JP6565386B2 - Polyolefin resin composition for deformation recovery structure and deformation recovery structure - Google Patents

Description

  The present invention relates to a polyolefin-based resin composition for deformation-recoverable structures having flame retardancy and a deformation-recoverable structure, and in particular, has excellent flame retardancy and does not cause problems during molding, Relates to a polyolefin-based resin composition that constitutes a structure having excellent deformation recoverability when the load is removed after being continuously deformed by a continuous load, and a deformation recoverable structure comprising the same.

  Conventionally, deformation-recoverable structures, for example, bedding such as beds, cushion materials for homes, vehicles, ships, aircraft seats, etc., have been made of urethane foam, non-elastic crimped cotton, and non-elastic crimped fibers. Bonded resin cotton or hard cotton has been used.

  In recent years, an attempt has been made to use a three-dimensional network structure obtained by extruding a thermoplastic resin in a loop shape by extrusion molding, heat-bonding the strands, and cooling and solidifying the strands as the cushioning material. As the thermoplastic resin, it is known to use a polyester-based elastomer, a polyurethane-based elastomer, or a polyamide-based elastomer (see, for example, Patent Document 1: Japanese Patent Application Laid-Open No. 07-068061). Patent Document 2 (Japanese Patent Laid-Open No. 2004-218116) and Patent Document 3 (Japanese Patent Laid-Open No. 2006-2001117) describe an ethylene-vinyl acetate copolymer (EVA) or an ethylene / α-olefin copolymer. A certain polyethylene-based resin is disclosed, and Patent Document 4 (Japanese Patent Laid-Open No. 2002-061059) discloses a three-dimensional structure formed by blending 5 to 30% by weight of SBS with polypropylene.

There are cases where flame retardant properties are required for the above-mentioned bedding such as beds and cushioning materials for home use, seats for vehicles, ships and aircraft.
For this problem, for example, in Patent Document 5 (Japanese Patent Laid-Open No. 08-098748), the thermoplastic resin fibers constituting the reinforcing layer and the thermoplastic elastic resin continuous filaments constituting the cushion body have 1000 phosphorus. A bed mat is disclosed which is contained in the range of ~ 20000 ppm. However, the flame retardant decomposes during molding, generating white smoke and a strange odor, and has a problem that a strange odor remains even after molding.
To deal with this problem, for example, Patent Document 6 (Japanese Patent Laid-Open No. 2001-072798) discloses a salt composed of a specific phosphate ester flame retardant (A), a triazine compound, and cyanuric acid or isocyanuric acid. A flame retardant thermoplastic resin composition containing a flame retardant (B) is disclosed. However, although the flame retardant combination is effective for polyester-based elastomers, as described in Comparative Example 14, the effect is insufficient for polyolefins such as polypropylene.
Furthermore, the phosphorus-based flame retardant is liable to form a burnt material at the time of molding, not only deteriorating the appearance of the molded product, but also has a problem that the burnt material adheres to the molding machine and the moldability tends to deteriorate.

Japanese Patent Application Laid-Open No. 07-068061 JP 2004-218116 A JP 2006-200117 A JP 2002-061059 A Japanese Patent Application Laid-Open No. 08-098748 JP 2001-072798 A

  In view of the above-mentioned problems of the prior art, the object of the present invention is to have excellent flame retardancy, and does not cause problems during molding, and further, after being continuously deformed by a continuous load, the load is reduced. The present invention provides a polyolefin resin composition that constitutes a structure having excellent deformation recovery properties when removed and a deformation recovery structure comprising the same.

As a result of intensive studies to solve the above problems, the present inventor uses a resin composition containing 1 to 15 parts by weight of a halogen-based flame retardant with respect to 100 parts by weight of a specific polyolefin resin. It has been found that the structure obtained does not cause defects such as burns at the time of molding, exhibits excellent flame retardancy, and further exhibits an unprecedented property of exhibiting excellent deformation recovery properties. Completed.
The present invention provides the following polyolefin resin composition for a deformable structure and a deformable structure comprising the same.

[1] Polyolefin resin composition for deformation-recoverable structure containing 1 to 15 parts by weight of halogenated flame retardant (D) with respect to 100 parts by weight of polyolefin resin having the following characteristics (y1) and (y2) object.
(Y1) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 1.0 to 100 g / 10 minutes.
(Y2) Melting peak temperature (Tm) is 60-170 degreeC.
[2] The polyolefin system for deformation-recoverable structure according to [1], further comprising 0.1 to 10 parts by weight of a flame retardant aid (E) with respect to 100 parts by weight of the polyolefin resin. Resin composition.
[3] The polyolefin resin composition for deformation-recoverable structure according to [1] or [2], wherein the halogen flame retardant (D) is a bromine flame retardant.
[4] The polyolefin resin is 1 to 99 parts by weight of the following component (A) and 1 to 99 parts by weight of the following component (B) (provided that the total of the component (A) and the component (B) is 100 parts by weight) The polyolefin resin composition for deformation-recoverable structures according to any one of [1] to [3], comprising a polypropylene resin composition (X) comprising
Component (A): One or more propylene homopolymers and / or propylene-α-olefin copolymers satisfying the following (a1) to (a2).
(A1) The melting peak temperature (Tm) is 121 to 170 ° C.
(A2) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.1 to 500 g / 10 minutes.
Component (B): At least one propylene-α-olefin copolymer satisfying the following (b1).
(B1) It is composed of 51 to 90% by weight of propylene, 10 to 49% by weight of ethylene and / or an α-olefin having 4 to 10 carbon atoms.

[5] Part or all of the polypropylene resin composition (X) is 1 to 99 parts by weight of component (A ′) satisfying (a1) and (a2), and component (B) satisfying (b1) ') A polypropylene resin composition (X') obtained by sequential polymerization of 1 to 99 parts by weight (provided that the total amount of (A ') and (B') is 100 parts by weight). The polyolefin-based resin composition for deformation-recoverable structure according to [4], which is characterized by the following.
[6] The polyolefin resin composition for deformation-recoverable structure according to [5], wherein the polypropylene resin composition (X ′) is obtained by sequential polymerization using a metallocene catalyst.
[7] The component (B ′) is at least one propylene-α-olefin copolymer composed of 83 to 90% by weight of propylene and 10 to 17% by weight of ethylene [5] Alternatively, the polyolefin resin composition for deformation-recoverable structure according to [6].
[8] A deformation recoverable structure comprising the polyolefin resin composition for a deformable structure according to any one of [1] to [7].
[9] The deformation-recoverable structure is formed by twisting a continuous linear body made of a plurality of strands obtained by extrusion into a three-dimensional random loop so that at least a part of contact portions of the plurality of loops is fused. The deformation-recoverable structure according to [8], wherein the structure has a three-dimensional network structure.

  The polyolefin-based resin composition for deformation-recoverable structure of the present invention provides a structure that does not cause defects such as burns during molding, exhibits excellent flame retardancy, and further exhibits excellent deformation-recovery properties .

The polyolefin resin composition for deformation-recoverable structure of the present invention (hereinafter also referred to as “polyolefin resin composition for deformation-recoverable structure (Y)”) has the following characteristics (y1) and (y2). 1 to 15 parts by weight of the halogen-based flame retardant (D) is contained with respect to 100 parts by weight of the polyolefin resin.
(Y1) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 1.0 to 100 g / 10 minutes.
(Y2) Melting peak temperature (Tm) is 60-170 degreeC Hereinafter, it demonstrates in detail for every item.

[Halogen flame retardant (D)]
The flame retardant used in the present invention needs to be a halogen-based flame retardant. When a flame retardant other than a halogen flame retardant, for example, a phosphorus flame retardant is used, a deformation comprising a polyolefin resin composition (Y) for a deformable structure is included if it contains an amount sufficient to develop a sufficient flame retardant effect. Deformability of the recoverable structure is inferior.
As the halogen flame retardant, for example, organic halogenated aromatic compounds such as halogenated diphenyl compounds, halogenated bisphenol compounds, halogenated bisphenol-bis (alkyl ether) compounds, halogenated phthalimide compounds, and the like are preferable. Bisphenol-bis (alkyl ether) compounds are more preferred.
Examples of the halogenated bisphenol bis (alkyl ether) compounds include (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl) methane. 1- (3,5-dibromo-4-2,3-dibromopropoxyphenyl) -2- (3-bromo-4-2,3-dibromopropoxyphenyl) ethane, 1- (3,5-dibromo-4 -2,3-dibromopropoxyphenyl) -3- (3-bromo-4-2,3-dibromopropoxyphenyl) propane, 2,2-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) ) Propane, (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3-chloro-4-2,3-dibromopropoxyphenyl) 1- (3,5-dichloro-4-2,3-dibromopropoxyphenyl) -2- (3-chloro-4-2,3-dibromopropoxyphenyl) ethane, 1- (3,5-dichloro- 4-2,3-dibromopropoxyphenyl) -3- (3-chloro-4-2,3-dibromopropoxyphenyl) propane, bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) methane, 1,2-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) ethane, 1,3-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) propane, bis ( 3,5-dichloro-4-2,3-dibromopropoxyphenyl) methane, 1,2-bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) ethane, 1,3 Bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) propane, 2-bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) propane, (3,5-dibromo-4 -2,3-dibromopropoxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl) ketone, (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3-chloro- 4-2,3-dibromopropoxyphenyl) ketone, bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) ketone, bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) Ketone, (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl) ether (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3-chloro-4-2,3-dibromopropoxyphenyl) ether, bis (3,5-dibromo-4-2,3 -Dibromopropoxyphenyl) ether, bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) ether, (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo- 4-2,3-dibromopropoxyphenyl) thioether, (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3-chloro-4-2,3-dibromopropoxyphenyl) thioether, bis (3 , 5-Dibromo-4-2,3-dibromopropoxyphenyl) thioether, bis (3,5-dichloro-4-2,3-dibromopropo Siphenyl) thioether, (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl) sulfone, (3,5-dichloro-4-2, 3-dibromopropoxyphenyl)-(3-chloro-4-2,3-dibromopropoxyphenyl) sulfone, bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) sulfone, bis (3,5- Dichloro-4-2,3-dibromopropoxyphenyl) sulfone, among which brominated bisphenol A (brominated aliphatic ether), brominated bisphenol S (brominated aliphatic ether), chlorinated bisphenol A (chlorinated) Aliphatic ether), chlorinated bisphenol S (chlorinated aliphatic ether), Love Romo bisphenol A, etherified tetrabromobisphenol S preferred.

Examples of etherified tetrabromobisphenol A include tetrabromobisphenol A-bis (2,3-dibromopropyl ether) and 2,2-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) propane. The Examples of etherified tetrabromobisphenol S include bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) sulfone.
Among these halogen flame retardants, bromine flame retardants have a high flame retardant effect and can be decomposed even when subjected to a thermal history during the production and molding of the polyolefin resin composition for deformation-recoverable structures of the present invention. Is preferable.
These halogen flame retardants may be used alone or in combination of two or more. For example, a halogenated diphenyl compound and a halogenated bisphenol compound may be used in combination.
In addition to the halogen-based flame retardant, other organic flame retardants that do not fall under the halogen-based flame retardant such as phosphorus-based and nitrogen-based flame retardants can also be used.

In the polyolefin resin composition (Y) for a deformable structure according to the present invention, the content of the halogen flame retardant (D) is 1 to 15 parts by weight, preferably 2 with respect to 100 parts by weight of the polyolefin resin. -10 parts by weight, more preferably 2-5 parts by weight. When the content of the halogen-based flame retardant (D) is in the above range, the effect of improving the flame retardancy is high, and desirable results are obtained in the formability and economic efficiency such as deformation recovery characteristics and the occurrence of burning during molding.
In addition, since various products are commercially available from many companies and it is possible to obtain desired products, these halogen flame retardants (D) can be purchased and used.

[Flame Retardant (E)]
The polyolefin resin composition (Y) for deformation-recoverable structure of the present invention can further contain a flame retardant aid (E). In the present invention, the flame retardant aid (E) to be used is not particularly limited, and various compounds can be used as desired. Among them, an antimony compound is preferable. The flame retardant aid (E) represented by the antimony compound is used to increase the flame retardant effect by being contained in the polyolefin resin together with the halogen flame retardant (D).
Specific examples of antimony compounds include antimony halides such as antimony trioxide, antimony pentoxide, antimony trichloride, and antimony pentachloride, antimony trisulfide, antimony pentasulfide, sodium antimonate, and antimony tartrate. Can be mentioned.
In the present invention, the antimony compound includes metal antimony. As the antimony compound used in the present invention, antimony trioxide is preferable.
Moreover, these flame retardant adjuvants (E) may be used independently and may use 2 or more types together.

In the polyolefin resin composition (Y) for deformation-recoverable structure of the present invention, the content of the flame retardant aid (E) used as desired is 0.1 to 10 with respect to 100 parts by weight of the polyolefin resin. Part by weight is preferable, more preferably 0.5 to 10 parts by weight, still more preferably 0.5 to 6 parts by weight, and particularly preferably 1 to 3 parts by weight. When the content of the flame retardant aid (E) is in the above range, the effect of improving the flame retardancy is high, and desirable results are obtained in the formability and economical efficiency such as deformation recovery characteristics and occurrence of burning during molding.
The flame retardant aid (E) has a flame retardant effect in combination with the halogen flame retardant (D), and the total weight of the halogen flame retardant (D) and the flame retardant aid (E) On the other hand, it is preferably used in the range of 30 to 60% by weight.
In addition, since various flame retardant adjuvants (E) are commercially available from many companies and it is possible to obtain desired products, they can be purchased and used.

[Polyolefin resin]
The polyolefin resin constituting the polyolefin resin composition (Y) for deformation-recoverable structure of the present invention satisfies the following characteristics (y1) and (y2).

Characteristic (y1): Melt flow rate (MFR: 230 ° C., 2.16 kg load)
The melt flow rate (MFR) of the polyolefin resin constituting the polyolefin resin composition (Y) of the present invention is 1.0 to 100 g / 10 min.
Here, MFR is measured according to JIS K7210: 1999 method A, condition M (230 ° C., 2.16 kg load).
When the MFR of the polyolefin resin is in the above range, the load at the time of molding the polyolefin resin composition (Y) is small, the molding itself is easy to mold, and the molding stability, particularly used for extrusion molding. The molding stability in the case is good. The preferable range of the melt flow rate (MFR) of the polyolefin resin is 2.0 to 50 g / 10 minutes, more preferably 5.0 to 30 g / 10 minutes, and particularly preferably 5.0 to 20 g / 10 minutes.

Characteristic (y2): Melting peak temperature (Tm)
The melting peak temperature of the polyolefin resin of the present invention is 60 to 170 ° C.
When the melting peak temperature is in the above range, the structure obtained from the polyolefin-based resin composition (Y) of the present invention can retain its shape in a daily use environment, for example, in a high temperature environment such as an automobile interior. Heat resistance can be expressed.
A preferable range of the melting peak temperature is 121 ° C to 170 ° C. When the melting peak temperature is 121 ° C. or higher, the structure obtained from the polyolefin resin composition (Y) of the present invention exhibits heat resistance sufficient to maintain its shape at a high temperature, preferably 121 ° C. or higher. Since it becomes easy, restrictions on the use environment are reduced.
A more preferable range of the melting peak temperature is 125 to 170 ° C, more preferably 130 to 170 ° C, and particularly preferably 135 to 170 ° C.

Although there is no restriction | limiting in particular in the kind of polyolefin resin which comprises the polyolefin resin composition (Y) for deformation recovery structure of this invention, The polypropylene resin composition (X) and / or (X ') mentioned later are preferable.
Examples of polyolefin resins other than the polypropylene resin composition (X) and / or (X ′) include ethylene-α-olefin copolymers such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and ethylene-based resins. Examples include polyethylene resins typified by elastomers and ethylene-vinyl acetate copolymers, and polyolefins such as 1-butene homopolymer, 1-butene-propylene copolymer, and 1-butene-ethylene copolymer. In particular, linear low density polyethylene, ethylene elastomer, and ethylene-vinyl acetate copolymer can be preferably used.

  When the polyolefin resin contains the polypropylene resin composition (X) and / or (X ′), the melt flow rate (MFR) of the polyolefin resin composition (Y) is the component (A) and / or Considering the MFR of (A ′), the MFR of the component (B) and / or (B ′) and the MFR of the third component other than the polypropylene resin composition (X) and / or (X ′) are appropriately determined. It can be adjusted by selecting.

Other characteristics:
The polyolefin resin composition (Y) for deformation-recoverable structure of the present invention preferably has a flexural modulus of 20 to 500 MPa, more preferably 40 to 400 MPa, still more preferably 50 to 300 MPa, and particularly preferably 50. ~ 250 MPa.
When the polyolefin-based resin contains the polypropylene-based resin composition (X) and / or (X ′), the flexural modulus is determined by the component (A) and / or (A ′) and the component (B) or (B The composition can be adjusted to a desired value by appropriately selecting the composition, content ratio, and the content of the following other components.
A flexural modulus within the above range is preferable because it is easy to balance flexibility, ease of deformation, and deformation recovery.

  In addition, the polyolefin resin composition (Y) for deformation-recoverable structure of the present invention preferably has a tensile yield stress of 20 MPa or less, more preferably 15 MPa or less, still more preferably 12 MPa or less, and particularly preferably 10 MPa or less. And most preferably not observed. If the tensile yield stress is within the above range, it is easy to develop deformation recovery properties, which is preferable.

A preferred aspect of the polyolefin resin composition (Y) for a deformable structure according to the present invention is that the polyolefin resin is 1 to 99 parts by weight of the following component (A) and 1 to 99 parts by weight of the following component (B) (however, And a total of 100 parts by weight of component (A) and component (B)).
Component (A): One or more propylene homopolymers and / or propylene-α-olefin copolymers satisfying the following (a1) to (a2).
(A1) The melting peak temperature (Tm) is 121 to 170 ° C.
(A2) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.1 to 500 g / 10 minutes.
Component (B): At least one propylene-α-olefin copolymer satisfying the following (b1).
(B1) It is composed of 51 to 90% by weight of propylene, 10 to 49% by weight of ethylene and / or an α-olefin having 4 to 10 carbon atoms.

  Another preferable aspect of the polyolefin-based resin composition (Y) for a deformable structure according to the present invention is that a part or all of the polypropylene-based resin composition (X) is the above-described (a1) and (a2). 1 to 99 parts by weight of the component (A ′) satisfying and 1 to 99 parts by weight of the component (B ′) satisfying the above (b1) (however, the total amount of (A ′) and (B ′) is 100 parts by weight. Is a polypropylene resin composition (X ′) obtained by sequential polymerization.

[Component (A) or (A ′)]
The component (A) or (A ′) used in the present invention preferably satisfies the above characteristics (a1) and (a2).
Each of the above characteristics will be specifically described below. In addition, a component (A ') originates in the polypropylene resin composition (X') demonstrated below.

Characteristic (a1): Melting peak temperature (Tm)
The melting peak temperature (Tm) of the component (A) or (A ′) used in the present invention is preferably 121 to 170 ° C.
Component (A) or (A ′) is composed of one or more propylene homopolymers and / or propylene-α-olefin copolymers, and in the case of two or more components, two or more components As a blended product, the melting peak temperature may be 121 ° C to 170 ° C.
Examples of the combination of two or more types of component (A) or (A ′) include a case where the component (A) or (A ′) is composed of two or more types of propylene homopolymers or a case where the component (A) or (A ′) is composed of two or more types of propylene-α-olefin copolymers. Examples include one or more types of propylene homopolymer and propylene-α-olefin copolymer.
When the melting peak temperature is in the above range, the structure obtained from the polyolefin resin composition (Y) for deformation-recoverable structure of the present invention can maintain its shape at high temperature, preferably at 121 ° C. or higher. Heat resistance can be expressed, and the restrictions on the use environment are reduced.
A more preferable range of the melting peak temperature is 125 ° C to 170 ° C, more preferably 130 ° C to 170 ° C, and particularly preferably 135 ° C to 170 ° C.

Characteristic (a2): Melt flow rate (MFR: 230 ° C., 2.16 kg load)
The melt flow rate (MFR) of the component (A) or (A ′) used in the present invention is preferably 0.1 to 500 g / 10 minutes.
Component (A) or (A ′) is composed of one or more propylene homopolymers and / or propylene-α-olefin copolymers, and in the case of two or more components, two or more components As the blended product, the MFR may be 0.1 to 500 g / 10 minutes.
Here, MFR is measured according to JIS K7210: 1999 method A, condition M (230 ° C., 2.16 kg load).
When the MFR is in the above range, the load during molding of the polyolefin resin composition (Y) for deformation-recoverable structure of the present invention is reduced, the molding itself becomes easy, and the molding stability is further improved. Properties, particularly molding stability when used for extrusion molding.
A more preferable range of MFR is 1.0 to 500 g / 10 minutes, further preferably 5.0 to 200 g / 10 minutes, and particularly preferably 5.0 to 100 g / 10 minutes.

Other characteristics:
The component (A) or (A ′) used in the present invention preferably satisfies the above characteristics (a1) and (a2), but as the component (A) or (A ′), a propylene-α-olefin copolymer is used. When a polymer is used, component (A) or (A ′) has a propylene content of more than 90% by weight and less than 100% by weight, and an α-olefin content of more than 0% by weight and less than 10% by weight. More preferably.
When a propylene-α-olefin copolymer is used as the component (A) or (A ′), the α-olefin is preferably ethylene and / or butene.
The manufacturing method of a component (A) is not specifically limited, It can select suitably from a commercially available propylene homopolymer and a propylene-alpha-olefin copolymer. Specific examples include the trade name “Novatech PP” manufactured by Nippon Polypro Co., Ltd. and the trade name “Wintech”.

[Component (B) or (B ′)]
Component (B) or (B ′) used in the present invention comprises at least one propylene-α-olefin copolymer that satisfies the above-mentioned characteristic (b1).
The above characteristics will be specifically described below. In addition, a component (B ') originates in the polypropylene resin composition (X') demonstrated below.

Characteristic (b1): Content of propylene and α-olefin Component (B) or (B ′) used in the present invention is 51 to 90% by weight of propylene, ethylene and / or α-olefin 10 having 4 to 10 carbon atoms. It preferably consists of ~ 49% by weight.
When the propylene content is in the above range, the compatibility with the component (A) or (A ′) is high, and the interface is not easily destroyed at the time of deformation. Therefore, the polyolefin-based resin composition for deformation-recoverable structure of the present invention Since the deformation recovery property of the structure obtained from (Y) is less likely to be lowered, and the component (B) or (B ′) is less likely to undergo plastic deformation during deformation, the polyolefin resin composition (Y ), The deformation recovery property of the structure obtained from is less likely to deteriorate.
The preferred range of the propylene content is 60% by weight or more and 90% by weight or less, more preferably 70% by weight or more and 90% by weight or less, still more preferably 80% by weight or more and 90% by weight or less, and particularly preferably 83% by weight. % To 90% by weight.

Other characteristics:
The component (B) or (B ′) used in the present invention preferably satisfies the above characteristic (b1), and the α-olefin is more preferably ethylene and / or butene.
The manufacturing method of a component (B) is not specifically limited, It can select suitably from a commercially available propylene-alpha-olefin copolymer. Specifically, ExxonMobil brand name “Vistamaxx”, Dow Chemical brand name “Versify”, Mitsui Chemicals brand name “Toughmer PN”, “Notio SN”, “Toughmer XM”, Sumitomo Chemical The brand name “Tough Selenium” manufactured by the company may be mentioned.

[Polypropylene resin composition (X)]
The polypropylene resin composition (X) used in the present invention comprises 1 to 99 parts by weight of the above component (A) and / or (A ′) and 1 to 99 parts by weight of the following components (B) and / or (B ′). Consists of parts. However, the total of the component (A) and / or (A ′) and the component (B) and / or (B ′) is 100 parts by weight. In addition, the components (A ′) and (B ′) are derived from the polypropylene resin composition (X ′) described below.
When the content of component (A) and / or (A ′) is in the above range, the structure obtained from the polyolefin resin composition (Y) for deformation-recoverable structure of the present invention is preferably at a high temperature, preferably Since the heat resistance sufficient to maintain the shape in an environment of 121 ° C. or higher can be exhibited, the use environment is less restricted, and plastic deformation is less likely to occur during deformation. Therefore, the polyolefin resin composition of the present invention The deformation recovery property of the structure obtained from (Y) is unlikely to decrease.
The preferred range of the component (A) and / or (A ′) in the polypropylene resin composition (X) and / or (X ′) is 1 to 70 parts by weight, more preferably 10 to 60 parts by weight, More preferably, it is 20-50 weight part.

[Polypropylene resin composition (X ′)]
1 to 99 parts by weight of the component (A ′) satisfying the above (a1) and (a2) and the component (B ′) satisfying the above (b1) in a part or all of the polypropylene resin composition (X) A polypropylene-based resin composition (X ′) obtained by sequentially polymerizing 1 to 99 parts by weight (provided that the total amount of (A ′) and (B ′) is 100 parts by weight) can be used.
The method for producing the polypropylene resin composition (X ′) is not particularly limited, and for example, the method described in JP-A-2005-132799 can be used. Is incorporated herein.
The catalyst for producing the polypropylene resin composition (X ′) is not particularly limited, but from the polypropylene resin composition (X ′), the polyolefin resin composition (Y), and further from the polyolefin resin composition (Y). It is preferable to use a metallocene catalyst because it becomes easy to suppress stickiness of the produced deformable structure.
The polypropylene-based resin composition (X ′) may be appropriately selected from commercially available products, and examples of commercially available products include Nippon Polypro Co., Ltd. trade name “Newcon”, trade name “Wellnex”, and the like. .

[Other ingredients]
Various other components such as other resins or additives are added to the polyolefin resin composition (Y) for deformation-recoverable structure of the present invention within the range not impairing the object of the present invention. Can do.

(1) Additive In the polyolefin resin composition (Y) for deformation-recoverable structure of the present invention, an additive such as an antioxidant that can be added to the polyolefin resin is appropriately added as long as the effects of the present invention are not hindered. Can be contained.
Specifically, 2,6-di-t-butyl-p-cresol (BHT), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (BASF Japan) And trade name “IRGANOX 1010”) and n-octadecyl-3- (4′-hydroxy-3,5′-di-t-butylphenyl) propionate (trade name “IRGANOX 1076” manufactured by BASF Japan). Phenol stabilizers such as bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and tris (2,4-di-t-butylphenyl) phosphite Lubricants represented by higher fatty acid amides such as oleic acid amide and erucic acid amide, higher fatty acid esters and silicone oils, Antistatic agent represented by glycerin ester, sorbitan acid ester, polyethylene glycol ester and the like of fatty acid having 8 to 22 carbon atoms, sorbitol nucleating agent (for example, trade name “Gelol MD” manufactured by Shin Nippon Rika Co., Ltd.), aroma Group phosphates (for example, trade names “NA-21” and “NA-11” manufactured by ADEKA), trade names “Millad” series manufactured by Milliken, trade names “Hyperform” manufactured by Milliken, talc, high-density polyethylene Nucleating agents represented by, such as anti-blocking agents represented by silica, calcium carbonate, talc, etc., molecular weight regulators represented by organic peroxides, crosslinking aids, higher fatty acid metal salts such as calcium stearate, Neutralizers, light stabilizers, UV absorbers, metal inertness typified by hydrotalcite , Peroxides, fillers, antibacterial and antifungal agents, fluorescent whitening agents, antifogging agents, colorants, pigments, natural oils, synthetic oils, waxes, etc. may be added, Amount.

  As antibacterial and antibacterial agents, the brand name “Novalon” manufactured by Toagosei Co., Ltd., the brand name “Zeomic” manufactured by Sinanen Zeomic Co., the brand name “Bacte Killer” manufactured by Fuji Chemical Co., Ltd., and the brand name “Ion Pure” manufactured by Ishizuka Glass Examples include silver antibacterial agents, organic antibacterial agents exemplified by trade name “Royal Guard” manufactured by ADEKA and trade name “Wasaolo” manufactured by Mitsubishi Chemical Foods, Inc. The use of antibacterial agents is preferred. The content of the antibacterial agent and the antibacterial agent may be appropriately adjusted according to the desired antibacterial and antibacterial performance, but is about 0.1 to 10% by weight in the polyolefin resin composition (Y) of the present invention. It can be exemplified.

(2) Other polymers In addition, in the polyolefin resin composition (Y) for deformation-recoverable structure of the present invention, an elastomer or alicyclic hydrocarbon that can be added to the polyolefin resin as long as the effects of the present invention are not hindered. A modifier such as a resin can be appropriately contained.
The content of the other polymer is not particularly limited as long as the effects of the present invention are not hindered, but is usually 100 parts by weight or less with respect to 100 parts by weight of the polyolefin resin composition (Y).

  Specifically, petroleum resins, terpene resins, rosin resins, coumarone indene resins, and alicyclic hydrocarbon resins represented by hydrogenated derivatives thereof, for example, trade name “Apel” manufactured by Mitsui Chemicals, Inc. A cyclic olefin (co) polymer represented by a trade name “TOPAS” manufactured by Polyplastics Co., Ltd., a trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd., or “ZEONEX” may be added.

  Further, a styrene-based elastomer can be added, and the styrene-based elastomer can be appropriately selected from commercially available ones. For example, as a hydrogenated product of a styrene-butadiene block copolymer, Kraton “Clayton G” from Polymer Japan Co., Ltd., “Tough Tech” from Asahi Kasei Chemicals, Inc., “Septon” from Kuraray Co., Ltd. as a hydrogenated product of styrene-isoprene block copolymer. As a hydrogenated product of styrene-vinylated polyisoprene block copolymer, Kuraray Co., Ltd. under the trade name “Hibler”, and as a hydrogenated product of styrene-butadiene random copolymer, “Dynalon” from JSR Co., Ltd. The product is sold under the product name. It may be.

[Production Method of Polyolefin Resin Composition (Y)]
The polyolefin resin composition (Y) of the present invention is an arbitrary polyolefin, preferably the components (A) and (B) constituting the above-described polypropylene resin composition (X), and / or the above-mentioned polypropylene resin. Composition (X ′), halogenated flame retardant (D) and, if necessary, flame retardant aid (E) and other additives, polymer components in Henschel mixer, V blender, ribbon blender, tumbler blender, etc. Can be mixed and obtained. Further, if necessary, it can also be obtained by a method of melt-kneading with a kneader such as a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer after the mixing step.
Moreover, each component may be mixed and / or melt-kneaded at the same time, or may be mixed and / or melt-kneaded after making a part of the master batch.

[Deformation recovery structure]
The deformation-recoverable structure comprising the polyolefin-based resin composition (Y) for a deformation-recoverable structure of the present invention has excellent flame retardancy, does not cause problems during molding, and is further subjected to a continuous load. After being continuously deformed, it has excellent deformation recovery properties when the load is removed.
The shape, forming method, and use of the structure are not particularly limited, but are used for applications that require deformation recovery when the load is removed after being continuously deformed by a continuous load.
For example, by injection molding or extrusion molding, a flat body, rod shape, spiral shape, or a molded body having an irregular cross section or hollow cross section is applied to an application similar to a buffer spring, or applied to a support such as a cushion. Cases.
Moreover, it can also be used as one component of the structure which has a core-sheath structure or has a side-by-side structure.
As an example of a suitable application form, a continuous linear body composed of a plurality of strands obtained by extrusion is twisted into a three-dimensional random loop, and at least a part of contact portions of the plurality of loops is fused. Examples thereof include a network structure having a three-dimensional network structure, and a structure made of a fiber assembly exemplified in Japanese Patent Application Laid-Open No. 2012-112072, and Japanese Patent Application Laid-Open No. 5-163657.

As a particularly preferred application form, a continuous linear body made of a plurality of strands obtained by extrusion molding is twisted into a three-dimensional random loop, and at least a part of contact portions of the plurality of loops is fused. Examples thereof include a network structure having a three-dimensional network structure.
The net-like structure may be used, for example, as a bedding such as a bed, or as a cushioning material for home use, seats for vehicles, ships, and aircraft. Flammability is required. Moreover, since a person lies down or sits down for a long time, it is continuously deformed by a continuous load. In addition, after removing the load, in order to use it again as a cushioning material, it is necessary to recover the deformation to such an extent that there is no practical problem.
Furthermore, since there are cases where a load is applied at a high temperature (for example, 70 ° C.) in an automobile cushion, a cushioning part, a bed cushion with a heating function, etc., a deformation recovery property at a high temperature is also required.
In recent years, there has been a need in hospitals to clean the cushion itself, and in some cases, sterilization, and resistance to steam sterilization at a high temperature, preferably 121 ° C. or higher, is required. It can be said that it is a particularly suitable application form as a deformation recoverable thermal structure in which the polypropylene resin composition (X) and / or (X ′) is applied to the polyolefin resin composition (Y) for a structure.

  In addition to the above, for example, for the purpose of improving drainage, improving air permeability, retaining earth and sand, etc. A deformation recoverable structure using the polyolefin resin composition (Y) for recoverable structure can be suitably used. In these applications, for example, since it is assumed that the outdoor environment is in a high temperature environment during the daytime and is deformed by the load of a person, vehicle, animal, etc., the polyolefin resin composition (Y) is particularly preferable. By using a deformation recoverable structure to which the polypropylene resin composition (X) and / or (X ′) is applied, it is expected to easily restore the original shape. Furthermore, since it has excellent shape retention at high temperatures, preferably at 121 ° C. or higher, it can be applied to cleaning with a steam cleaner. Moreover, since the structure using the polyolefin-based resin composition (Y) of the present invention is flexible, it has followability to various shapes and can be expected to expand the application range.

As a method for producing the network structure, a known method may be appropriately employed. For example, Japanese Patent Application Laid-Open No. 2013-040437, Japanese Patent Application Laid-Open No. 7-173753, Japanese Patent No. 5549438, and Japanese Patent No. 5559436. Although the method of patent 5454733 is mentioned, it is not limited to these.
In addition, when applied to an application in which a load under high temperature is applied, it is molded at a temperature not higher than a temperature at which the shape of the structure can be maintained, preferably at a temperature not lower than an assumed use condition temperature and not higher than a temperature at which the shape of the structure can be maintained. It is preferable to adjust the state of the structure for about 10 seconds to 1 day since deformation recovery at high temperatures is more likely to be improved.
In the case of the structure of the present invention, for example, temperatures of 40 ° C., 50 ° C., 60 ° C., 70 ° C., 80 ° C., 90 ° C., 100 ° C., 110 ° C., 120 ° C., 130 ° C., 140 ° C., 150 ° C., 160 ° C. Conditions can be exemplified.

In addition, when the molded body is applied to a use similar to a buffer spring, when applied to a support such as a cushion, and further, in any case of applying the network structure to a cushion material, A deformation form that is continuously deformed by a continuous load is a bending deformation.
For example, in the case of the network structure, the seemingly deformed form tends to be seen as a compressive deformation. However, if attention is paid to each filament constituting the network structure, the deformed form is a bending deformation.
Therefore, it is possible to sufficiently analogize the deformation recoverability of the various structures listed in the above example by continuously bending and deforming with the continued load, and then evaluating the deformation recovery when the load is removed. it can.

[Flame retardance]
The deformation recovery structure obtained from the polyolefin resin composition (Y) for deformation recovery structure of the present invention has excellent flame retardancy.
Various methods for evaluating flame retardancy are known, but according to Reference 1 (Plastic Vol 52, No. 3, P102, 2001), representative methods include UL-94 test method, oxygen An exponential method (JIS K7201) may be mentioned.
Among these test methods, the oxygen index method can express the comparison between materials by numerical values, and is considered appropriate as a method for evaluating the flame retardancy of the deformation-recoverable structure of the present invention in which various shapes are assumed. Therefore, in the present invention, flame retardancy is evaluated by the oxygen index method.
According to the reference 1, those having an oxygen index exceeding 21 are considered to be difficult to burn at an oxygen concentration (21%) in the air, and those having 27 or more are generally considered to be self-extinguishing. Yes. Therefore, the oxygen index of the polyolefin resin composition (Y) for deformation-recoverable structure of the present invention exceeds 21, preferably 25 or more, more preferably 27 or more, and particularly preferably 30 or more.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.
The polyolefin resin compositions used in the examples and comparative examples, their constituent components, and various physical properties of the deformation recoverable structures were measured and evaluated according to the following evaluation methods.

[Physical properties of each resin]
(1) Melt flow rate (MFR, unit: g / 10 minutes):
Measured in accordance with JIS K7210: 1999, Method A, Condition M (230 ° C., 2.16 kg load).
In addition, about (A-1) used in the Example, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl) is used as an antioxidant with respect to 100 parts by weight of (A-1). -4′-hydroxyphenyl) propionate] methane (trade name “IRGANOX1010”, manufactured by BASF Japan Ltd.) 0.05 parts by weight, tris (2,4-di-t-butyl) which is a phosphite antioxidant Phenyl) phosphite (trade name “IRGAFOS 168”, manufactured by BASF Japan Ltd.) 0.05 parts by weight was charged into a Henschel mixer, mixed at 750 rpm for 1 minute at room temperature, and then a single screw extruder having a screw diameter of 30 mm. The melted resin is melt-kneaded at a discharge rate of 6 kg / hr and an extruder temperature of 200 ° C., and the molten resin extruded from the strand die is cooled and solidified in a cooling water tank. The strand was taken out and measured using pellets obtained by cutting the strand into a diameter of about 2 mm and a length of about 3 mm using a strand cutter.
(2) Melting peak temperature (melting point) (Tm, unit: ° C.):
Using a differential scanning calorimeter (DSC), once the temperature was raised to 200 ° C. and the heat history was erased, the temperature was lowered to 40 ° C. at a temperature lowering rate of 10 ° C./min, and the temperature rising rate was 10 ° C./min again. The temperature at the top of the endothermic peak at the time of measurement was taken as the melting peak temperature (melting point) (Tm).
In addition, about (A-1) used in the Example, it measured using the pellet obtained by the method similar to the said (1).

(3) α-olefin content (unit: wt%)
About the commercially available propylene-alpha-olefin copolymer component (B), the value of the catalog description published by the manufacturer was used.
About component (A ') and (B') in polypropylene resin composition (X '), it measured by the method as described in Unexamined-Japanese-Patent No. 2005-132799.
The components (A ′) and (B ′) correspond to the components (A) and (B) described in JP-A-2005-132979, respectively.
(4) Content of the components (A ′) and (B ′) in the polypropylene resin composition (X ′) (unit: wt%)
The measurement was performed by the method described in JP-A-2005-132979 described above.
The components (A ′) and (B ′) correspond to the components (A) and (B) described in JP-A-2005-132979, respectively.

(5) Residual strain (unit:%)
(I) Preparation of sample Polyolefin resin composition (Y) was molded into a sheet by a compression molding method.
Spacers used: length 200 mm, width 200 mm, thickness 1 mm.
Compression molding conditions:
(A) Preheating process: preheating time 7 minutes, preheating temperature 200 ° C., preheating pressure 0.1 MPa
(A) Pressurization step: pressurization time 3 minutes, pressurization temperature 200 ° C., pressurization pressure 8 MPa
(C) Cooling step: Cooling time 3 minutes, cooling temperature 30 ° C., cooling pressure 12 MPa
After the sheet obtained by molding under the above-mentioned conditions is adjusted in a gear oven under conditions of 100 ° C. and 1 hour, and further subjected to conditions under conditions of 23 ° C. and 50% relative humidity for 48 hours or more. Then, a structure having a length of 140 mm, a width of 10 mm, and a thickness of 1 mm was prepared by cutting with a cutter knife and subjected to the following test.
(Ii) Constant displacement bending test Two glass plates having a length of 220 mm, a width of 150 mm, and a thickness of 3 mm were arranged in parallel on a work table with an interval of 100 mm.
A marked line is attached to each position of 20 mm from both ends in the length direction of the structure manufactured by the above-described method (that is, the distance between marked lines is 100 mm), and the structure is attached to each of the opposite end portions of the glass plate. The structure was placed so that the marked lines coincided with each other, and the portion where the structure and the glass plate overlap was firmly fixed with cellophane tape. The glass plates on which the structures were fixed were overlapped through a spacer having a thickness of 50 mm so that the surfaces fixed with cellophane tape faced each other and the four corners of the glass plates overlapped.
In this state, the structure is bent so that the gap between the marked lines becomes 50 mm through the space, and the deformation amount of 50% is given to the original length between the marked lines of 100 mm. . In addition, 3 sheets per sample and 1 to 5 types of samples were fixed to a set of glass plates.
Then, in the gear oven adjusted to 23 ° C. and 50% relative humidity or 40 ° C. or in the gear oven adjusted to 70 ° C. for 22 hours, the same conditions are applied. Then, the vicinity of the marked line of the structure attached to the glass plate was cut with sharp scissors or a cutter knife to remove the load.
The cut structure was immediately brought into a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity, and the condition was adjusted for 30 minutes. The cut structure remained bent to some extent, and the distance between both ends cut in the bent state was measured using a ruler. This distance was set to L1.
Further, the bending deformation of the structure cut on the workbench was extended so as to be parallel to the workbench, and the lengths of the cut ends were measured using a ruler. This length was defined as L0.
Residual strain was determined using the following formula. Residual strain is an index of deformation recovery, and the smaller the value, the better the deformation recovery.
Residual strain = (L0−L1) / L0 × 100 (%)

(6) Flexural modulus (unit: MPa)
The flexural modulus of the injection molded product was measured according to JIS K7171.
(7) Tensile yield stress (unit: MPa)
The tensile yield stress of the injection molded product was measured according to JIS K7162.

(8) Heat resistance The structure 140 mm long, 10 mm wide and 1 mm thick obtained in the preparation of the sample described above (conditions are adjusted at 23 ° C. and 50% relative humidity) from both ends in the length direction. , Each marked with a marked line at a position of 20 mm (that is, distance between marked lines is 100 mm).
The end of the structure was sandwiched between clips and placed in a gear oven adjusted to 100 ° C. or 121 ° C. in a suspended state, and the state was adjusted for 15 minutes.
After completion of the condition adjustment, it was taken out from the gear oven, immediately brought into a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity, and the length (L2) between the marked lines was immediately measured for the unmelted structure.
Those that contract during the condition adjustment have an L2 of less than 100 mm, and those that sag due to expansion or dead weight have an L2 greater than 100 mm. For those melted by the above-mentioned condition adjustment, there was no heat resistance, and for those not melted, the absolute value of the amount of change (%) from the original distance between the marked lines of 100 mm was used as the heat resistance index, and the value was The smaller the value, the better the heat resistance.
(9) Flame retardance JIS K7201-2 using the structure of 140 mm in length, 10 mm in width and 1 mm in thickness obtained in the above-mentioned sample preparation section (conditions are adjusted at 23 ° C. and 50% relative humidity). The test was carried out in accordance with the procedure based on Table 3, 2007, test piece shape III, ignition method A method. The oxygen concentration was changed at intervals of 0.5% (volume fraction), and the oxygen concentration not exceeding the specification shown in Table 3 of JIS K7201-2 2007 was used as the oxygen index in the present invention. Those with an oxygen index of 21 are difficult to burn in the air.
(10) Failure during molding In the above-mentioned sample preparation section, the presence or absence of discoloration (so-called discoloration) was observed when the polyolefin resin composition (Y) was molded into a sheet by the compression molding method. No change was indicated by ○, and change (with discoloration) was indicated by ×.
(11) Odor Using the structure of 140 mm in length, 10 mm in width and 1 mm in thickness obtained in the above-mentioned sample preparation section (condition adjustment conditions are 23 ° C., 50% relative humidity) Judged as follows. Equivalent to those that do not contain flame retardant ○, somewhat odor △, odor ×.

[Components of Polypropylene Resin Composition (X ′)]
The resin obtained in the following production example (X′-1) was used.

(Production Example X′-1)
(I) Preparation of prepolymerized catalyst (chemical treatment of silicate)
To a 10-liter glass separable flask with a stirring blade, 3.75 liters of distilled water was added slowly followed by 2.5 kg of concentrated sulfuric acid (96%). At 50 ° C., 1 kg of montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 25 μm, particle size distribution = 10-60 μm) was dispersed, heated to 90 ° C., and maintained at that temperature for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake.
7 liters of distilled water was added to this cake to reslurry it, and then filtered. This washing operation was performed until the pH of the washing liquid (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g.

(Drying silicate)
The silicate previously chemically treated was dried with a kiln dryer.
Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical, inner diameter 50 mm, heating zone 550 mm (electric furnace)
Rotating speed with lifting blade: 2rpm
Tilt angle: 20/520
Silicate supply rate: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Countercurrent drying temperature: 200 ° C. (powder temperature)

(Preparation of catalyst)
An autoclave with an internal volume of 16 liters equipped with a stirring and temperature control device was thoroughly replaced with nitrogen. 200 g of dry silicate was introduced, 1160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added, and the mixture was stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare 2,000 ml of silicate slurry.
Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the silicate slurry prepared above and reacted at 25 ° C. for 1 hour. In parallel, (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium 2,180 mg (0.3 mM) and mixed heptane 870 ml Then, 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. After stirring for 1 hour, 5,000 ml was added with mixed heptane. Prepared.

(Prepolymerization / washing)
Subsequently, the temperature in the tank was raised to 40 ° C., and when the temperature was stabilized, propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours.
After completion of the prepolymerization, the remaining monomer was purged, the stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted to 2,400 ml. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 5,600 ml of mixed heptane were further added, stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then the supernatant was added to 5,600 ml. Excluded. This operation was further repeated 3 times.
When the component analysis of the supernatant liquid was performed, the concentration of the organoaluminum component was 1.23 mmol / L, the Zr concentration was 8.6 × 10 ⁻⁶ g / L, and the abundance in the supernatant with respect to the amount charged. Was 0.016%. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure. A prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained.
Using this prepolymerized catalyst, a propylene-ethylene block copolymer was produced according to the following procedure.

(Ii) First polymerization step A horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade was sufficiently dried, and the inside was sufficiently replaced with nitrogen gas. While stirring at a rotation speed of 30 rpm in the presence of a polypropylene powder bed, 0.568 g / hr of the prepolymerized catalyst prepared as described above (as the amount of solid catalyst excluding the prepolymerized powder) in the upstream part of the reactor, Triisobutylaluminum was continuously fed at 15.0 mmol / hr. The monomer mixed gas is continuously reacted so that the reactor temperature is maintained at 65 ° C., the pressure is maintained at 2.1 MPaG, the ethylene / propylene molar ratio in the reactor gas phase is 0.07, and the hydrogen concentration is 100 ppm. It was made to distribute | circulate in a container and vapor phase polymerization was performed.
The polymer powder produced by the reaction was continuously extracted from the downstream portion of the reactor so that the amount of the powder bed in the reactor was constant. At this time, the amount of the polymer extracted when the steady state was reached was 10.0 kg / hr.
When the propylene-ethylene random copolymer obtained in the first polymerization step was analyzed, the MFR was 6.0 g / 10 min and the ethylene content was 2.2 wt%.

(Iii) Second polymerization step The propylene-ethylene random copolymer extracted from the first step was continuously supplied to a horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade. While stirring at a rotational speed of 25 rpm, the temperature of the reactor is maintained at 70 ° C., the pressure is maintained at 2.0 MPaG, and the ethylene / propylene molar ratio in the gas phase in the reactor is 0.453, and the hydrogen concentration is 330 ppm. A monomer mixed gas was continuously passed through the reactor to carry out gas phase polymerization.
The polymer powder produced by the reaction was continuously extracted from the downstream portion of the reactor so that the amount of the powder bed in the reactor was constant. At this time, oxygen was supplied as an activity inhibitor so that the amount of polymer extracted was 17.9 kg / hr, and the polymerization reaction amount in the second polymerization step was controlled. The activity was 31.4 kg / g-catalyst.
Various analysis results of the polypropylene resin (X′-1) thus obtained are shown in Table 1.

  Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) as an additive (antioxidant) was added to 100 parts by weight of the obtained polypropylene resin (X′-1). ) Propionate] methane (trade name “IRGANOX1010”, manufactured by BASF Japan Ltd.) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite (product), which is a phosphite antioxidant 0.05 parts by weight of “IRGAFOS 168” (manufactured by BASF Japan Ltd.) was charged into a Henschel mixer, mixed at 750 rpm for 1 minute at room temperature, and then KZW-25 extruder manufactured by Technobel with a screw diameter of 25 mm. From a strand die, melt kneaded at a screw speed of 250 rpm, a discharge rate of 15 kg / hr, and an extruder temperature of 200 ° C. The melted resin is taken out while being cooled and solidified in a cooling water tank, and the strand is cut into a diameter of about 2 mm and a length of about 3 mm using a strand cutter to obtain a polypropylene resin composition (X′-1). It was.

[Propylene Homopolymer (A)]
(A-1) Propylene homopolymer powder obtained by a known method (propylene homopolymer, MFR 12 g / 10 min, Tm = 161 ° C.)

[Propylene-α-olefin copolymer (B)]
(B-1) manufactured by ExxonMobil, trade name “Vistamaxx 6202” (propylene-ethylene copolymer, MFR 20 g / 10 min, ethylene content 15% by weight)

[Flame Retardant (D)]
(D-1) Halogen-based flame retardant, manufactured by Suzuhiro Chemical Co., Ltd., trade name “Fire Cut P-680” (2,2-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) propane)
(D-2) Flame retardants other than halogen flame retardants, manufactured by ADEKA Corporation, trade name “ADK STAB FP-2200” (phosphate flame retardants)

[Flame Retardant (E)]
(E-1) Flame retardant aid, Suzuhiro Chemical Co., Ltd., trade name “Fire Cut AT-3” (antimony trioxide)

[Example 1]
40% by weight of the polypropylene resin composition (X′-1) obtained in Production Example X′-1, 10% by weight of a propylene homopolymer (A-1), and a propylene-α-olefin copolymer (B -1) 50% by weight was blended with a Henschel mixer to obtain a polypropylene resin composition (X-1). Further, 2 parts by weight of (D-1) and 1 part by weight of flame retardant aid (E-1) are added as halogen-based flame retardants to 100 parts by weight of the polypropylene resin composition (X-1). Blended with a mixer, melt-kneaded with a twin-screw extruder, taken out while the molten resin extruded from the strand die was cooled and solidified in a cooling water tank, and the strand was made into a diameter of about 3 mm and a length of about 2 mm using a strand cutter. By cutting, a polyolefin resin composition (Y-1) pellet was obtained.
The twin screw extruder is KZW-25 manufactured by Technobel, the screw speed is 400 RPM, the discharge rate is 20 kg / h, and the kneading temperature is 80, 160, 190 from the bottom of the hopper (the same temperature up to the die outlet). ) C setting.
The obtained pellets were formed into a sheet shape by the compression molding method by the method described above, and a structure was obtained by the method described above.
The evaluation results of the obtained structure are summarized in Table 2.

[Example 2]
In Example 1, the same operation as in Example 1 was performed except that (D-1) was changed to 3 parts by weight and the flame retardant aid (E-1) was changed to 1.5 parts by weight as the halogen-based flame retardant. It was. (The obtained polyolefin resin composition was defined as (Y-2).)
The evaluation results are summarized in Table 2. Compared with Example 1, the flame retardancy was further improved.

[Comparative Example 1]
In Example 1, the same operation as in Example 1 was performed except that the halogen-based flame retardant and the flame retardant aid were not added. (The obtained polyolefin resin composition was defined as (Y-3).)
The evaluation results are summarized in Table 2. Compared with Example 1, the flame retardancy was worsened, and the oxygen index was less than 21.

[Comparative Example 2]
40% by weight of the polypropylene resin composition (X′-1) obtained in Production Example X′-1, 10% by weight of a propylene homopolymer (A-1), and a propylene-α-olefin copolymer (B -1) 50% by weight was blended with a Henschel mixer to obtain a polypropylene resin composition (X-1). Further, 11.1 parts by weight of (D-2) as a flame retardant other than the halogen flame retardant is added to 100 parts by weight of the polypropylene resin composition (X-1), blended with a Henschel mixer, and biaxial. Polyolefin resin composition by melting and kneading in an extruder, taking out the molten resin extruded from the strand die while cooling and solidifying in a cooling water tank, and cutting the strand into a diameter of about 3 mm and a length of about 2 mm using a strand cutter A product (Y-4) pellet was obtained.
The twin screw extruder is KZW-25 manufactured by Technobel, the screw speed is 400 RPM, the discharge rate is 20 kg / h, and the kneading temperature is 80, 160, 190 from the bottom of the hopper (the same temperature up to the die outlet). ) C setting.
The obtained pellets were formed into a sheet shape by the compression molding method by the method described above, and a structure was obtained by the method described above.
The evaluation results of the obtained structure are summarized in Table 2. Although the oxygen index exceeded 21, the resin at the peripheral edge of the spacer was discolored during molding by the compression molding method, and a burnt substance was generated. Compared to the examples, the deformation recovery was slightly inferior.

[Comparative Example 3]
In Comparative Example 2, the same operation as in Comparative Example 2 was performed except that (D-2) was changed to 25 parts by weight as a flame retardant other than the halogen flame retardant. (The obtained polyolefin resin composition was designated as (Y-5).)
The evaluation results of the obtained structure are summarized in Table 2. Although the oxygen index exceeded 21, the resin at the peripheral edge of the spacer was discolored during molding by the compression molding method, and a burnt substance was generated. Further, the deformation recovery was slightly inferior to the examples.

  The polyolefin-based resin composition for deformation-recoverable structure of the present invention provides a structure that does not cause defects such as burns during molding, exhibits excellent flame retardancy, and further exhibits excellent deformation recovery Because it can, industrial applicability is high.

Claims (12)

It possesses the following characteristics (y1) and (y2), and the following component (A ') 1 to 99 parts by weight and the following component (B') 1 to 99 parts by weight (however, component (A ') and component (B 1) The halogen-based flame retardant (D) is added in an amount of 1 to 100 parts by weight of the polyolefin-based resin containing the polypropylene-based resin composition (X ′), which is a sequential polymer composed of 100 parts by weight of the total of “)” . A polyolefin resin composition for deformation-recoverable structures, containing 15 parts by weight.
(Y1) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 1.0 to 100 g / 10 minutes.
(Y2) Melting peak temperature (Tm) is 60-170 degreeC.
Component (A ′): One or more propylene homopolymers and / or propylene-α-olefin copolymers satisfying the following (a1) to (a2).
(A1) The melting peak temperature (Tm) is 121 to 170 ° C.
(A2) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.1 to 500 g / 10 minutes.
Component (B ′): at least one propylene-α-olefin copolymer satisfying the following (b1).
(B1) Being composed of more than 70% by weight of propylene and 90% by weight or less, 10% by weight or more and less than 30% by weight of ethylene and / or a C 4-10 α-olefin.   The polyolefin resin composition for deformation-recoverable structure according to claim 1, further comprising 0.1 to 10 parts by weight of a flame retardant aid (E) with respect to 100 parts by weight of the polyolefin resin. .   The polyolefin resin composition for deformation-recoverable structure according to claim 1, wherein the halogen flame retardant is a bromine flame retardant. The polyolefin resin for deformation-recoverable structure according to any one of claims 1 to 3, wherein the polypropylene resin composition (X ') is a metallocene polypropylene resin composition which is a sequential polymer. Composition. The component (B ') is at least one propylene-α-olefin copolymer composed of 83 to 90% by weight of propylene and 10 to 17% by weight of ethylene . The polyolefin resin composition for deformation recoverable structures according to any one of the above. A deformation recoverable structure comprising the polyolefin resin composition for a deformable structure according to any one of claims 1 to 5 . The deformable structure is formed by twisting a continuous linear body made of a plurality of strands obtained by extrusion molding into a three-dimensional random loop shape and fusing at least a part of contact portions of the plurality of loops. The deformation-recoverable structure according to claim 6 , which has a three-dimensional network structure. 1 to 99 parts by weight of the following component (A ′) and 1 to 99 parts by weight of the following component (B ′) (provided that the component (A ′) and the component (B) 1) The halogen-based flame retardant (D) is added in an amount of 1 to 100 parts by weight of the polyolefin-based resin containing the polypropylene-based resin composition (X ′), which is a sequential polymer composed of 100 parts by weight of the total of “)”. A deformation recoverable structure comprising a polyolefin resin composition containing 15 parts by weight,
A network structure having a three-dimensional network structure in which a continuous linear body composed of a plurality of strands obtained by extrusion is twisted into a three-dimensional random loop, and at least a part of contact portions of the plurality of loops is fused. A deformation-recoverable structure characterized by being a body.
(Y1) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 1.0 to 100 g / 10 minutes.
(Y2) Melting peak temperature (Tm) is 60-170 degreeC.
Component (A ′): One or more propylene homopolymers and / or propylene-α-olefin copolymers satisfying the following (a1) to (a2).
(A1) The melting peak temperature (Tm) is 121 to 170 ° C.
(A2) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.1 to 500 g / 10 minutes.
Component (B ′): at least one propylene-α-olefin copolymer satisfying the following (b1).
(B1) Propylene is 51 wt% or more and 90 wt% or less, ethylene and / or α-olefin having 4 to 10 carbon atoms is 10 wt% or more and 49 wt% or less. The deformation-recoverable structure according to claim 8, further comprising 0.1 to 10 parts by weight of a flame retardant aid (E) with respect to 100 parts by weight of the polyolefin-based resin. The deformation recoverable structure according to claim 8 or 9, wherein the halogen flame retardant is a bromine flame retardant. The deformation recoverable structure according to any one of claims 8 to 10, wherein the polypropylene resin composition (X ') is a metallocene polypropylene resin composition which is a sequential polymer. The component (B ') is at least one propylene-α-olefin copolymer composed of 83 to 90% by weight of propylene and 10 to 17% by weight of ethylene. The deformation recoverable structure according to any one of the above.