent data of extensional viscosity. The value of the extensional viscosity at the time of 3.5 seconds (that is, strain amount 3.5) of the obtained extensional viscosity curve was taken as ηe (3.5) [unit: Pa · s].

(V) Measurement of the branching index g 'at an absolute molecular weight Mabs of 1,000,000:
According to the method described above, measurement was performed using GPC equipped with a light scattering meter and a viscometer in the detector, and the branching index g ′ was determined based on the analysis method described above.

(Vi) Detection of long chain branched structure using ¹³ C-NMR:
According to the method described above, measurement using ¹³ C-NMR was performed to determine the presence or absence of a long chain branched structure.

(Vii) Measurement of softening temperature:
The softening temperature of the alicyclic hydrocarbon resin (B) was measured in accordance with JIS K2207: 1996 (ring and ball method). The unit is ° C.

2. Materials used (1) Polypropylene resin (A-1)
The following polypropylene resins were used.
Polypropylene resin (A-1-1a): Propylene homopolymer having long chain branching produced by macromonomer copolymerization method, manufactured by Nippon Polypro Co., Ltd., trade name "WAYMAX (registered trademark) MFX6", MFR = 2 g / 10 min, strain hardening degree λ = 8.3, Tm = 154 ° C., branch index g ′ = 0.88 at an absolute molecular weight Mabs of 1,000,000, having a long chain branch structure by measurement of ¹³ C-NMR Confirmation.
Polypropylene resin (A-1-1b): Propylene homopolymer having long-chain branching produced by macromonomer copolymerization method, manufactured by Nippon Polypro Co., Ltd., trade name “WAYMAX® MFX3”, MFR = 8.8 g / 10 min, strain hardening degree λ = 7.8, Tm = 154 ° C., branching index g ′ = 0.85 at an absolute molecular weight Mabs of 1,000,000 and having a long chain branched structure by measurement of ¹³ C-NMR Confirm that.
Polypropylene resin (A-1-1c): Propylene homopolymer having long chain branching produced by macromonomer copolymerization method, manufactured by Nippon Polypro Co., Ltd., trade name "WAYMAX (registered trademark) MFX8", MFR = 1.0 g / 10 min, strain hardening degree λ = 9.7, Tm = 154 ° C., branching index g ′ = 0.89 at an absolute molecular weight Mabs of 1,000,000 and having a long chain branching structure by measurement of ¹³ C-NMR Confirm that.

(2) Other polypropylene resins (C)
The following other polypropylene resins were used.
Polypropylene resin (C-1): Propylene homopolymer, manufactured by Nippon Polypropylene Corporation, trade name "Novatec (registered trademark) FL4", MFR = 4.6 g / 10 min, strain hardening degree λ = 0.9, It confirmed that it did not have a long chain branched structure by the measurement of Tm = 163 degreeC and ¹³ C-NMR.
Polypropylene resin (C-2): Propylene homopolymer, manufactured by Nippon Polypropylene Corporation, trade name "Novatec (registered trademark) FY 6", MFR = 2.4 g / 10 min, strain hardening degree λ = 0.9, It confirmed that it did not have a long chain branched structure by the measurement of Tm = 161 degreeC and ¹³ C-NMR.
Polypropylene resin (C-3): Propylene-α-olefin copolymer, manufactured by Nippon Polypropylene Corporation, trade name “Novatec (registered trademark) FW3GT”, MFR = 7.0 g / 10 min, strain hardening degree λ = 0.9, Tm = 146 ° C., ¹³ C-NMR measurement confirmed that the product had no long chain branched structure.

(3) Alicyclic hydrocarbon resin (B)
The following alicyclic hydrocarbon resin was used.
Alicyclic hydrocarbon resin (B-1): alicyclic hydrocarbon resin: manufactured by Arakawa Chemical Co., Ltd., trade name "Alcon-P125", softening temperature = 125 ° C.
Alicyclic hydrocarbon resin (B-2): alicyclic hydrocarbon resin: manufactured by Arakawa Chemical Co., Ltd., trade name "Alcon-P100", softening temperature = 100 ° C.
Alicyclic hydrocarbon resin (B-3): alicyclic hydrocarbon resin: manufactured by Arakawa Chemical Co., Ltd., trade name "Alcon-P140", softening temperature = 140 ° C.

(4) Other resin (D)
The following resins were used.
(D-1): Hydrogenated styrenic elastomer (HSBR): manufactured by JSR Corporation, trade name "Dynalon 1320P"

Example 1
Production of resin composition (A) 10% by mass of a polypropylene resin (A-1-1a) having a long chain branched structure, and 90% by mass of another polypropylene resin (C-1) After stirring and mixing for 3 minutes with a Henschel mixer, the mixture is melt-kneaded with a twin-screw extruder, and the molten resin extruded from the strand die is taken out while cooling and solidifying in a cooling water tank, The resin composition (A) was obtained by cutting into 3 mm and a length of about 2 mm.
In addition, the screw rotation speed is 300 rpm and the kneading temperature is C1 / C2 / C3 to C7 / head from the bottom of the hopper using a “KZW-25” twin screw extruder manufactured by Technobel Co., Ltd. with a screw diameter of 25 mm for the twin screw extruder /Dies=150.degree. C./180.degree. C./230.degree. C./230.degree. C./230.degree.
The obtained resin composition (A) has MFR (A) = 3.8 g / 10 min, strain hardening degree λ = 1.9, crystallization temperature Tc (A) = 125 ° C., isothermal crystallization time t (A) ) = 233 seconds.

Production of polypropylene resin composition (X) 100 parts by mass of the obtained resin composition (A) is blended with 10 parts by mass of an alicyclic hydrocarbon resin (B-1) to obtain a Henschel mixer The mixture was stirred and mixed for 3 minutes and then melt-kneaded with a twin-screw extruder, and the molten resin extruded from the strand die was pulled out while being cooled and solidified in a cooling water tank, and the strand was about 3 mm in diameter and long using a strand cutter. The polypropylene resin composition (X) was obtained by cutting into pieces of about 2 mm.
As a twin-screw extruder, a “KZW-15” twin-screw extruder manufactured by Technobel Co., Ltd. with a screw diameter of 25 mm was used, and polypropylene resin composition (X) was produced under the same conditions as the production of resin composition (A). I made it.
The obtained polypropylene resin composition (X) had an isothermal crystallization time t (X) = 307 seconds, and exceeded 1.00 with t (X) / t (A) = 1.32.

-Production of sheet A single-layer T-die with a lip opening of 0.7 mm and a die width of 330 mm, to which a 35 mm diameter (diameter) extruder was connected, was used. The polypropylene resin composition (X) was charged into the extruder, and melt extrusion was performed under the conditions of a resin temperature of 260 ° C. and a discharge amount of the extruder of 11.5 kg / h. The melt-extruded sheet was cooled and solidified while pressed against a first roll rotating at 6 m / min at 10 ° C. with an air knife to obtain a 100 μm-thick monolayer evaluation sheet for transparency evaluation. In addition, the temperature of the first roll was changed to 30 ° C., and the rotational speed was changed to 2 m / min, to obtain a 300 μm-thick single-layer sheet for thermoformability evaluation.

· Physical property evaluation (1) Transparency (internal haze)
It measured based on JIS-K7136: 2000 using the 100-micrometer-thick single layer sheet obtained by sheet forming mentioned above.
The internal haze is a flow of 2 slides from the haze value (%) measured in a state in which a film coated with liquid paraffin on both surfaces is sandwiched between two slides of 1.3 mm thickness. It is measured by subtracting the haze value (%) measured in a state of being in close contact with paraffin. In addition, it means that it is opaque, so that the obtained value is large. The internal haze value considered to be good in transparency is 6% or less, preferably 5% or less, more preferably 4% or less.

(2) Sheet Formability The solidified state of the sheet at the time of forming a single-layer sheet having a thickness of 300 μm was visually observed and evaluated based on the criteria shown below.
:: The ear does not warp even when in contact with the air of the ear holder, the adhesion to the roll is good, the sheet is uniformly cooled, and the transparency of the entire sheet is uniform.
X: Solidification occurs due to contact with air of the ear clamp, and the ear curls back to the ear clamp side, solidification of the sheet starts before roll contact, adhesion to the roll is poor, and crystallization occurs unevenly And the sheet is partially cloudy.

(3) Drawdown Resistance A test piece of 280 mm × 280 mm in size was cut out from the 300 μm thick single layer sheet obtained by the sheet molding described above, and was fixed horizontally to a frame of inner size 260 mm × 260 mm. Lead to the heating furnace in the tester where the heaters are arranged up and down using a dripping tester manufactured by Misuzu Erie and heated at an ambient temperature of 200 ° C, and change over time of the vertical displacement of the central part of the sample from the start of heating Was measured by a laser beam.
With heating, the sheet sags once (displacement in the negative direction), recoils by stress relaxation (displacement in the positive direction), and then sags again by its own weight. The sheet position (displacement) at the start of heating is A (mm), the maximum tension return position (displacement) is B (mm), and the position (displacement) 10 seconds after the maximum tension return is C (mm). The downability was evaluated according to the criteria shown below.
:: B-A ≧ -5 mm and C-B ≧ -10 mm
X: B-A <-5 mm and / or C-B <-10 mm
Here, that B−A−5−5 mm means that the sheet is tensioned during thermoforming and a beautiful appearance without wrinkles can be formed, and that C−BB−10 mm is good. This means that the molding time range for obtaining such a molded body is sufficiently wide.
The physical property evaluation results of the obtained composition and sheet are shown in Table 1.
Since t (X) / t (A) exceeded 1.32 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 2)
In the production of the resin composition (A) of Example 1, the compounding ratio of the polypropylene resin (A-1-1a) having a long chain branched structure and the other polypropylene resin (C-1) is 20:80. Evaluation was performed in the same manner as in Example 1 except that the conditions were changed as described above. The evaluation results are shown in Table 1.
Since t (X) / t (A) exceeded 1.30 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 3)
In the production of the polypropylene resin composition (X) of Example 2, the compounding amount of the alicyclic hydrocarbon resin (B-1) was changed to 5 parts by mass with respect to 100 parts by mass of the resin composition (A) Evaluation was performed in the same manner as Example 2 except for the above. The evaluation results are shown in Table 1.
Since t (X) / t (A) exceeded 1.10 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 4)
Example of Example 2 except that in the production of the sheet of Example 2, a dry blend of 5 parts by mass of another resin (D-1) was added to 100 parts by mass of the polypropylene resin composition (X) in an extruder. Evaluation was performed in the same manner as 2. The evaluation results are shown in Table 1.
Since t (X) / t (A) exceeded 1.30 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Comparative example 1)
In the production of the resin composition (A) of Example 1, only the other polypropylene resin (C-1) is used, and in the production of the polypropylene resin composition (X), the alicyclic hydrocarbon resin (B-) is used. Evaluation was performed in the same manner as Example 1 except that 1) was not blended. The results are shown in Table 1.
Since the polypropylene resin (A-1-1) which has a long chain branched structure is not contained in the resin composition (A), it was a result inferior to drawdown resistance.

(Comparative example 2)
Evaluation was performed in the same manner as in Example 2 except that the alicyclic hydrocarbon resin (B-1) was not blended in the production of the polypropylene resin composition (X) of Example 2. The results are shown in Table 1.
Since the alicyclic hydrocarbon resin (B-1) is not contained, t (X) / t (A) is 1.00, crystallization is fast, transparency is inferior, and sheet formability is inferior. It was the result.

(Comparative example 3)
In the production of the polypropylene resin composition (X) of Example 2, the compounding amount of the alicyclic hydrocarbon resin (B-1) was changed to 50 parts by mass with respect to 100 parts by mass of the resin composition (A) Evaluation was performed in the same manner as Example 2 except for the above. The results are shown in Table 1.
The melt resin was melt-kneaded with a twin-screw extruder, and it was tried to cool the molten resin extruded from the strand die with a cooling water bath, but because the solidification time was long, it could not be fed into the cutter in a strand state and pellets were obtained I could not.

(Example 5)
In the production of the resin composition (A) of Example 1, the compounding ratio of the polypropylene resin (A-1-1a) having a long chain branched structure to the other polypropylene resin (C-1) is 5:95. Evaluation was performed in the same manner as in Example 1 except that the conditions were changed as described above. The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.24 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 6)
In the production of the polypropylene resin composition (X) of Example 2, the compounding amount of the alicyclic hydrocarbon resin (B-1) was changed to 15 parts by mass with respect to 100 parts by mass of the resin composition (A) Evaluation was performed in the same manner as Example 2 except for the above. The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.33 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 7)
In the production of the polypropylene resin composition (X) of Example 2, the compounding amount of the alicyclic hydrocarbon resin (B-1) was changed to 30 parts by mass with respect to 100 parts by mass of the resin composition (A) Evaluation was performed in the same manner as Example 2 except for the above. The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.87 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 8)
In the production of the resin composition (A) of Example 1, the compounding ratio of the polypropylene resin (A-1-1a) having a long chain branched structure and the other polypropylene resin (C-1) is 30:70. Evaluation was performed in the same manner as in Example 1 except that the conditions were changed as described above. The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.31 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 9)
In the production of the resin composition (A) of Example 1, the compounding ratio of the polypropylene resin (A-1-1a) having a long chain branched structure and the other polypropylene resin (C-1) is 50: 50. Evaluation was carried out in the same manner as in Example 1 except that the above was changed. The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.30 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 10)
In the production of the resin composition (A) of Example 1, the compounding ratio of the polypropylene resin (A-1-1a) having a long chain branched structure to the other polypropylene resin (C-1) is 70:30. Evaluation was performed in the same manner as in Example 1 except that the conditions were changed as described above. The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.37 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 11)
In the production of the resin composition (A) of Example 1, evaluation was performed in the same manner as in Example 1 except that only a polypropylene resin (A-1-1a) having a long chain branched structure was used. The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.12 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 12)
Example 2 except that in the production of the resin composition (A) of Example 2, the polypropylene resin (A-1-1a) having a long chain branched structure is changed to a polypropylene resin (A-1-1b). The same evaluation was performed. The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.29 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 13)
Example 2 except that in the production of the resin composition (A) of Example 2, the polypropylene resin (A-1-1a) having a long chain branched structure is changed to a polypropylene resin (A-1-1c). The same evaluation was performed. The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.24 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 14)
The same as Example 2, except that in the production of the polypropylene resin composition (X) of Example 2, the alicyclic hydrocarbon resin (B-1) is changed to an alicyclic hydrocarbon resin (B-2) It was evaluated. The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.34 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 15)
The same as Example 2, except that in the production of the polypropylene resin composition (X) of Example 2, the alicyclic hydrocarbon resin (B-1) is changed to an alicyclic hydrocarbon resin (B-3) It was evaluated. The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.22 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 16)
In the production of the resin composition (A) of Example 2, evaluation was performed in the same manner as in Example 2 except that the other polypropylene resin (C-1) was changed to another polypropylene resin (C-2). The The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.27 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Example 17)
In the production of the resin composition (A) of Example 2, evaluation was performed in the same manner as in Example 2 except that the other polypropylene resin (C-1) was changed to another polypropylene resin (C-3). The The results are shown in Table 2.
Since t (X) / t (A) exceeded 1.17 and 1.00, it was a result excellent in transparency and sheet formability. Moreover, since the resin composition (A) satisfied all the requirements of the present invention, it was a result excellent in drawdown resistance.

(Comparative example 4)
Evaluation was performed in the same manner as in Example 2 except that only the other polypropylene resin (C-1) was used in the production of the resin composition (A) of Example 2. The results are shown in Table 2.
Since the polypropylene resin (A-1-1) which has a long chain branched structure is not contained in the resin composition (A), it was a result inferior to drawdown resistance.

  The polypropylene-based resin composition of the present invention suppresses crystallization, is excellent in sheet formability, and the obtained sheet is excellent in transparency and is excellent in drawdown resistance and spreadability at the time of thermoforming. It is extremely useful for the production of large-sized molded articles excellent in meat and moldability.

Claims (8)

Polypropylene containing 1 to 40 parts by mass of an alicyclic hydrocarbon resin (B) having a softening temperature of 70 ° C. to 160 ° C. with respect to 100 parts by mass of a resin composition (A) containing a polypropylene resin (A-1) Based resin composition (X),
The resin composition (A) satisfies the following requirements (a1) and (a2),
The polypropylene resin composition (X) satisfies the following requirement (x1).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) is 40 g / 10 min or less.
(A2) The degree of strain hardening λ is 1.1 or more.
(X1) The isothermal crystallization time (t (X)) (seconds) of the polypropylene resin composition (X) determined by a differential scanning calorimeter (DSC) satisfies the following formula (x-1).
t (X) / t (A)> 1.00 ... Formula (x-1)
(In the above formula, t (A) is the isothermal crystallization time (seconds) of the resin composition (A) measured at a temperature 10 ° C. higher than the crystallization start temperature (Tc (A)) of the resin composition (A) T (X) is the isothermal crystallization time (seconds) of the polypropylene resin composition (X) measured at a temperature 10 ° C. higher than the crystallization start temperature (Tc (A)) of the resin composition (A) is there.) The polypropylene resin composition according to claim 1, wherein the resin composition (A) satisfies the following requirements (a1 ') to (a2').
(A1 ') MFR (A) is 30 g / 10 minutes or less.
(A2 ') The strain hardening degree λ is 1.3 or more. The polypropylene resin composition according to claim 1, wherein the resin composition (A) satisfies the following requirements (a1 ′ ′) to (a2 ′ ′).
(A1 ′ ′) MFR (A) is 20 g / 10 min or less.
(A2 ′ ′) The strain hardening degree λ is 1.5 or more.   The polypropylene resin composition according to any one of claims 1 to 3, wherein the polypropylene resin (A-1) is a polypropylene resin (A-1-1) having a long chain branched structure.   The polypropylene resin composition according to claim 4, wherein the polypropylene resin (A-1-1) is a polypropylene resin produced by a method other than a crosslinking method.   The extruded sheet for thermoforming which has a polypropylene resin composition of any one of Claims 1-5.   In the production of the extruded sheet for thermoforming according to claim 6, in the step of extruding the polypropylene resin composition in a molten state and cooling and solidifying it into a sheet, one side or both sides of the sheet is formed by a metal belt or an elastic metal roll. A method for producing a thermoformed extruded sheet, characterized by pressing and cooling and solidifying.   A formed body which is a thermoformed body of the extruded sheet for thermoforming according to claim 6 or 7.