JP6459826B2 - Polypropylene resin laminate for thermoforming and molded body thereof - Google Patents

Description

  The present invention relates to a novel thermoforming polypropylene resin laminate and a molded body thereof.

  Polypropylene resins have a high melting point and are lightweight, and therefore can be applied to various applications. Conventionally, a polypropylene resin having a low MFR and a high melt tension has been used as a polypropylene resin for a sheet used in the production of a molded product by a thermoforming method such as a vacuum forming method or a pressure forming method. However, the sheet using such a polypropylene resin often has low gloss. In such a case, a sheet having an improved appearance defect can be obtained by using a mirror surface roll having an extremely smooth surface during extrusion molding. However, when the sheet thus obtained is thermoformed, a phenomenon such as so-called “glossy return” occurs in which the gloss is severely lowered compared with that before thermoforming. This is because the relaxation time of the polypropylene-based resin is long, so the residual stress of the sheet after extrusion molding becomes large, and the sheet surface becomes rough due to this residual stress during thermoforming. It is thought that there is.

  In order to improve gloss return, a laminated sheet obtained by laminating a polypropylene resin sheet as a base material layer and a polypropylene resin having a high MFR on the surface of the base material layer as a surface layer has been proposed (for example, Patent Documents 1 and 2). In these methods, a polypropylene resin having a high MFR has a short relaxation time, and during extrusion molding, the relaxation ends before the resin solidifies, so that the residual stress of the sheet after extrusion molding can be eliminated or reduced, Therefore, the effect of improving gloss return is recognized.

JP-A-2004-276240 JP 58-153643 A

  In recent years, the demand for thermoforming sheets and thermoformed bodies has increased further. For example, the relaxation time of the resin on the surface layer can be shortened so that extrusion molding can be performed at a higher speed, or deep drawing can be performed. Thus, studies have been made to increase the melt tension of the resin of the base material layer. However, as in Patent Documents 1 and 2, in the laminated sheet mainly focusing on the level of MFR of the resin, there is a problem that a lamination failure that is considered to be caused by the roughness of the interface between the base material layer and the surface layer occurs. Has occurred. When poor stacking occurs, wrinkles are generated on the surface of the sheet, and wrinkles are generated on the sheet after thermoforming.

  As described above, a polypropylene-based resin laminate having an improved appearance and improved appearance and an excellent appearance has not been found so far.

  In view of the present situation, an object of the present invention is to provide a polypropylene-based resin laminate that has a high gloss and an excellent appearance, in which gloss return does not easily occur and stacking failure does not easily occur.

  As a result of intensive studies, the inventors of the present invention have compatibility with the base material layer by using a polypropylene resin composition containing a polypropylene resin having a long-chain branched structure and having a specific MFR and melt tension as a surface layer. However, the present inventors have found that the above problems can be solved and have completed the present invention.

  That is, this invention is laminated | stacked on the single side | surface or both surfaces of the base material layer containing the polypropylene resin composition (A) which has the following characteristics (Ai)-(A-iii), and the following, And a surface layer containing a polypropylene resin composition (B) having the following characteristics (Bi) to (B-iii).

Characteristic (Ai): Polypropylene resin (X1) having a long-chain branched structure and / or MFR having a melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) of 0.1 to 15 g / 10 min. Is composed of a linear polypropylene resin (X2) having 0.1 to 3.0 g / 10 min and other polypropylene resin (X3) used as necessary.
Characteristic (A-ii): MFR (temperature 230 ° C., load 2.16 kg) is smaller than MFR of the polypropylene resin composition (B).
Characteristic (A-iii): Melt tension (MT) at 230 ° C. is 5 to 30 g.
Characteristic (Bi): It consists of a polypropylene resin (Y1) having a long-chain branched structure and another polypropylene resin (Y2) used as necessary.
Characteristic (B-ii): Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 3.0 to 100 g / 10 min.
Characteristic (B-iii): Melt tension (MT) at 230 ° C. is 1.0 g or more.

  According to the present invention, the polypropylene resin having a long chain branched structure exhibits a high melt tension. By applying this to the resin for the surface layer, the substrate layer and the surface are maintained while maintaining a high MFR. The difference in melt tension with the layer can be reduced, and the surface layer can be stably laminated. That is, it is possible not only to suppress the occurrence of “glossy return” during thermoforming, but also to improve poor stacking. Moreover, since the resin composition of the surface layer has a high MFR and a relaxation time is short, high gloss can be expressed.

  Another invention of the present invention is that the polypropylene-based resins (X1) and (Y1) having a long-chain branched structure have a branching index g ′ at an absolute molecular weight Mabs of 500,000 of 0.3 or more and less than 1.0. A polypropylene resin laminate for thermoforming as described above.

  According to the present invention, the polypropylene resins (X1) and (Y1) having a long-chain branched structure exhibit high melt tension and, in addition, little gel is generated, so that a laminate having a good appearance can be obtained. .

Another invention of the present invention is the above-described polypropylene-based resin laminate for thermoforming that contains a crystal nucleating agent in the surface layer.
According to the present invention, the crystal nucleating agent produces many fine spherulites when the resin is cooled, so that the gloss can be further increased.

  Another invention of the present invention is the above-described polypropylene resin laminate for thermoforming, wherein the total thickness of the surface layers is 1 to 50% with respect to the thickness of the laminate.

  According to this invention, since the base material layer with higher melt tension occupies more than half of the laminate, it is possible to suppress molding defects such as sag (drawdown) during heating and uneven thickness.

  Another invention of the present invention is the above-described polypropylene resin laminate for thermoforming in which the polypropylene resins (X1) and (Y1) have a long-chain branched structure formed during polymerization.

  According to this invention, the polypropylene resin having a long chain branching structure is a polypropylene resin having a comb chain structure, which is a long chain branching method without chemical or physical modification. The generation of gel is suppressed, and a laminate having an excellent appearance can be obtained.

  In another aspect of the present invention, the gloss of the surface layer is 80% or more, and the gloss of the surface layer when it is thermoformed into a molded product is 70% or more. Polypropylene resin laminate for use.

  By using a polypropylene resin composition containing a polypropylene resin (Y1) having a long-chain branched structure as a surface layer according to the present invention, a polypropylene resin containing a polypropylene resin having a high melt tension, a polypropylene resin having a low MFR, etc. Even with the base material layer made of the resin composition (A), it is possible to obtain a polypropylene-based resin laminate having high gloss and excellent appearance, in which glossy return hardly occurs and stacking failure hardly occurs. Since the laminate does not easily cause gloss return even after thermoforming, it is possible to provide a thermoformed article having high gloss and excellent appearance.

  Hereinafter, embodiments of the present invention will be described in detail.

  The polypropylene-based laminate for thermoforming of the present invention comprises a base material layer comprising a polypropylene resin composition (A) having the following characteristics (Ai) to (A-iii), and one surface of the base material layer or A polypropylene resin laminate for thermoforming, comprising a surface layer containing a polypropylene resin composition (B) having the following characteristics (Bi) to (B-iii) laminated on both surfaces.

Characteristic (Ai): Polypropylene resin (X1) having a long-chain branched structure and / or MFR having a melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) of 0.1 to 15 g / 10 min. Is composed of a linear polypropylene resin (X2) having 0.1 to 3.0 g / 10 min and other polypropylene resin (X3) used as necessary.
Characteristic (A-ii): MFR (temperature 230 ° C., load 2.16 kg) is smaller than MFR of the polypropylene resin composition (B).
Characteristic (A-iii): Melt tension (MT) at 230 ° C. is 5 to 30 g.
Characteristic (Bi): It consists of a polypropylene resin (Y1) having a long-chain branched structure and another polypropylene resin (Y2) used as necessary.
Characteristic (B-ii): Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 3.0 to 100 g / 10 min.
Characteristic (B-iii): Melt tension (MT) at 230 ° C. is 1.0 g or more.

1. Polypropylene resin composition (A)
The polypropylene resin composition (A) constituting the base material layer needs to satisfy the following properties (Ai) to (A-iii).

1.1. (Ai): Polypropylene resin to be used The polypropylene resin composition (A) used in the present invention is a polypropylene resin (X1) having a long chain branched structure having an MFR of 0.1 to 15 g / 10 min. ) And / or a linear polypropylene resin (X2) having an MFR of 0.1 to 3.0 g / 10 min and another polypropylene resin (X3) used as necessary. .

  Long-chain branching refers to a branched structure of a molecular chain consisting of several tens or more main chain carbon atoms and several hundred or more in molecular weight, and the number of carbons formed by copolymerization with an α-olefin such as 1-butene. A distinction is made from several short chain branches. A method for producing such a polypropylene resin is known to those skilled in the art (for example, JP-A-2015-40213). Specific synthesis examples are described in the following examples.

There are several methods for examining whether long-chain branching is present in polypropylene, but the method based on the rheological properties of the resin is easily used. As a stricter identification method, there are a method using the relationship between molecular weight and viscosity, a method using ¹³ C-NMR, and the like. For the latter, Macromol. Chem. Phys. 2003, vol. Refer to 204 and 1738 for detailed explanation. The branching index g ′ as a direct indicator that the polypropylene resin has a long-chain branch structure will be described later.

  The linear polypropylene resin is a general-purpose linear polypropylene resin known to those skilled in the art, and is not particularly limited. In addition to homopolymers, random copolymers and block copolymers with olefins such as ethylene. Includes coalescence. The linear polypropylene resin includes a polypropylene resin having no long chain branched structure.

  As the polypropylene resin (X1) having a long chain branched structure and the linear polypropylene resin (X2), a propylene homopolymer, a propylene / α-olefin random copolymer, a propylene / α-olefin block copolymer, Or a mixture thereof.

  Other polypropylene resin (X3) is not particularly limited as long as the polypropylene resin composition (A) satisfies (A-ii) and (A-iii), and MFR is 0.1 to 100 and MT is 0. 0.1 to 40 propylene homopolymer, propylene / α-olefin random copolymer, propylene / α-olefin block copolymer, or a mixture thereof (however, (X1), (X2), or ( X1) and (X2) are excluded). Examples of the α-olefin include ethylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1.

The contents of the polypropylene resin (X1) and the polypropylene resin (X2) are not particularly limited, but are preferably 10% by weight or more, more preferably 20% by weight or more, and further preferably 60% by weight or more. The upper limit is 100% by weight. By including these polypropylene-based resins, the melt tension of the polypropylene-based resin composition (A) is increased, dripping at the time of heating in thermoforming (drawing down), and the rising portion and the standing wall portion of the thermoformed body. Molding defects such as uneven thickness can be suppressed. If the MFR is within the above range, it has an appropriate melt viscosity, so that the moldability is good and the load on the extruder can be reduced. On the other hand, the content of the polypropylene resin (X3) is preferably 0 to 90% by weight, more preferably 0 to 80% by weight, and still more preferably 0 to 40% by weight.
When the polypropylene resin (X1) and the linear polypropylene resin (X2) are independent and satisfy (A-ii) and (A-iii), the polypropylene resin (X3) may be omitted.

1.2. Characteristic (A-ii): MFR
The melt flow rate (MFR) of the polypropylene resin composition (A) used in the present invention is smaller than the MFR of the polypropylene resin composition (B). The melt flow rate (MFR) of the polypropylene resin composition (A) is, for example, 0.05 to 80 g / 10 minutes, preferably 0.1 to 20 g / 10 minutes, more preferably 0.2 to 10 g / minute. 10 minutes, more preferably 0.3 to 10 g / 10 minutes. When the melt flow rate (MFR) of the polypropylene resin composition (A) is smaller than the MFR of the polypropylene resin composition (B), the surface layer has, for example, the function of enhancing gloss, without damaging the function. It is possible to effectively suppress the drooping (drawdown).

  Here, MFR is a value measured according to JIS K7210 at a heating temperature of 230 ° C. and a load of 21.2 N (2.16 kg).

1.3. (A-iii): MT
Further, the polypropylene resin composition (A) has a melt tension (MT) at 230 ° C. of 5 to 30 g by a melt tension tester. Here, MT is Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd. Capillary: Diameter 2.0 mm, Length 40 mm, Cylinder diameter: 9.55 mm, Cylinder extrusion speed: 20 mm / min, Take-off speed: 4.0 m / Min., Temperature: 230 ° C. The melt tension as measured is expressed in grams. The lower limit value is more preferably 7.0 g or more, and even more preferably 12 g or more. The upper limit is preferably 27 g or less, more preferably 25 g or less. If the melt tension is within the above range, drooping down during thermoforming can be effectively suppressed, so that a thermoformed body having both excellent molding process characteristics (for example, extensibility) and mechanical properties and a beautiful appearance can be obtained. I can do it.

2. Polypropylene resin composition (B)
The polypropylene resin composition (B) used in the present invention needs to satisfy the following characteristics (Bi) to (B-iii).

2.1. Characteristic (Bi): Polypropylene resin (Y1) having a long-chain branched structure
The polypropylene resin composition (B) used in the present invention needs to contain a polypropylene resin (Y1) having a long chain branched structure. The polypropylene resin (Y1) having a long chain branched structure is the same as the polypropylene resin (X1) described in item 1 above except for the MFR range, and will be described in item 3 below. Specific synthesis examples are also described in the following examples.

  The content of the polypropylene resin (Y1) having a long chain branched structure is not particularly limited, but is preferably 10% or more, and more preferably 20% or more. By including the polypropylene resin (Y1) having a long-chain branched structure, the difference in melt tension between the surface layer and the base material layer is reduced, and the compatibility between the surface layer and the base material layer is improved. It is possible to effectively suppress poor stacking such as rough interface with the layer.

  Other polypropylene resin (Y2) is not particularly limited as long as the polypropylene resin composition (B) satisfies (B-ii) and (B-iii), and MFR is 0.1 to 100 and MT is 0. 0.1 to 40 propylene homopolymer, propylene / α-olefin random copolymer, propylene / α-olefin block copolymer, or a mixture thereof (excluding cases corresponding to (Y1)) . Examples of the α-olefin include ethylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1. Preferable polypropylene resins (Y2) include linear propylene homopolymers, propylene / ethylene random copolymers, or propylene / ethylene block copolymers.

The content of the polypropylene resin (Y1) is not particularly limited, but it is preferably 10% by weight or more, more preferably 20% by weight or more, and further preferably 25% by weight or more. On the other hand, the content of the polypropylene resin (Y2) is preferably 0 to 90% by weight, more preferably 0 to 80% by weight, and still more preferably 0 to 75% by weight.
When the polypropylene resin (Y1) is alone and satisfies (B-ii) and (B-iii), the polypropylene resin (Y2) may be omitted. When the polypropylene resin (Y1) alone does not satisfy (B-ii) or (B-iii), a polypropylene resin composition can be obtained by using a specific MFR or MT polypropylene resin (Y2). The MFR and MT of (B) can be adjusted to a desired value.

2.2. Characteristic (B-ii): MFR
The melt flow rate (MFR) of the polypropylene resin composition (B) used in the present invention is 3.0 to 100 g / 10 minutes, and the lower limit is preferably 5.0 / 10 minutes or more, more preferably The upper limit is preferably 50 g / 10 min or less, more preferably 15 g / 10 min or less. If the MFR is 3.0 g / 10 min or more, the flowability of the molten resin is good, the surface roughness can be suppressed, and the relaxation time is short. Therefore, when the sheet is formed with an extruder, the residual stress after extrusion is small. Thus, gloss return can be effectively suppressed even when thermoformed. On the other hand, if it is 100 g / 10 minutes or less, the melt tension of the molten resin can be maintained, and the interface roughness between the base material layer and the surface layer can be suppressed.

  Here, MFR is a value measured according to JIS K7210 at a heating temperature of 230 ° C. and a load of 21.2 N (2.16 kg).

2.3. Characteristic (B-iii): Melt tension (MT)
Furthermore, the polypropylene resin composition (B) has a melt tension (MT) of 1.0 g or more. The measurement conditions are as described above. The upper limit of MT is not particularly required, but if MT is 40 g or less, the fluidity is improved and surface roughness can be suppressed. Therefore, it is preferably 40 g or less, more preferably 35 g or less. Preferably it is 30 g or less. When the melt tension is in the above range, the compatibility between the base material layer and the surface layer is improved, and when the multilayer sheet is formed, the interface roughness between the base material layer and the surface layer can be effectively suppressed.

3. Polypropylene resins having a long-chain branched structure (X1) and (Y1)
As a direct indicator that the polypropylene resins (X1) and (Y1) having a long-chain branch structure have a long-chain branch, a branching index g ′ can be mentioned. g ′ is given by the ratio of the intrinsic viscosity [η] lin of the linear polymer having the same molecular weight as the intrinsic viscosity [η] br of the polymer having a long chain branched structure, that is, [η] br / [η] lin. When a long chain branched structure is present, the value is smaller than 1.

  The definition is described in, for example, “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983), and is an index well known to those skilled in the art.

  g 'can be obtained as a function of the absolute molecular weight Mabs by using a GPC equipped with a light scatterometer and a viscometer as described below, for example.

  The polypropylene resins (X1) and (Y1) having a long-chain branched structure used in the present invention have a g ′ of 0.3 or more and less than 1.0 when the absolute molecular weight Mabs determined by light scattering is 500,000. It is preferable. The lower limit is more preferably 0.5 or more, still more preferably 0.7 or more, and most preferably 0.8 or more. The upper limit value is more preferably 0.95 or less, still more preferably 0.9 or less.

  As described in detail below, the polypropylene resins (X1) and (Y1) having a long-chain branched structure according to the present invention have a balance of the ratio between the main chain and the branched chain when g ′ is 0.3 or more. The formation of the gel can be suppressed, and a laminated sheet having a good appearance can be obtained. On the other hand, when g ′ is 1, it means that there is no long chain branching, and the melt tension tends to be insufficient, which is not suitable for the present invention.

In the present invention, the polypropylene resin having a long chain branched structure preferably has a comb chain structure.
According to “Encyclopedia of Polymer Science and Engineering vol. 2” (John Wiley & Sons 1985 p.485), the g ′ value of the comb polymer is represented by the following formula.

Here, g is a branching index defined by the rotation radius ratio of the polymer, and ε is a constant determined by the shape of the branched chain and the solvent. According to Table 3 of 487, a value of about 0.7 to 1.0 is reported for the comb chain in a good solvent. λ is the ratio of the main chain in the comb chain, and p is the average number of branches. According to this equation, the number of branches is extremely large for a comb chain, that is, p is infinite, and g ′ = g ^ε = λ ^ε , which is not less than the value of λ ^ε. In general, there will be a lower limit.

  On the other hand, the conventionally known random branched chain formula, which is considered to occur in the case of electron beam irradiation or peroxide modification, is given by the 485 page formula (19) in the same document. In the chain, as the number of branch points increases, the g ′ and g values monotonously decrease, especially without the lower limit. That is, in the present invention, the fact that the g ′ value has a minimum value as a function of the absolute molecular weight Mabs means that it has a comb chain structure.

  Further, in a branched polymer having a structure close to a comb chain in which g ′ is in the above range, the degree of decrease in melt tension is small when kneading is repeated, and this occurs in the process of industrially producing a molded product. For example, when the end material generated by cutting the end portion at the time of forming a sheet or a film is used again as a recycled material, the physical properties and the moldability are reduced, which is preferable.

  A specific method for calculating g 'is as follows.

  Waters Alliance GPCV2000 is used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). As the light scattering detector, a DAWN-E manufactured by Wyatt Technology, a multi-angle laser light scattering detector (MALLS) is used. The detectors are connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (added with an antioxidant Irganox 1076 manufactured by BASF Japan Ltd. at a concentration of 0.5 mg / mL).

  The flow rate is 1 mL / min, and two columns of Tosoh Corporation GMHHR-H (S) HT are connected and used. The temperature of the column, sample injection section, and each detector is 140 ° C. The sample concentration is 1 mg / mL and the injection volume (sample loop volume) is 0.2175 mL.

  In order to obtain the absolute molecular weight (Mabs) obtained from MALLS, the mean square inertia radius (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, the data processing software ASTRA (version 4.73.04) attached to MALLS is used. The calculation is performed with reference to the following documents.

References:
1. “Developments in Polymer Characterization-4” (JV 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)

[Calculation of branching index (g ′)]
The branching index (g ′) is determined by the intrinsic viscosity ([η] br) obtained by measuring a sample with the above Viscometer and the intrinsic viscosity ([η] obtained by measuring a linear polymer (linear polymer) separately). ] Lin) and ([η] br / [η] lin).

  When a long-chain branched structure is introduced into a polymer molecule, the radius of inertia becomes smaller than that of a linear polymer molecule having the same molecular weight. Since the intrinsic viscosity becomes smaller as the inertia radius becomes smaller, the intrinsic viscosity ([η] br) of the branched polymer with respect to the intrinsic viscosity ([η] lin) of the linear polymer having the same molecular weight as the long-chain branched structure is introduced. The ratio ([η] br / [η] lin) becomes smaller.

  Therefore, when the branching index (g ′ = [η] br / [η] lin) is a value smaller than 1, it means that a long chain branch is introduced. Here, as a linear polymer for obtaining [η] lin, a commercially available homopolypropylene (Novatec PP (registered trademark) grade name: FY6 manufactured by Nippon Polypro Co., Ltd.) is used. In the present invention, FY6 produced using a Ziegler catalyst and not subjected to modification treatment is regarded as a linear (linear) polypropylene. The fact that the logarithm of [η] lin of a linear polymer has a linear relationship with the logarithm of molecular weight is known as the Mark-Houwink-Sakurada equation, so [η] lin is appropriately set on the low molecular weight side or the high molecular weight side. Extrapolation can be used to obtain numerical values.

4). Method for Producing Polypropylene Resin (X1) and (Y1) Having Long Chain Branched Structure Polypropylene resin (X1) and (Y1) having a long chain branched structure are particularly limited as long as the above properties are satisfied. Although it is not a thing, the method using the macromer copolymerization method which has a comb chain structure and a long chain branched structure is formed at the time of superposition | polymerization is preferable. Examples of such methods include, for example, methods disclosed in JP-T-2001-525460, JP-A-10-338717, JP-A-2002-523575, and JP-A-2009-57542. It is done. In particular, the macromer copolymerization method disclosed in Japanese Patent Application Laid-Open No. 2009-57542 is suitable for the present invention because it does not generate gel and can obtain a long-chain branched polypropylene resin. This method produces a polypropylene having a long-chain branched structure using a catalyst in which a catalyst component having a specific structure having macromer-producing ability and a catalyst component having a specific structure having high molecular weight and macromer copolymerization ability are combined. It is a method to do. According to this, industrially effective methods such as bulk polymerization and gas phase polymerization, particularly single-stage polymerization under practical pressure-temperature conditions, and the amount of hydrogen as a molecular weight regulator, the amount of catalyst, and the catalyst ratio In addition to the average molecular weight of the polymer produced, the molecular weight distribution, the bias of the molecular weight distribution toward the high molecular weight side, the very high molecular weight component, and branching (amount, length, distribution) can be controlled. it can. This makes it possible to control the melt properties that characterize polypropylene having a long-chain branch structure, such as MFR, melt tension MT, and branching index g ′.

5. Other components Moreover, unless the effect of this invention is impaired, each layer of a base material layer and a surface layer may contain a polyethylene-type resin, an elastomer, etc. as another thermoplastic resin.

6). Crystal Nucleating Agent In the present invention, it is preferable that a crystal nucleating agent is blended in the surface layer.

  In that case, the compounding amount of the crystal nucleating agent is usually in the range of 0.01 to 1 part by weight, preferably 0.02 to 0.8 part by weight, with respect to 100 parts by weight of the propylene-based resin composition (B). More preferably, it is 0.04-0.5 weight part. When the blending amount of the crystal nucleating agent is within the above range, the effect of the crystal nucleating agent is sufficiently exhibited and a laminate having high gloss can be obtained.

  Examples of the crystal nucleating agent preferably used in the present invention include amide nucleating agents such as aromatic carboxylic acid metal salts, aromatic phosphate metal salts, sorbitol derivatives, and metal salts of rosin. Among these crystal nucleating agents, Pt-butyl aluminum benzoate, 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, 2,2′-methylenebisphosphate (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 (syn-6-oxide) aluminum hydroxide salt and an organic compound, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, sodium salt of rosin and the like are preferable.

  A commercially available crystal nucleating agent can be used. For example, the brand name Adeka Stub NA21 manufactured by Adeka Corporation, the brand name Gelall MD manufactured by Shin Nippon Rika Co., Ltd., and the brand names Milad NX3988 and Milad NX8000 manufactured by Milliken are listed.

7). Other compounding agents For the base material layer and surface layer of the polypropylene resin laminate for thermoforming of the present invention, an antioxidant, a neutralizing agent, a light stabilizer, an ultraviolet absorber, an inorganic filler, and an anti-blocking agent In addition, various additives such as a lubricant, an antistatic agent, a metal deactivator, a colorant, and other polymers that can be used for polypropylene can be blended within a range that does not impair the object of the present invention.

  Examples of antioxidants include phenolic antioxidants, phosphite antioxidants, and thio antioxidants, and examples of neutralizing agents include higher fatty acid salts such as calcium stearate and zinc stearate. Examples of the light stabilizer and the ultraviolet absorber include hindered amines, nickel complex compounds, benzotriazoles, and benzophenones.

  Examples of the inorganic filler include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate and the like, and examples of the lubricant include higher fatty acid amides such as stearic acid amide.

  Furthermore, examples of the antistatic agent include fatty acid partial esters such as glycerin fatty acid monoester, and examples of the metal deactivator include triazines, phosphones, epoxies, triazoles, hydrazides, and oxamides. it can.

8). Preparation Method of Polypropylene Resin Compositions (A) and (B) As a preparation method of the polypropylene resin compositions (A) and (B) used in the present invention, a powdery or pellet-like polypropylene resin, and Examples thereof include a method of mixing a crystal nucleating agent and other compounding agents that can be blended in each layer as necessary, using a dry blend, a Henschel mixer, or the like, and a method of melt-kneading using a single screw or twin screw extruder.

  Further, depending on the situation, only the crystal nucleating agent may be separately fed during the production of the polypropylene thermoforming sheet.

9. Laminate The polypropylene resin laminate of the present invention is described in detail below.

9.1. Layer Configuration The polypropylene resin laminate for thermoforming of the present invention is a laminate having a polypropylene resin composition (A) as a base material layer and a polypropylene resin composition (B) as a surface layer. Examples of the layer configuration include two types and two layers of surface layer / base material layer and two types and three layers such as surface layer / base material layer / surface layer, as long as the effect of the present invention is not inhibited. 3 types and 3 layers such as surface layer / base material layer / other resin layer and 3 types and 5 layers such as surface layer / base material layer / other resin layer / base material layer / surface layer A plurality of layers can be included with the resin layer interposed therebetween, and for example, a layer having a necessary function according to the purpose, such as a gas barrier layer, a foam layer, or an impact resistance imparting layer, can be provided.

  The total thickness of the surface layers laminated on one or both sides of the base material layer is preferably 1 to 50% of the entire laminate, more preferably 2 to 45%, and even more preferably 5 to 40%. . If the thickness of both surface layers is in the above range, it is possible to suppress the roughening of the interface while maintaining high gloss.

  As long as the effects of the present invention are not impaired, a printed layer, a decorative layer, or the like can be provided outside the surface layer. An adhesive layer or the like can be provided between the base material layer and another resin layer.

9.2. Production of Laminate The production method of the polypropylene resin laminate for thermoforming of the present invention is not particularly limited, but a coextrusion method is preferable because productivity and layer configuration can be easily adjusted. The production method using a co-extrusion T-die molding machine will be described with more specific examples. The propylene polymer composition used in the present invention is put into an extruder for each layer, and after heat-melt kneading at a temperature of 200 to 280 ° C. , Make a laminated structure with a feed block, extrude into a sheet form from the die lip of the T die, cool and solidify the laminated molten sheet by air knife method, air chamber method, polishing roll method, swing roll method, belt cast method, water cooling method etc. Then, it is taken up by a take-up machine to produce a laminated sheet.

10. Production of Thermoformed Body The polypropylene resin laminate for thermoforming of the present invention is suitably used for thermoforming. In general, thermoforming is to heat and soften a plastic sheet and press it against a desired mold to eliminate the air in the gap between the mold and the material, and then close the mold to the mold by atmospheric pressure. There are vacuum forming to perform, pressure forming to form using compressed air at atmospheric pressure or higher, and vacuum / pressure forming using both vacuum and compressed air. Moreover, since the polypropylene resin laminate for thermoforming of the present invention has high gloss on the surface that is not in contact with the mold, it can be used particularly preferably in male molding using only a male mold. Applications of the thermoformed article obtained by the above thermoforming include industrial members such as automobile interior and exterior, various containers used in the food packaging field and the like, container lids, and the like.

11. Form of Laminate and Thermoformed Body The polypropylene resin laminate for thermoforming of the present invention is a laminate used in the case of manufacturing containers, lids, molded products, etc. used in the packaging material field and various industrial members by thermoforming. An excellent appearance and high gloss are required not only for the laminate itself but also for the thermoformed body. Therefore, the thermoforming polypropylene resin laminate of the present invention preferably has a surface layer gloss of 80% or more. Further, in a molded product obtained by thermoforming this laminate, the gloss of the surface layer is preferably 70% or more, and more preferably 75% or more. When the gloss is within the above range, a high-quality thermoformed article can be obtained. Therefore, the polypropylene resin laminate for thermoforming of the present invention can be suitably used for industrial members for automobile interior and exterior, packaging containers for food products, daily necessities, and the like.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

12 Measurement method of various physical properties (i) MFR
Measured in accordance with JIS K7210: 1999 Method A (ISO 1133: 1997), Condition M (230 ° C., 2.16 kg load). The unit is g / 10 minutes.

(Ii) Melt tension (MT)
It measured on the following conditions using the Toyo Seiki Seisakusho Capillograph.
・ Capillary: Diameter 2.0mm, length 40mm
・ Cylinder diameter: 9.55mm
・ Cylinder extrusion speed: 20 mm / min ・ Pickup speed: 4.0 m / min ・ Temperature: 230 ° C.

  When the sample for MT measurement is made of a plurality of polypropylene resins, these resins are dry blended, put into a single screw extruder with a screw diameter of 30 mmφ, and melt kneaded at a screw rotation speed of 30 rpm and a temperature of 230 ° C. Extrusion and MT measurement were carried out using the resulting granulated composition.

(Iii) Branch index g ′
Using a GPC equipped with a differential refractometer (RI), a viscosity detector (Viscometer), and a light scattering detector (MALLS) as detectors, a branching index g ′ when the absolute molecular weight Mabs was 500,000 was determined. The specific measurement method, analysis method, and calculation method are as described in item 3 above.

13. Production Example of Polypropylene Resin Having Long Chain Branched Structure by Macromer Copolymerization Method [Production Example PP-1]
<Synthesis example 1 of catalyst component (A)>
Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium: (component [A-1] ( Synthesis of complex 1):
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium is disclosed in JP 2012-149160 A. The same procedure as described in Synthesis Example 1 was performed.

<Synthesis example 2 of catalyst component (A)>
Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium: (synthesis of component [A-1] (complex 2)):
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is carried out according to the method described in Example 7 of JP-A-11-240909. It carried out like.

<Catalyst synthesis example 1>
(I) Chemical treatment of ion-exchange layered silicate In a separable flask, 96% sulfuric acid (668 g) was added to 2,264 g of distilled water, and then montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL: average particle size 19 μm) as a layered silicate ) 400 g was added. The slurry was heated at 90 ° C. for 210 minutes. When this reaction slurry was added to 4,000 g of distilled water and filtered, 810 g of a cake-like solid was obtained.

  Next, 432 g of lithium sulfate and 1,924 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution. The slurry was reacted at room temperature for 120 minutes. After adding 4,000 g of distilled water to the slurry, the mixture was filtered, further washed with distilled water to pH 5-6, and filtered to obtain 760 g of a cake-like solid.

  The obtained solid was preliminarily dried overnight at 100 ° C. under a nitrogen stream, and then coarse particles of 53 μm or more were removed, followed by drying under reduced pressure at 200 ° C. for 2 hours to obtain 220 g of chemically treated smectite.

  The composition of this chemically treated smectite is Al: 6.45 wt%, Si: 38.30 wt%, Mg: 0.98 wt%, Fe: 1.88 wt%, Li: 0.16 wt%, Al / Si = 0.175 [mol / mol].

(Ii) Catalyst preparation and prepolymerization In a three-necked flask (volume: 1 L), 20 g of the chemically treated smectite obtained above was placed, and heptane (132 mL) was added to form a slurry, which was triisobutylaluminum (25 mmol: concentration) 143 mg / mL heptane solution (68.0 mL) was added, and the mixture was stirred for 1 hour, washed with heptane until the residual liquid ratio became 1/100, and heptane was added so that the total volume became 100 mL.

  In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)-] prepared in Synthesis Example 1 of the catalyst component (A) was used. 4- (4-i-propylphenyl) indenyl}] hafnium (210 μmol) is dissolved in toluene (42 mL) (solution 1), and the catalyst component (A) is synthesized in another flask (volume 200 mL). Rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (90 μmol) prepared in Example 2 was dissolved in toluene (18 mL) (solution 2 ).

  Triisobutylaluminum (0.84 mmol: 1.2 mL of a heptane solution with a concentration of 143 mg / mL) was added to a 1 L flask containing the chemically treated smectite, and then the above solution 1 was added and stirred at room temperature for 20 minutes. Thereafter, triisobutylaluminum (0.36 mmol: 0.50 mL of a heptane solution having a concentration of 143 mg / mL) was added, and then the above solution 2 was added and stirred at room temperature for 1 hour.

  Thereafter, 338 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.

  After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 4 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 1 hour. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (12 mmol: 17.0 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.

  This solid was dried under reduced pressure for 1 hour to obtain 52.8 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.82.

  Hereinafter, this is referred to as “preliminary polymerization catalyst 1”.

<Polymerization>
After sufficiently replacing the inside of the stirring autoclave with an internal volume of 200 liters with propylene, 40 kg of sufficiently dehydrated liquefied propylene was introduced. Hydrogen 9.2 L (0.82 g) and triisobutylaluminum (0.12 mol: 0.47 L of a heptane solution with a concentration of 50 g / L) were added thereto, and the internal temperature was raised to 70 ° C. Next, 2.1 g (by weight excluding the prepolymerized polymer) of the prepolymerized catalyst 1 was injected with argon to start the polymerization, and the internal temperature was maintained at 70 ° C. After 2 hours, 100 ml of ethanol was injected, purged of unreacted propylene, and the inside of the autoclave was purged with nitrogen to terminate the polymerization. The obtained polymer was dried at 90 ° C. under a nitrogen stream for 1 hour to obtain 18.8 kg of a polymer. The catalytic activity was 9000 g PP / g catalyst.

<Granulation>
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, which is a phenolic antioxidant, with respect to 100 parts by weight of the polypropylene powder obtained by polymerization. G] methane (trade name: IRGANOX 1010, manufactured by Ciba Specialty Chemicals) 0.05 part by weight, tris (2,4-di-t-butylphenyl) phosphite (trade name: IRGAFOS) which is a phosphite antioxidant 168, 0.05 parts by weight of Ciba Specialty Chemicals Co., Ltd.) and 0.05 part by weight of calcium stearate (trade name: calcium stearate, manufactured by Nippon Oil & Fats Co., Ltd.) as a neutralizing agent After mixing for 3 minutes at room temperature with a stirring mixer (Henschel mixer, trade name), melt mixing with a twin screw extruder Kneaded to obtain pellet PP-1. The MFR was 10 g / 10 min, the MT was 5 g, and the branching index g ′ at an absolute molecular weight Mabs of 500,000 was 0.9.

[Production Example PP-2]
The polymerization was carried out in the same manner as in Production Example 1 except that 5.8 liters of hydrogen to be added and 2.6 g of the prepolymerized catalyst 1 to be used (by weight excluding the prepolymerized polymer) were used. A polymer (hereinafter referred to as “PP-2”) was obtained. The catalytic activity was 8000 g PP / g catalyst. The MFR was 2.2 g / 10 min, the MT was 13 g, and the branching index g ′ at an absolute molecular weight Mabs of 500,000 was 0.9.

[Production Example PP-3]
The same procedure as in Production Example 1 was carried out except that 3.8 liters of hydrogen to be added and 2.8 g of the prepolymerized catalyst 1 to be used (by weight excluding the prepolymerized polymer) were used, and 17.4 kg of a polymer ( Hereinafter, referred to as “PP-3”). The catalytic activity was 6210 g PP / g catalyst, and the pelletized product had an MFR of 1.0 g / 10 min, an MT of 21 g, a branching index g ′ of 0.9 g at an absolute molecular weight Mabs of 500,000, and 0.9.

14 Other resins used In addition to the polypropylene resins having the long-chain branched structure, the polypropylene resins used in Examples and Comparative Examples are as follows.

PP-4: MFR = 0.8 g / 10 min, MT = 2.9 g, g ′ = 1.0 (Novatech PP EG8B <trade name> manufactured by Nippon Polypro Co., Ltd.)
PP-5: MFR = 21 g / 10 min, MT = 0.1 g, g ′ = 1.0 (Novatech PP MA1B <trade name> manufactured by Nippon Polypro Co., Ltd.)
PP-6: MFR = 0.32 g / 10 min, MT = 6.0 g, g ′ = 1.0 (Novatech PP EC9 <trade name> manufactured by Nippon Polypro Co., Ltd.)
PP-7: MFR = 11 g / 10 min, MT = 0.8 g, g ′ = 1.0 (Novatech PP MA38 <trade name> manufactured by Nippon Polypro Co., Ltd.)
PP-8: MFR = 0.5 g / 10 min, MT = 1.8 g, g ′ = 1.0 (Novatech PP EA9 <trade name> manufactured by Nippon Polypro Co., Ltd.)
PP-9: MFR = 1.3 g / 10 min, MT = 1.9 g, g ′ = 1.0 (Novatech PP EG7F <trade name> manufactured by Nippon Polypro Co., Ltd.)
PP-10: MFR = 2.6 g / 10 min, MT = 1.1 g (Novatech PP FY6 <trade name> manufactured by Nippon Polypro Co., Ltd.)
PP-11: MFR = 7.0 g / 10 min, MT = 0.2 g, g ′ = 1.0 (WINTEC WFW4 <product name> manufactured by Nippon Polypro Co., Ltd.)

[Example 1]
Molding of laminated sheet PP-1 was used as a polypropylene resin (Y1) having a long-chain branched structure to obtain a polypropylene resin composition (B). A master batch pellet of Millid NX8000, trade name of Milliken, which is a crystal nucleating agent, was added and dry blended so that the amount of the crystal nucleating agent component was 0.5 parts by weight, to obtain a crystal nucleating agent-containing resin composition. This resin composition was put into both surface layer sides of a feed block having two types and three layers from an extruder having a screw diameter of 45 mm heated to 230 ° C., and PP-3 was 240 as a propylene resin composition for a base material layer (A). It put into the intermediate | middle layer side of the said feed block from the extruder with a screw diameter of 65 mm heated to ° C. These are extruded into a sheet form from a T-type die having a width of 750 mm heated to 230 ° C., and sandwiched between two mirror rolls (with hard chrome plating applied) in which cooling water of 70 ° C. is circulated. It was cooled and solidified, and was taken out to obtain a polypropylene resin laminated sheet for thermoforming. The thickness of the laminated sheet is 0.2 mm for both surface layers, 1.6 mm for the base material layer, and 2.0 mm in total (total sheet thickness).

Evaluation of Laminated Sheet (1) Sheet Appearance Evaluation The appearance of the sheet was visually confirmed and evaluated according to the following criteria.
◯: There is no surface roughness and no interface roughness between the surface layer and the base material layer, and the appearance is excellent.
X: Surface roughness and interface roughness occur, and the sheet is not good.

(2) Surface gloss measurement The glossiness (GROSS) on the surface layer side was measured by a 60-degree mirror method according to JIS K7105.

Evaluation of Thermoformed Body The molded resin laminated sheet was sandwiched between two iron frames (33 mm × 33 mm × 2 mm) having a 30 cm square hole in the center and set horizontally in a heat insulating box. Next, an upper and lower heater heated to 450 ° C. (the upper and lower heaters heat the resin sheet from a distance of 15 cm from the installed sheet surface) so that the resin sheet sandwiched in the iron frame can be heated uniformly. It was slid and installed. The sheet in the iron frame once hangs down in the direction of the lower surface heater by heating, and then when the temperature rises uniformly in the thickness direction of the sheet, the resin sheet becomes horizontal again (hereinafter referred to as a tension point). After further heating for 15 seconds from this tension point, the sheet was pressed with a plug having a length of 20 cm in the vertical direction from above to obtain a deep-drawn thermoformed body. A 5 cm square test piece was cut out from the center of the side surface of the obtained deep-drawn thermoformed body, and the glossiness of the surface layer of this test piece was measured by a 60-degree mirror method according to JIS K7105. This thermoformed body was evaluated according to the following criteria.
○: No gloss return (decrease in glossiness of 25% or less) and excellent gloss (glossiness of 75% or more).
(Triangle | delta): It is a level which does not have a glossiness fall (gloss reduction of 25% or less) and there is no problem in appearance, but the glossiness is less than 75%.
X: Glossiness occurs (loss of gloss exceeds 25%) and gloss is lost.

  The evaluation results are shown in Table 1.

[Example 2]
It implemented like Example 1 except having used what blended 75 weight% of PP-1 and 25 weight% of PP-4 as a polypropylene resin composition (B). The evaluation results are shown in Table 1.

[Example 3]
The same procedure as in Example 1 was performed except that a polypropylene resin composition (B) blended with 25 wt% PP-1 and 75 wt% PP-5 was used. The evaluation results are shown in Table 1.

[Example 4]
It implemented similarly to Example 1 except having used PP-6 as a polypropylene resin composition (A) for base material layers. The evaluation results are shown in Table 1.

[Example 5]
Example 1 except that the laminated sheet was manufactured so that the thickness of the laminated sheet was 0.1 mm for both surface layers and 1.8 mm for the base layer, and the total thickness was 2.0 mm (total sheet thickness). It carried out like. The evaluation results are shown in Table 1.

[Example 6]
PP-6 was used as the polypropylene resin composition (A) for the base material layer, and the thickness of the laminated sheet was 0.1 mm for both surface layers and 1.8 mm for the base material layer, totaling 2.0 mm (total Sheet thickness) was carried out in the same manner as in Example 1 except that a laminated sheet was produced. The evaluation results are shown in Table 1.

[Example 7]
The same operation as in Example 1 was carried out except that a polypropylene resin composition (B) blended with 45% by weight of PP-2 and 55% by weight of PP-7 was used. The evaluation results are shown in Table 1.

[Example 8]
A polypropylene resin composition (B) blended with 45% by weight of PP-2 and 55% by weight of PP-7, and a polypropylene resin composition (A) for the base layer of PP-3. Instead, it carried out like Example 1 except having used PP-6. The evaluation results are shown in Table 1.

[Example 9]
It implemented like Example 1 except not having added a crystal nucleating agent to a polypropylene resin composition (B). The evaluation results are shown in Table 1.

[Comparative Examples 1-8]
As shown in Table 2, with respect to Example 1, except that PP-2, PP-4, PP-5, PP-7 to PP-11 were used as the polypropylene resin composition (B). 1 was carried out. The evaluation results are shown in Table 2.

[Consideration by contrast between Example and Comparative Example]
Considering each of the above Examples and Comparative Examples in contrast, the polypropylene resin laminates for thermoforming of Examples 1 to 9 that satisfy each requirement in the configuration of the present invention have a good lamination state, and the surface It can be seen that there is no roughness, excellent appearance, and high gloss. Moreover, it is clear that the thermoformed body maintains gloss without delustering.

  Therefore, it can be clearly understood that the provisions of the constituent requirements for the polypropylene-based resin composition (B) in the configuration of the present invention are reasonable and verified by experimental data.

  In Comparative Examples 1 to 7, the polypropylene resin composition (B) does not contain the polypropylene resin (Y1) containing a long chain branched structure, and MFR and MT are also outside the scope of the present invention. The roughness of the interface between the base material layer and the surface layer occurred, and the appearance of the laminated sheet was bad. Furthermore, regarding the molded body after thermoforming, in Comparative Examples 1 and 2, it was in a glossy state and the gloss could not be maintained. Moreover, in Comparative Examples 3-7, although it did not become the state of glossiness, the surface roughness and interface roughness of the lamination sheet were reflected also in the thermoformed body, and the external appearance was bad.

  In Comparative Example 8, the MFR and MT of the polypropylene resin composition (B) are outside the scope of the present invention, so that the molded body after thermoforming becomes glossy and cannot maintain gloss. There wasn't.

  From the above comparative evaluation, the validity of the effects and requirements in the present invention are clear.

  The polypropylene-based resin laminate for thermoforming of the present invention is excellent in gloss and appearance, and further, the molded product after thermoforming is excellent in gloss and appearance. Therefore, it can be used in the field of packaging materials where cosmetics of molded products are required, household appliances, industrial parts such as automobile interiors and the like.

Claims (6)

A base material layer comprising a polypropylene resin composition (A) having the following characteristics (Ai) to (A-iii) and laminated on one or both sides of the base material layer, the following characteristics (Bi And a surface layer containing a polypropylene resin composition (B) having (B-iii).
Characteristic (Ai): Polypropylene resin (X1) having a long-chain branched structure and / or MFR having a melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) of 0.1 to 15 g / 10 min. Is composed of a linear polypropylene resin (X2) having 0.1 to 3.0 g / 10 min and other polypropylene resin (X3) used as necessary.
Characteristic (A-ii): MFR (temperature 230 ° C., load 2.16 kg) is smaller than MFR of the polypropylene resin composition (B).
Characteristic (A-iii): Melt tension (MT) at 230 ° C. is 5 to 30 g.
Characteristic (Bi): It consists of a polypropylene resin (Y1) having a long-chain branched structure and another polypropylene resin (Y2) used as necessary.
Characteristic (B-ii): Melt flow rate (MFR) (temperature 230 ° C., load 2.16 kg) is 3.0 to 100 g / 10 min.
Characteristic (B-iii): Melt tension (MT) at 230 ° C. is 1.0 g or more.   2. The branching index g ′ when the absolute molecular weight Mabs of the polypropylene resins (X1) and (Y1) having a long-chain branched structure is 500,000 is 0.3 or more and less than 1.0. The polypropylene resin laminate for thermoforming as described.   2. The polypropylene resin laminate for thermoforming according to claim 1, wherein the surface layer contains a crystal nucleating agent.   The total of the thickness of a surface layer is 1 to 50% with respect to the thickness of a laminated body, The polypropylene-type resin laminated body for thermoforming of Claim 1 or 2 characterized by the above-mentioned.   The polypropylene resin laminate for thermoforming according to any one of claims 1 to 4, wherein the polypropylene resins (X1) and (Y1) have a long-chain branched structure formed during polymerization.   The gloss of the surface layer is 80% or more, and the gloss of the surface layer when formed into a molded product by thermoforming is 70% or more. Polypropylene resin laminate for thermoforming.