JP6875833B2 - A silane-modified polyolefin composition for a three-dimensional network fiber assembly, a silane crosslinked polypropylene composition for a three-dimensional network fiber assembly, a silane-modified polyolefin composition for a three-dimensional network fiber assembly, and a three-dimensional network fiber using these. Molded body for aggregate, crosslinked molded body for three-dimensional reticulated fiber aggregate, and three-dimensional reticulated fiber aggregate - Google Patents

Description

The present invention relates to silane-modified polyolefins, silane-crosslinked polyolefins, and silane-modified polyolefin compositions, and molded articles, crosslinked molded articles, and three-dimensional network fiber aggregates using these.

In recent years, furniture using a three-dimensional net-like fiber aggregate obtained by extruding a thermoplastic resin into a loop as a cushioning material such as a cushioning material, and bedding such as pillows and bed mats have become widespread.

This three-dimensional network fiber assembly is generally manufactured as follows. That is, a thermoplastic resin such as polyethylene is melted in an extruder, and the melted resin is extruded from a die having a large number of holes to form a strand. A water tank is provided below the die, and when the strands naturally flow down and land in the water tank, and the strands stay in the water, the resin is solidified by cooling with water, and a three-dimensional network with loop-like entanglement. A fiber aggregate is produced (Patent Document 1). As the thermoplastic resin used for molding, ethylene / α-olefin copolymers, polyurethane foams, polyesters and the like have been studied.

In cushioning materials such as bedding using a three-dimensional network fiber aggregate made of a thermoplastic resin, a load causes strain in the compression and tension directions of the fiber, and this strain occurs for a long time or repeatedly to cause the fiber aggregate. The cushioning material does not recover its original thickness and is gradually crushed in the compression direction to impair the cushioning property, which is a problem. It is known that settling becomes remarkable at high temperatures, and when heated bedding such as an electric blanket is used, problems such as partial deformation of the bedding occur. These are due to the fact that the thermoplastic resin constituting the three-dimensional network fiber aggregate flows or plastically deforms under a load at a high temperature.

Therefore, in order to improve the heat resistance, which is a major weak point of the polyethylene resin, a graft reaction product obtained by grafting an ethylenically unsaturated silane compound to a specific ethylene / α-olefin copolymer polymerized by a metallocene catalyst. And a polyethylene-based resin composition for a three-dimensional network structure containing a silanol condensation catalyst has been proposed (Patent Document 2).

On the other hand, in order to provide a three-dimensional network fiber aggregate (three-dimensional network fiber aggregate) having better chemical resistance and low odor, a specific propylene / α-olefin can be used instead of polyurethane foam or polyester. It has been proposed to use a polymer (Patent Document 3). Further, in order to provide a three-dimensional network fiber aggregate having better chemical resistance and high heat resistance and low odor, a polymer alloy containing a specific propylene-based polymer and a propylene homopolymer is used. Has been proposed (Patent Document 4).

International Publication No. 2012/035736 Pamphlet Japanese Unexamined Patent Publication No. 2013-181117 Japanese Patent No. 5873225 Japanese Patent No. 5894716

However, in the technique of Patent Document 2, in order to secure special moldability such as thermal adhesiveness, a specific ethylene / α-olefin copolymer having a low melting point and a relatively small molecular weight due to its suitability for the molding method is used. It is premised on the use of coalescence. Therefore, it is difficult to secure sufficient heat resistance, the shape retention under high temperature becomes insufficient, and problems such as settling and deformation still occur.

On the other hand, although the techniques of Patent Documents 3 and 4 have an improving effect on thermal deformation and settling at high temperatures, the improving effect is not sufficient, and the settling after repeated load is still significantly depressed or settled. It was found that there is a risk of deformation. Further, the techniques of Patent Documents 3 and 4 presuppose the use of a specific metallocene-based propylene copolymer or a specific polymer alloy containing such a metallocene-based propylene copolymer and a propylene homopolymer.

The present invention has been made in view of the above circumstances, and is a silane-modified polyolefin having excellent heat resistance and shape retention, which can realize a three-dimensional network fiber aggregate having excellent heat resistance deformation and shape restoration. It is an object of the present invention to provide a silane crosslinked polyolefin, a silane-modified polyolefin composition, and a molded article, a crosslinked molded article, a three-dimensional network fiber aggregate, and the like using the same.

It should be noted that the present invention is not limited to the purpose described here, and it is an action and effect derived by each configuration shown in the embodiment for carrying out the invention described later, and it is also possible to exert an action and effect that cannot be obtained by the conventional technique. It can be positioned as another purpose.

As a result of intensive research to achieve the above object, the present inventors have excellent heat resistance and shape retention of modified polyolefin containing a specific modified polypropylene, and by using this, heat resistance. Further, they have found that a three-dimensional network fiber aggregate having excellent shape retention can be realized, and have completed the present invention. That is, the present invention provides various specific aspects shown below.

[1] A silane-modified polyolefin containing at least a silane-modified polypropylene obtained by grafting an alkoxysilane to a propylene-based copolymer and having one of the melting point peaks measured by a differential scanning calorimeter (DSC) of 110 ° C. or higher.
[2] The silane-modified polyolefin according to [1], which further contains a silane-modified polyethylene obtained by grafting an alkoxysilane to an ethylene-based (co) polymer.
[3] The silane-modified polyolefin according to [1] or [2], wherein the amount of the alkoxysilane introduced is 0.1 to 5% by mass with respect to the total amount of the silane-modified polyolefin.
[4] Any of [1] to [3] in which the melt flow rate (measured according to MFR, JIS K7210 (1999) at a temperature of 230 ° C. and a load of 2.16 kg) is 2 to 50 g / 10 minutes. The silane-modified polyolefin according to item 1.
[5] The silane-modified polyolefin according to any one of [1] to [4], wherein the alkoxysilane is a polymerization residue of an unsaturated silane compound represented by the following formula (1).
R-Si (R') ₃ ... (1)
(In the formula, R is an ethylenically unsaturated hydrocarbon group, R'is a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms independently of each other, and at least of R'. One is an alkoxy group having 1 to 10 carbon atoms.)
[6] The silane-modified polyolefin according to any one of [1] to [5], wherein the density of the propylene-based copolymer is 0.850 to 0.930 g / cm ^3.
[7] The silane-modified polyolefin according to any one of [2] to [6], wherein the ethylene-based (co) polymer has a density of 0.850 to 0.930 g / cm ^3.

[8] A silane-crosslinked polyolefin containing a crosslinked product of the silane-modified polyolefin according to any one of [1] to [7], having a bending elasticity of 50 to 600 MPa, and a gel fraction of 40% or more.
[9] A three-dimensional network fiber aggregate containing a crosslinked product of the silane-modified polyolefin according to any one of [1] to [7], having a bending elasticity of 50 to 600 MPa, and a gel fraction of 40% or more. For silane cross-linked polypropylene.

[10] A silane-modified polyolefin composition containing at least the silane-modified polyolefin according to any one of [1] to [7] and a silanol condensation catalyst.
[11] A molded product obtained by molding the silane-modified polyolefin composition according to [10].
[12] A crosslinked molded article obtained by cross-linking the molded article according to [11].
[13] A three-dimensional network fiber aggregate obtained by molding the silane-modified polyolefin composition according to [10].

According to the present invention, a silane-modified polyolefin, a silane-crosslinked polyolefin, and a silane-modified polyolefin composition having excellent heat resistance and shape retention, which can realize a three-dimensional network fiber aggregate having excellent heat-resistant deformability and shape restoration property. , And a molded body, a crosslinked molded body, a three-dimensional network fiber aggregate, etc. using these are realized. Therefore, for example, even when it comes into contact with high-temperature steam for disinfection, its shape can be maintained due to its excellent deformation suppressing property and shape restoring property, and the problem of thermal deformation and settling can be improved. Therefore, it can be suitably used in products used in a high temperature environment such as electric blankets and hot water bottles.

Hereinafter, embodiments of the present invention will be described in detail, but the following embodiments are examples (representative examples) of embodiments of the present invention, and the present invention is not limited thereto. The present invention can be arbitrarily modified and implemented without departing from the gist thereof. In addition, in this specification, when a numerical value or a physical property value is put before and after using "~", it is used as including the value before and after that. Further, in the present specification, "% by mass" and "% by weight", and "parts by mass" and "parts by weight" have the same meanings. Further, the (co) polymer means to include both a homopolymer composed of only one polymer component and a copolymer composed of two or more copolymer components.

[Silane-modified polyolefin]
The silane-modified polyolefin of the present embodiment contains at least a silane-modified polypropylene obtained by grafting an alkoxysilane to a propylene-based copolymer, and one of the melting point peaks measured by a differential scanning calorimeter (DSC) is 110 ° C. or higher. It is a modified polyolefin.

[Propene-based copolymer]
The propylene-based copolymer that can be used as a raw material for silane modification includes a propylene unit, an α-olefin unit other than propylene (however, the “α-olefin” here also includes ethylene) and α. -Copolymers with monomeric units other than olefins can be mentioned. Examples of α-olefins other than propylene include 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-Tetradecene, 1-Pentadecene, 1-Hexadecene, 1-Hexene, 1-Ocdecene, 1-Nonadecene, 1-Eicocene, 3-Methyl-1-butene, 3-Methyl-1-pentene, 4-Methyl-1- Examples thereof include butene, 2-ethyl-1-hexene and 2,2,4-trimethyl-1-pentene, but the present invention is not particularly limited thereto. Among these, ethylene and α-olefin having 4 to 10 carbon atoms are preferable, and ethylene, 1-butene, 1-hexene and 1-octene are more preferable. In the propylene-based copolymer, any two or more kinds of α-olefin units may be contained. Further, the propylene-based copolymer may be a random copolymer or a block copolymer.

Specific examples of the propylene-based copolymer include a propylene / ethylene copolymer, a propylene / α-olefin copolymer having 4 to 8 carbon atoms, a propylene / ethylene / α-olefin copolymer having 4 to 20 carbon atoms, and the like. Can be mentioned. Here, the propylene-based copolymer may contain at least one or more propylene units, but may contain two or more propylene units.

The content ratio of the propylene unit in the propylene-based copolymer is higher than that of the entire propylene-based copolymer from the viewpoints of cushioning property, heat resistance, shape retention, etc. of the obtained three-dimensional network fiber aggregate and the like. It is 50 to 99.9% by mass, preferably 50 to 99.8% by mass, more preferably 50 to 99.5% by mass, still more preferably 50 to 99.0% by mass, and particularly preferably. Is 50-98.0% by mass. On the other hand, the content ratio of the α-olefin unit other than the propylene unit and the monomer unit other than the α-olefin in the propylene-based copolymer is the total with respect to the entire propylene-based copolymer for the same reason. It is 0.1 to 50% by mass, preferably 0.2% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and particularly preferably 2% by mass. That is all.

Among these, a propylene / ethylene copolymer is more preferable from the viewpoint of a balance between heat resistance, fluidity, and flexibility. The propylene / ethylene copolymer is preferably a copolymer of 50 to 99% by mass of one or more kinds of propylene and 1 to 50% by mass of ethylene. As the propylene-based copolymer, one type may be used alone, or two or more types may be used in combination as appropriate.

The density of the propylene-based copolymer (measured by JIS K6922-1, 2: 1997) is not particularly limited, but is 0.850 to 0.930 g / cm from the viewpoint of cushioning property, heat resistance, heat resistance deformation property, and the like. ^{It is preferably 3} , more preferably 0.860 to 0.925 g / cm ³ , and even more preferably 0.880 to 0.920 g / cm ³ .

The melt flow rate of the propylene copolymer (measured according to MFR, JIS K7210 (1999) at a temperature of 230 ° C. and a load of 2.16 kg) is not particularly limited, but is 0.1 to 5 g / 10 minutes. It is preferably 0.2 to 4.5 g / 10 minutes, and even more preferably 0.3 to 4.0 g / 10 minutes. When the MFR of the propylene-based copolymer as a raw material is large, the gel fraction after the cross-linking treatment decreases when the three-dimensional network fiber aggregate is formed, so that the permanent strain tends to increase and the settling tends to increase. Further, if the MFR of the propylene-based copolymer as a raw material is small, the strand diameter increases due to the high melt tension when the three-dimensional network fiber aggregate is formed, and the molten strand is difficult to be deformed and loop formation is difficult. Therefore, the flexibility of the three-dimensional network fiber aggregate tends to decrease.

[Ethylene-based (co) polymer]
The silane-modified polyolefin of the present embodiment may further contain a silane-modified polyethylene obtained by grafting an alkoxysilane to an ethylene-based (co) polymer from the viewpoint of improving flexibility and the like. Examples of the ethylene-based (co) polymer that can be used as a raw material for silane modification include ethylene homopolymers, unit ethylene units, and the above-mentioned α-olefin units other than ethylene units and monomer units other than α-olefins. Copolymers can be mentioned. In the ethylene (based) copolymer, any two or more kinds of α-olefin units may be contained.

Here, the content ratio of the ethylene unit of the ethylene-based (co) polymer is 51 to 100% by mass with respect to the entire ethylene-based copolymer. In the case of the ethylene-based copolymer, the content ratio of the α-olefin unit other than the ethylene unit and the monomer unit other than the α-olefin is 0. It is 1 to 49% by mass, preferably 0.2% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 2% by mass or more. is there.

As the ethylene-based copolymer, from the viewpoint of excellent balance between heat resistance and strength, high-pressure low-density polyethylene, high-density polyethylene, ethylene / α-olefin copolymer having 4 to 20 carbon atoms and the like are preferable, and ethylene is preferable. -A α-olefin copolymer having 4 to 20 carbon atoms is more preferable. Here, the ethylene-based copolymer may contain at least one kind of ethylene unit, but may also contain two or more kinds of ethylene units. As the ethylene-based (co) polymer, one type may be used alone, or two or more types may be used in combination as appropriate.

The ethylene-based (co) polymer can be produced by various known methods, and is not particularly limited. For example, examples of the catalyst used include a Ziegler-Natta catalyst, a metallocene catalyst, and the like. Among these, an ethylene-based (co) polymer produced by a metallocene catalyst is preferable from the viewpoint of melting point, impact resistance, molecular weight distribution and the like.

The density of the ethylene-based (co) polymer (measured by JIS K6922-1, 2: 1997) is not particularly limited, but is 0.850 to 0.940 g / cm ^{3 from the viewpoint of heat resistance and flexibility.} It is preferably 0.860 to 0.930 g / cm ³ , and even more preferably 0.865 to 0.920 g / cm ³ .

The melt flow rate of the ethylene-based (co) polymer (measured according to MFR, JIS K7210 (1999) at a temperature of 190 ° C. and a load of 2.16 kg) is not particularly limited, but is 0.1 to 5 g / 10. Minutes are preferable, more preferably 0.2 to 4.5 g / 10 minutes, still more preferably 0.3 to 4.0 g / 10 minutes. If the MFR of the ethylene-based (co) polymer used as a raw material is large, the loops of the strands during extrusion molding of a plurality of strands are not stable when forming a three-dimensional network fiber aggregate, and the strand diameter also differs for each strand. This tends to occur, and the uniformity of the obtained three-dimensional network fiber aggregate tends to decrease. Further, if the MFR of the ethylene-based (co) polymer used as a raw material is small, the motor load during extrusion molding is large, the resin pressure rises, and the strand diameter increases when forming a three-dimensional network fiber aggregate. The flexibility of the resulting three-dimensional reticulated fiber aggregate tends to decrease.

As the above ethylene-based (co) polymer, various grades can be obtained as commercial products. For example, DuPont Dow Elastomer Engage (registered trademark) series, Nippon Polyethylene Kernel (registered trademark) series, Dow DuPont Elastomer Engage (registered trademark) series, Mitsui Chemicals Toughmer (registered trademark) series, Mitsui Applicable products can be selected and used from the Evolu (registered trademark) series manufactured by Kagaku Co., Ltd.

[Alkoxysilane]
The silane-modified polypropylene and the optional component silane-modified polyethylene contained in the silane-modified polyolefin of the present embodiment are the above-mentioned propylene-based copolymer or ethylene-based (co) polymer grafted with alkoxysilane. The alkoxysilane to be graft-introduced is not particularly limited as long as it is a silane compound having an alkoxy group, but is preferably a polymerization residue of the unsaturated silane compound represented by the following formula (1).

R-Si (R') ₃ ... (1)
In the above formula (1), R is an ethylenically unsaturated hydrocarbon group, and R'is a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms independently of each other. At least one of them is an alkoxy group having 1 to 10 carbon atoms. R serves as a binding site when a graft is introduced into a propylene-based copolymer or an ethylene-based (co) polymer.

In the above formula (1), R is preferably an ethylenically unsaturated hydrocarbon group having 2 to 10 carbon atoms, and more preferably an ethylenically unsaturated hydrocarbon group having 2 to 6 carbon atoms. Specific examples thereof include an alkenyl group such as a vinyl group, a propenyl group, a butenyl group and a cyclohexenyl group.

In the above formula (1), R'is preferably a hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and more preferably a hydrocarbon group having 1 to 4 carbon atoms or 1 to 4 carbon atoms. It is an alkoxy group of 4. Further, at least one of R'is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms.

In the above formula (1), the hydrocarbon group having 1 to 10 carbon atoms of R'may be any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, but is an aliphatic hydrocarbon. It is preferably a hydrocarbon group. The alkoxy group having 1 to 10 carbon atoms of R'may be linear, branched or cyclic, but is preferably linear or branched. Specific examples of the hydrocarbon group of R'include an alkyl group typified by a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, or a phenyl group. Examples thereof include an aryl group represented by, but the present invention is not particularly limited thereto. Specific examples of the alkoxy group of R'include, but are not limited to, a methoxy group, an ethoxy group, an isopropoxy group, a β-methoxyethoxy group and the like.

In the above formula (1), at least one of the three R's is an alkoxy group, but it is preferable that two or more R's are alkoxy groups, and all three R's are alkoxy groups. Is more preferable.

As the unsaturated silane compound, vinyl trialkoxysilane typified by vinyltrimethoxysilane, vinyltriethoxysilane, propenyltrimethoxysilane and the like are particularly preferable. This is because the ethylenically unsaturated hydrocarbon group facilitates silane modification of polyolefins such as propylene-based copolymers and ethylene-based (co) copolymers, and the three alkoxy groups cause the cross-linking reaction described later. Because it can be done. That is, the alkoxy group of the alkoxysilane graft-introduced into the polyolefin reacts with water in the presence of a silanol condensation catalyst to hydrolyze to generate a silanol group, and the silanol groups are dehydrated and condensed to cause silane modification. A cross-linking reaction occurs in which polyolefins (silane-modified polypropylene or silane-modified polyethylene) are bonded to each other. The unsaturated silane compound may be used alone or in combination of two or more.

The amount of alkoxysilane introduced into the silane-modified polyolefin (the amount of unsaturated silane compound introduced into the raw material polyolefin) is not particularly limited, but the viscosity, handleability, heat resistance, heat resistance deformability, and shape retention during molding are not particularly limited. From the viewpoint of properties and the like, it is preferably 0.1 to 5% by mass with respect to the total amount of the silane-modified polyolefin. The amount of modification with such alkoxysilane is more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, and more preferably 5.0% by mass or less, more preferably 3. It is 0.0% by mass or less, more preferably 2.5% by mass or less. The amount of alkoxysilane introduced is the mass ratio of alkoxysilane (unsaturated silane compound to be introduced) to the total amount of polyolefin before modification. The sample is heated and burned to incinerate, and the ash is alkali-melted to be pure. It can be quantified after being dissolved in water and confirmed by ICP emission spectrometry using a high-frequency plasma emission spectrometer.

The silane-modified polyolefin may be grafted with a compound other than alkoxysilane (unsaturated silane compound) (hereinafter, also referred to as "other graft compound") as long as the effect of the present invention is not impaired. Other graft compounds include, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, etacrilic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and these. Examples thereof include acid anhydrides, but the present invention is not particularly limited thereto.

[Silane modification]
As described above, the silane-modified polyolefin of the present embodiment can be produced by graft-introducing alkoxysilane into a polyolefin such as a propylene-based copolymer or an ethylene-based (co) polymer as a raw material and silane-modifying. .. The method of silane modification can be carried out according to a known method and is not particularly limited. For example, solution denaturation, melt denaturation, solid phase denaturation by irradiation with an electron beam or ionizing radiation, denaturation in a supercritical fluid, and the like are preferably used. Among these, melt modification having excellent equipment and cost competitiveness is preferable, and melt kneading modification using an extruder having excellent continuous productivity is more preferable. Examples of the apparatus used for melt-kneading modification include a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll mixer, and the like. Among these, a single-screw extruder and a twin-screw extruder having excellent continuous productivity are preferable.

In general, the introduction of an alkoxysilane graft into a polyolefin such as a propylene-based copolymer or an ethylene-based (co) polymer cleaves the carbon-hydrogen bond of the polyolefin to generate a carbon radical, and an unsaturated functional group is added thereto. It can be carried out by a graft polymerization reaction such as addition. As the source of carbon radicals, in addition to the above-mentioned electron beam and ionizing radiation, a method of raising the temperature or a radical generator such as an organic or inorganic peroxide can be used. From the viewpoint of cost and operability, it is preferable to use an organic peroxide.

The radical generator used in producing the silane-modified polyolefin is not particularly limited, and for example, an organic peroxide contained in the hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and ketone peroxide group. And azo compounds and the like.

Specifically, the hydroperoxide group includes cumene hydroperoxide, tertiary butyl hydroperoxide and the like. The dialkyl peroxide group includes dicumyl peroxide, ditershally butyl peroxide, 2,5-dimethyl-2,5-ditershally butylperoxyhexane, and 2,5-dimethyl-2,5-ditershally butylperoxy. Hexane-3 and the like can be mentioned. Examples of the diacyl peroxide group include lauryl peroxide and benzoyl peroxide. Examples of the peroxyester group include tertiary peroxyacetate, tertiary butylperoxybenzoate, tertiary butylperoxyisopropyl carbonate and the like. Examples of the ketone peroxide group include cyclohexanone peroxide and the like. Examples of the azo compound include azobisisobutyronitrile and methylazoisobutyrate. One of these radical generators may be used alone, or two or more of these radical generators may be used in combination as appropriate.

Commonly used operations for melt extrusion modification include polyolefins such as propylene-based copolymers and ethylene-based (co) polymers as raw materials, and precursor compounds of alkoxysilane to be graft-introduced (for example, unsaturated silane compounds). , And if necessary, a radical generator such as organic peroxide is blended, blended and put into a kneader or extruder, extruded while heating, melting and kneading, and the molten resin coming out of the tip die is put into a water tank. To obtain a silane-modified polyolefin (silane-modified polypropylene, silane-modified polyethylene) by cooling with or the like.

The blending ratio of the polyolefin such as the propylene-based copolymer or the ethylene-based (co) polymer as the raw material and the precursor compound of the alkoxysilane to be graft-introduced (for example, the unsaturated silane compound) is the desired introduction ratio of the alkoxysilane. It may be set as appropriate according to the above, and is not particularly limited. From the viewpoint of obtaining a desired amount of silane modification and reducing the residue of unreacted material, 1 to 10 parts by mass of the precursor compound of alkoxysilane is preferable, and more preferably 2 to 7 parts by mass with respect to 100 parts by mass of the raw material polyolefin. It is a department.

The amount of the radical generator to be blended as necessary can be appropriately adjusted and is not particularly limited, but in the case of an organic peroxide, a desired silane modification amount can be obtained and the obtained silane modification can be obtained. From the viewpoint of suppressing deterioration of polyolefin, 0.1 to 10 parts by mass of organic peroxide is preferable, and 0.5 parts by mass is more preferable with respect to 100 parts by mass of the precursor compound (for example, unsaturated silane compound) of alkoxysilane. ~ 5 parts by mass.

Further, as the melt extrusion modification condition, for example, when a single-screw extruder or a twin-screw extruder is used, it is preferable to extrude at a temperature of about 150 to 300 ° C.

[Compounding agent]
The silane-modified polyolefin of the present embodiment may contain a compounding agent commonly used in the resin composition as long as the effect of the present invention is not impaired. Examples of such a compounding agent include a heat stabilizer, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a crystal nucleating agent, a rust preventive, a viscosity modifier, and a pigment.

Specific examples of the antioxidant include, but are not limited to, phenol-based, sulfur-based, and phosphorus-based antioxidants. The content of the antioxidant is not particularly limited, but is preferably 0.1 to 1 part by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the silane-modified polyolefin.

Specific examples of the ultraviolet absorber include 2-hydroxy-4-normal-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, and 2-hydroxy-4-methoxy-4. Benzophenone systems such as -carboxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone; 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-5- Methylphenyl) Benzophenorizoles such as benzotriazoles; salicylate esters such as phenylsulfate and p-octylphenylsulfate can be mentioned, but are not particularly limited thereto. The content of the ultraviolet absorber is not particularly limited, but is preferably 0.01 to 1.0 part by mass, more preferably 0.1 to 0.8 part by mass with respect to 100 parts by mass of the total amount of the silane-modified polyolefin. is there.

As the viscosity modifier, a rubber compound oil, specifically, a paraffin-based process oil is preferable. The content of the viscosity modifier is preferably 0.5 to 5 parts by mass, more preferably 0.8 to 3 parts by mass, based on 100 parts by mass of the total amount of the silane-modified polyolefin.

[Physical characteristics]
The silane-modified polyolefin of the present embodiment has one of the melting point peaks measured by a differential scanning calorimetry (DSC) at 110 ° C. or higher. If the maximum temperature of the melting point peak is lower than 110 ° C., it is easily deformed by heat, and it is difficult to obtain sufficient shape retention under high temperature when the three-dimensional network fiber aggregate is formed. From this point of view, the melting point of the silane-modified polyolefin is preferably 130 ° C. or higher, more preferably 140 ° C. or higher. The upper limit of the melting point of the silane-modified polyolefin is not particularly limited. Generally, it is preferably 180 ° C. or lower. The melting point of the silane-modified polyolefin is determined by a differential scanning calorimetry (DSC), and is determined by measuring the peak derived from the crystal portion in the DSC. Specific examples of a more detailed measurement method will be shown in Examples described later.

The melt flow rate of the silane-modified polyolefin of the present embodiment (measured according to MFR, JIS K7210 (1999) at a temperature of 230 ° C. and a load of 2.16 kg) is not particularly limited, but is preferably 2 g / 10 minutes or more. , More preferably 3 g / 10 minutes or more, further preferably 4 g / 10 minutes or more, preferably 50 g / 10 minutes or less, more preferably 45 g / 10 minutes or less, still more preferably 30 g / 10 minutes or less. When the MFR is equal to or higher than the lower limit, the die well and the melt tension are low, so that the strand diameter is unlikely to increase, and the obtained three-dimensional network fiber aggregate is likely to form a loop along the side surface of the aggregate, resulting in a good repulsive feeling. It tends to be easy to make products with. Further, when the MFR is not more than the upper limit value, when a plurality of strands are extruded, the discharge of the strands tends to be stable, and it tends to be difficult to form a resin mass in which the plurality of strands are curled and solidified. Further, the loop formation and the fusion of the strands are stable, the strand diameter is likely to be uniform, the uniformity of the obtained three-dimensional network fiber aggregate is good, and the performance and quality as a product tend to be improved.

[Silane-modified polyolefin composition]
The silane-modified polyolefin composition of the present embodiment contains at least the above-mentioned silane-modified polyolefin and silanol condensation catalyst.

[Silanol condensation catalyst]
The silanol condensation catalyst used here is one or more selected from the group consisting of metal organic acid salts, titanates, borates, organic amines, ammonium salts, phosphonium salts, inorganic acids and organic acids, and inorganic acid esters. Examples include compounds.

Examples of metal organic acid salts include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, stannous acetate, stannous octanoate, cobalt naphthenate, lead octylate, lead naphthenate, and zinc octylate. , Zinc caprylate, iron 2-ethylhexanoate, iron octylate, iron stearate and the like, but are not particularly limited thereto. Examples of the titanate include, but are not limited to, tetrabutyl ester titanate, tetranonyl titanate ester, and bis (acetylacetonitrile) di-isopropyl titanate. Examples of the organic amine include, but are not limited to, ethylamine, dibutylamine, hexylamine, triethanolamine, dimethylsoyaamine, tetramethylguanidine, pyridine and the like. Examples of the ammonium salt include, but are not limited to, ammonium carbonate, tetramethylammonium hydroxide and the like. Examples of the phosphonium salt include, but are not limited to, tetramethylphosphonium hydroxide. Examples of the inorganic acid and the organic acid include, but are not limited to, sulfonic acids such as sulfuric acid, hydrochloric acid, acetic acid, stearic acid, maleic acid, toluene sulfonic acid, and alkylnaphthyl sulfonic acid. Examples of the inorganic acid ester include a phosphoric acid ester and the like.

Among these, metal organic acid salts, sulfonic acids, and phosphate esters are preferable, and tin metal carboxylates, such as dioctyltin dilaurate, alkylnaphthylsulfonic acid, and ethylhexyl phosphate esters, are more preferable. As the silanol condensation catalyst, one type may be used alone, or two or more types may be used in combination as appropriate.

The content of the silanol condensation catalyst is not particularly limited, but it suppresses early cross-linking during molding of the molded product before cross-linking and promotes the cross-linking reaction during the production of the silane-crosslinked polyolefin, resulting in a three-dimensional network fiber aggregate or the like. From the viewpoint of improving the heat resistance of the polyolefin, 0.0001 to 0.5 parts by mass is preferable, and 0.0001 to 0.3 parts by mass is more preferable with respect to 100 parts by mass of the silane-modified polyolefin.

The silanol condensation catalyst is preferably used as a silanol condensation catalyst-containing masterbatch in which a polyolefin and a silanol condensation catalyst are mixed. Examples of the polyolefin that can be used in this silanol condensation catalyst-containing masterbatch include polyethylene, polypropylene, and a propylene-ethylene copolymer. Examples of polypropylene include homopolypropylene and propylene which are polymers of propylene and copolymers of ethylene or α-olefins such as butene, hexene and octene (excluding propylene). Among these, homopolypropylene and propylene / ethylene copolymer are preferable from the viewpoint of flexibility and the like. Here, the propylene / ethylene copolymer is preferably a copolymer of 60 to 95% by mass of propylene and 5 to 40% by mass of ethylene. In the masterbatch of the silanol condensation catalyst, only one of these polyolefins may be used alone, or two or more of these polyolefins may be used in combination as appropriate.

When the silanol condensation catalyst is used as a silanol condensation catalyst-containing masterbatch in which polyolefin and silanol condensation catalyst are mixed, the content of the silanol condensation catalyst in the masterbatch is not particularly limited, but is usually 0.1 to 5.0. It is preferably about% by mass. A commercially available product can be used as the silanol condensation catalyst-containing masterbatch, and for example, "PZ010" manufactured by Mitsubishi Chemical Corporation can be used.

[Other ingredients]
In addition to the above-mentioned silane-modified polyolefin and silanol condensation catalyst, the silane-modified polyolefin composition includes various additives as other components, resins other than silane-modified polyolefin, and resins other than polyolefin in the masterbatch containing the silanol condensation catalyst. May be contained within a range that does not impair the effects of the present invention. For example, it may contain the above-mentioned compounding agent which can be blended with a silane-modified polyolefin.

Specific examples of other components include thermoplastic solid resins other than polyolefins, solid rubbers, liquid resins, softeners, plasticizers, and the like. These can also be used as a tackifier for improving adhesiveness or compatibility. For example, rosin and its derivatives, terpene resin and petroleum resin and their derivatives, alkyd resin, alkylphenol resin, terpenephenol resin, kumaron inden resin, synthetic terpene resin, alkylene resin, polyisobutylene, polybutadiene, polybutene, isobutylene and butadiene It may contain a polymer, mineral oil, process oil, pine oil, anthracene oil, pine root oil, plasticizer, animal and vegetable oil, polymer oil and the like.

[Silane crosslinked polyolefin]
By exposing the above-mentioned silane-modified polyolefin composition to a water-containing atmosphere, the cross-linking reaction between silanol groups can proceed to obtain a silane-crosslinked polyolefin. Various conditions can be adopted for the method of exposure to the water-containing atmosphere, and the method is not particularly limited. For example, a method of leaving in air containing water, a method of blowing air containing water vapor, a method of immersing in a water bath, a method of sprinkling hot water in a mist form, and the like can be mentioned.

More specifically, in the above silane-modified polyolefin composition, a hydrolyzable alkoxy group derived from an alkoxysilane (for example, an unsaturated silane compound) graft-introduced into a silane-modified polyolefin (silane-modified polypropylene, silane-modified polyethylene) is used. In the presence of a silanol condensation catalyst, a silanol group is generated by reacting with water and hydrolyzing, and further dehydration condensation of the silanol groups promotes a cross-linking reaction, and silane-modified polyolefins are bonded to each other to form silane. Produces crosslinked polyolefins (silane-crosslinked polypropylene, silane-crosslinked polyethylene).

The crosslinking conditions are determined by the conditions of exposure to the water-containing atmosphere, and are not particularly limited, but are usually preferably in the temperature range of 20 to 130 ° C. and preferably in the range of 10 minutes to 1 week, and more preferably in the temperature range of 20 to 130 ° C. It ranges from 1 hour to 160 hours. When air containing moisture is used, the relative humidity may be appropriately adjusted within the range of 1 to 100%.

From the viewpoint of exhibiting excellent properties over a long period of time, the gel fraction (crosslinking degree) of the silane crosslinked polyolefin is preferably 30% or more, more preferably 40% or more. The gel fraction can be determined by changing the graft ratio (denaturation amount) of alkoxysilane (unsaturated silane compound) in the silane-modified polyolefin, the type and blending amount of silanol condensation catalyst, and the conditions (temperature, time) for crosslinking. Can be adjusted. The upper limit of this gel fraction is not particularly limited, but usually 90% is a guideline. The gel fraction of the silane crosslinked polyolefin can be measured by the method described in the section of Examples described later.

[Molded product, crosslinked molded product]
Before the above-mentioned cross-linking treatment, the silane-modified polyolefin composition is molded into a predetermined shape by various molding methods such as extrusion molding, injection molding, and press molding to obtain a (non-crosslinked) molded product. Then, by exposing the obtained (uncrosslinked) molded product to a water-containing atmosphere, the cross-linking reaction between silanol groups can proceed to obtain a cross-linked molded product (silane-crosslinked polyolefin molded product).

[Three-dimensional network fiber aggregate]
Further, the silane-modified polyolefin composition is extruded to form a strand (molded product), and then the strands are heat-sealed to each other and then water-cooled to obtain a three-dimensional network fiber aggregate (crosslinked molded product). You can also do it. For example, the silane-modified polyolefin composition can be molded into a three-dimensional network fiber aggregate by a manufacturing apparatus and a molding method as described in International Publication No. 2012/035736. The three-dimensional network fiber aggregate thus obtained is preferably exposed to a water atmosphere as described above and used as a silane crosslinked polyolefin.

At this time, since the above-mentioned silane-modified polyolefin composition can be molded without cross-linking during molding, a three-dimensional network fiber aggregate that requires special moldability such as loopability and thermal adhesion immediately after molding can be obtained. It can be molded efficiently. Moreover, the obtained molded product has improved heat resistance, which is a major problem of ethylene-based copolymers such as ethylene / α-olefin copolymers, and the problem of settling is greatly improved even under a load at high temperature. It is possible to provide a three-dimensional network fiber aggregate exhibiting excellent cushioning properties.

[Use]
The uses of the silane-modified polyolefin, the silane-modified polyolefin composition, and the silane-crosslinked polyolefin of the present embodiment are not particularly limited. For example, bedding such as furniture, bed mats, pillows, etc .; can be suitably used as a cushioning material for vehicle seats, ships, and the like. When applied to these applications, it is preferable to use it as the above-mentioned three-dimensional network fiber aggregate. This three-dimensional network fiber aggregate can also be used as a laminate with other materials, if necessary. However, as described above, the shape of the molded body is not limited to the three-dimensional network fiber aggregate, and can be molded into a predetermined shape.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. Further, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-mentioned upper limit or lower limit value. , The range specified by the combination of the values of the following examples or the values of the examples may be used.

[material]
The raw materials used in Examples and Comparative Examples are shown below.

<Polypropylene>
-PP-1: Novatec PP (registered trademark) EG8 (manufactured by Japan Polypropylene Corporation, propylene / ethylene copolymer, MFR: 0.8 g / 10 minutes (230 ° C, 2.16 kg load), density: 0.90 g / cm ³ ) was used.

PP-2: Vistamax® 6102 (Exxon, propylene / ethylene copolymer, MFR: 3 g / 10 minutes (230 ° C, 2.16 kg load), density: 0.86 g / cm ³ ) used.

PP-3: Zelas (registered trademark) 7025 (manufactured by Mitsubishi Chemical Corporation, propylene-ethylene copolymer, MFR: 1.6 g / 10 minutes (230 ° C, 2.16 kg load), density: 0.89 g / cm ³ )It was used.

-PE-1: Engage (registered trademark) 8100 (manufactured by Dow DuPont Elastomer, ethylene-octene copolymer, MFR: 1.0 g / 10 minutes (190 ° C., 2.16 kg load), density: 0.87 g / cm ³ ) was used.

-PE-2: Engage (registered trademark) 8677 (manufactured by Dow DuPont Elastomer, ethylene-octene copolymer, MFR: 0.5 g / 10 minutes (190 ° C., 2.16 kg load), density: 0.87 g / cm ³ ) was used.

<Catalyst Masterbatch (MB)>
-Catalyst MB: PZ010 (manufactured by Mitsubishi Chemical Corporation, homopolypropylene containing tin catalyst (dioctyl tin dilaurate), MFR of homopolypropylene: 16 g / 10 minutes (230 ° C, 2.16 kg load), density of linear low-density polyethylene : 0.90 g / cm ³ ) was used.

[Measurement / evaluation method]
The methods for measuring and evaluating various physical properties and characteristics are as follows.

<Measurement of polyolefins and silane-modified polyolefins>
[Melting point]
Using a differential scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd., trade name "DSC6220", a sample of about 5 mg was heated from 20 ° C. to 200 ° C. at a heating rate of 100 ° C./min according to JIS K7121 (2010). After holding at 200 ° C. for 3 minutes, the temperature was lowered to -10 ° C at a cooling rate of 10 ° C./min, and then the temperature was raised to 200 ° C. at a heating rate of 10 ° C./min. (° C.) was calculated and used as the melting point.

[Melt flow rate (MFR)]
Measured at 230 ° C. and 2.16 kg load according to JIS K7210 (1999).

<Evaluation of silane crosslinked polyolefin>
[Gel fraction]
The mass% of the insoluble matter after Soxhlet extraction at the boiling point of xylene for 10 hours was measured.

[Flexural modulus]
Measurements were made using injection-molded test pieces having a thickness of 4 mm, a length of 800 mm, and a width of 10 mm in accordance with JIS K7171 (2008).

[Compressive permanent distortion]
A sheet-shaped molded product with a thickness of 2 mm that was injection-molded was punched into a circular shape with a diameter of 30 mm, and six sheets were stacked and compressed by 25% with a spacer in accordance with JIS K6262 (2013) for 24 hours at 23 ° C. Then, heat treatment was performed for 22 hours at the test temperatures (20 ° C., 50 ° C., 70 ° C.) shown in Table 1, each of which was decompressed. The compression set (CS: unit%) was calculated respectively. The lower the value of compression set, the better.

[Example 1]
80 parts by mass of polypropylene-1, 20 parts by mass of polypropylene-2, 3.0 parts by mass of vinyltrimethoxysilane (VTMOS), which is an unsaturated silane compound as an alkoxysilane precursor, and an organic peroxide as a radical generator. 1.0 part of a certain radical peroxide was stirred with a blender. After that, it was put into a twin-screw extruder (manufactured by Ikegai Corp., PCM45) set at a temperature of 220 ° C., and the strands coming out of the nozzle were cooled and solidified in a water tank and then cut into pellets to form a silane-modified polyolefin. I got A. The physical characteristics of the obtained silane-modified polyolefin A are shown in Table 1.

To 100 parts by mass of the silane-modified polyolefin A obtained above, 5 parts by mass of PZ010 was added as a catalyst MB to obtain a silane-modified polyolefin composition A. This was molded by an injection molding machine under the condition of 200 ° C. and immersed in warm water at 80 ° C. for 24 hours to produce a sheet-shaped molded product having a thickness of 2 mm containing the silane crosslinked polyolefin A. The flexural modulus, gel fraction, and compression set of the obtained sheet-shaped molded product were evaluated. The evaluation results are shown in Table 1.

[Example 2]
The same operation as in Example 1 was carried out except that 90 parts by mass of polypropylene-1 and 10 parts by mass of polyethylene-1 were used instead of polypropylene-1 and polypropylene-2 to obtain a silane-modified polyolefin B. Using the obtained silane-modified polyolefin B, the same operation as in Example 1 was carried out to prepare a silane-modified polyolefin composition B, and a sheet-shaped molded product having a thickness of 2 mm containing the silane-crosslinked polyolefin B was produced.
The silane-modified polyolefin B and the sheet-shaped molded product were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 3]
The same operation as in Example 1 was carried out except that 80 parts by mass of polypropylene-1, 10 parts by mass of polyethylene-1 and 10 parts by mass of polyethylene-2 were used instead of polypropylene-1 and polypropylene-2. Modified polyolefin C was obtained. Using the obtained silane-modified polyolefin C, the same operation as in Example 1 was carried out to prepare a silane-modified polyolefin composition C, and a sheet-shaped molded product having a thickness of 2 mm containing the silane-crosslinked polyolefin C was produced.
The silane-modified polyolefin C and the sheet-shaped molded product were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 4]
The same operation as in Example 1 was carried out except that 20 parts by mass of polypropylene-2 and 80 parts by mass of polypropylene-3 were used instead of polypropylene-1 and polypropylene-2 to obtain a silane-modified polyolefin D. Using the obtained silane-modified polyolefin D, the same operation as in Example 1 was carried out to prepare a silane-modified polyolefin composition D, and a sheet-shaped molded product having a thickness of 2 mm containing the silane-crosslinked polyolefin D was produced.
The silane-modified polyolefin D and the sheet-shaped molded product were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 1]
The same operation as in Example 1 was carried out except that the formulation of VTMOS and the radical generator was omitted, to obtain a polyolefin mixture E. Using the obtained polyolefin mixture E, the same operation as in Example 1 was carried out except that the formulation of the catalyst MB: PZ010 was omitted, to produce a sheet-shaped molded product having a thickness of 2 mm.
The polyolefin mixture E and the sheet-shaped molded product were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

From the above results, the following can be seen.
By using the silane-modified polyolefins A to D having a melting point of 150 to 165 ° C., the silane-crosslinked polyolefins A to D of Examples 1 to 4 are distorted in the compression set at 20, 50 and 70 ° C., which are indicators of settling. It was small and showed good results. Further, since the silane-crosslinked polyolefins A to D of Examples 1 to 4 use propylene-based copolymers having a small MFR, a gel fraction of 40% or more can be achieved. Since the silane-crosslinked polyolefins A to D of Examples 1 to 4 have low bending elasticity and excellent flexibility, excellent cushioning properties can be expected when used as a three-dimensional network fiber aggregate.

On the other hand, the polyolefin mixture E having a melting point of 150 ° C. in Comparative Example 1 showed a gel fraction of 0%, and the compression set at 20, 50 and 70 ° C. was large. Therefore, distortion tends to remain, and durability and heat resistance are inferior. From the comparison with Example 1 and Comparative Example 1, it was clarified that the silane-crosslinked polyolefin of the present invention has a small compression set and is excellent in durability and heat resistance.

From the above, the silane-crosslinked polyolefin, which is a silane-modified polypropylene crosslinked product obtained by grafting alkoxysilane to a propylene-based copolymer, can achieve a gel content of 40% or more, and has a shape restoration property with small compression set even at high temperatures. It was shown to be excellent and also excellent in heat-resistant deformation.

Since the silane-modified polyolefin of the present invention has excellent durability and heat resistance, it has low compression set even under heating conditions, is less likely to be settled or deformed by the use of electric bedding such as an electric blanket, and has heat resistance and deformation. A silane-crosslinked polyolefin having excellent shape restoration properties can be provided. Therefore, the silane-modified polyolefin and the silane-modified polyolefin composition of the present invention, and the molded article, the crosslinked molded article, the three-dimensional network fiber aggregate, and the like using them are, for example, bedding such as furniture, bed mat, and pillow. It can be widely and effectively used as a constituent material for cushioning materials for vehicles, marine seats, and the like.

Claims (11)

It contains a silane-modified polypropylene in which an alkoxysilane is grafted on a propylene-based copolymer and a silane-modified polyethylene in which an alkoxysilane is grafted on an ethylene-based (co) polymer.
One of the melting point peaks measured by a differential scanning calorimetry (DSC) is 110 ° C. or higher.
Silane-modified polyolefin composition for three-dimensional network fiber aggregate . The silane-modified polyolefin composition for a three-dimensional network fiber aggregate according to claim 1 , wherein the amount of the alkoxysilane introduced is 0.1 to 5% by mass with respect to the total amount of the silane-modified polyolefin. The tertiary according to claim 1 or 2, wherein the melt flow rate (measured according to MFR, JIS K7210 (1999) at a temperature of 230 ° C. and a load of 2.16 kg) is 2 to 50 g / 10 minutes. Silane-modified polyolefin composition for original reticulated fiber aggregates . The silane modification for a three-dimensional network fiber aggregate according to any one of claims 1 to 3, wherein the alkoxysilane is a polymerization residue of an unsaturated silane compound represented by the following formula (1). Polykoxy composition .
R-Si (R') ₃ ... (1)
(In the formula, R is an ethylenically unsaturated hydrocarbon group, R'is a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms independently of each other, and at least of R'. One is an alkoxy group having 1 to 10 carbon atoms.) Density of the propylene-based copolymer, a three-dimensional network fiber aggregate-body silane-modified polyolefin composition according to any one of 0.850~0.930g / cm ³ a is <br/> claims 1-4 Stuff. The ethylene (co) density of the polymer, three-dimensional network fiber aggregate-body silane-modified according to any one of <br/> claims 1-5 is 0.850~0.940g / cm ³ Polyolefin composition . A crosslinked product of the silane-modified polyolefin composition for a three-dimensional network fiber aggregate according to any one of claims 1 to 6 is contained.
Bending elasticity is 50 to 600 MPa,
Gel fraction is 40% or more
Silane cross-linked polypropylene composition for three-dimensional network fiber aggregate . The silane-modified polyolefin composition for a three-dimensional network fiber aggregate according to any one of claims 1 to 6 and
With silanol condensation catalyst
A silane-modified polyolefin composition for a three-dimensional network fiber aggregate containing at least . The silane-modified polyolefin composition for a three-dimensional network fiber aggregate according to claim 8 is formed.
Molded body for three-dimensional network fiber assembly . The molded product for a three-dimensional network fiber assembly according to claim 9 is crosslinked.
Cross-linked molded article for three-dimensional network fiber assembly . The silane-modified polyolefin composition for a three-dimensional network fiber aggregate according to claim 8 is formed.
Three-dimensional network fiber aggregate.