KR20070017123A - Thermoplastic elastomer composition, formed article and sealing material having low hardness - Google Patents

Abstract

[A] 5 to 60 mass% of ethylene-α-olefin-based copolymer having an intrinsic viscosity measured at 135 ° C. at 135 ° C. or higher of 3.5 dl / g, [B] 1 to 20 mass% of polyolefin resin, and [C] 0.1-50 of [D] hydrogenated diene polymer with respect to 100 mass parts of total of 30-94 mass% of mineral oil type softener (The total of [A], [B], and [C] is 100 mass%.). A thermoplastic elastomer composition containing a mass part and wherein at least the [A] ethylene-α-olefin-based copolymer and the [B] polyolefin-based resin are dynamically heat treated in the presence of a crosslinking agent, or [A] in the thermoplastic elastomer composition 20-80 mass% of ethylene-alpha-olefin type copolymers whose intrinsic viscosity measured at 135 degreeC in 135 degreeC / g or more in [A1] decalin solvent, and [C1] mineral oil type softener 20 (%) , The sum of [A1] and [C1] is 100% by mass.) It is a thermoplastic elastomer composition substituted with rubber. Excellent molding processability, low hardness, softeners such as mineral oil do not bleed out and have flexibility, excellent rubber elasticity (rebound elasticity, compression set), and recycling properties.

Thermoplastic elastomer composition, ethylene-alpha olefin copolymer, polyolefin resin, mineral oil softener, hydrogenated diene polymer, dielectric rubber, sealant, molded article

Description

Thermoplastic Elastomer Compositions, Molded Products, and Low Hardness Sealants {THERMOPLASTIC ELASTOMER COMPOSITION, FORMED ARTICLE AND SEALING MATERIAL HAVING LOW HARDNESS}

The present invention relates to a thermoplastic elastomer composition and a molded article using the same, a low hardness sealant, and more particularly, to excellent molding processability, low hardness, flexibility, excellent rubber elasticity (rebound elasticity, compression set), mineral A thermoplastic elastomer composition and a molded article without bleed-out of an oil-based softener, and a low hardness sealing material using the thermoplastic elastomer composition.

Sealants used for sealing materials for office equipment, automobiles, building materials, and the like are very soft, and improvement studies have been attempted from thermoplastic elastomer compositions useful as vulcanized rubber, vulcanized foam rubber, foamed polyurethane, or flexible materials. See Documents 1 to 3). Although the thermoplastic elastomer composition is disclosed in Patent Document 1 and the like, in the composition of this document, there is a problem in that the flexibility is not sufficient, and when a softener such as mineral oil is added, the softener bleeds out of the molded article and the rubber elasticity decreases. .

Although vulcanized rubber, vulcanized foam rubber, and foamed polyurethane satisfy characteristics such as flexibility and sealability, there is a problem that recent demands do not satisfy many recycling properties.

Patent Document 1: Patent Publication No. 2002-201313

Patent Document 2: Patent Publication No. 2002-251061

Patent Document 3: Patent Publication No. 7-234579

<Start of invention>

The present invention provides a thermoplastic elastomer composition, a molded article and a low-hardness sealant having excellent molding processability, low hardness, softness such as mineral oil, which does not bleed out, and is excellent in rubber elasticity (rebound elasticity, compression set). It aims to provide.

According to this invention, the thermoplastic elastomer composition shown below, its molded article, and the sealing material of low hardness are provided.

(1) 5-60 mass% of ethylene-alpha-olefin type copolymers whose intrinsic viscosity measured at 135 degreeC in [A] decalin solvent is 3.5 dl / g or more,

[B] 1 to 20% by mass of polyolefin resin, and

[C] With respect to 100 parts by mass in total of 30 to 94% by mass of mineral oil softener (the total of [A], [B] and [C] is 100% by mass),

(D) 0.1-50 mass parts of hydrogenated diene type polymers are included,

The thermoplastic elastomer composition in which at least the said [A] ethylene-alpha-olefin type copolymer and the said [B] polyolefin type resin are heat-processed dynamically in presence of a crosslinking agent.

(2) 20 to 80% by mass of an ethylene-α-olefin-based copolymer having an intrinsic viscosity measured at 135 ° C. at 135 ° C. or higher in [X] [A1] decane solvent, and

5 to 60% by mass of oil-extended rubber, including 20 to 80% by mass of [C1] mineral oil-based softener (the total of [A1] and [C1] is 100% by mass),

[B1] 1 to 20 mass% of polyolefin resin, and

With respect to 100 mass parts in total of 30-94 mass% of [C2] mineral oil type softeners (the sum of [X], [B1], and [C2] is 100 mass%),

[D1] Contains 0.1 to 50 parts by mass of a hydrogenated diene polymer,

The thermoplastic elastomer composition in which at least said [A1] ethylene-alpha-olefin type copolymer and said [B1] polyolefin type resin are heat-processed dynamically in presence of a crosslinking agent.

(3) Hydrogen of the polymer in which said hydrogenated diene polymer [D] contains the hydrogenated substance of the polymer containing the monomeric unit of a conjugated diene compound, and the monomeric unit of a conjugated diene compound, and the monomeric unit of a vinyl aromatic compound. The thermoplastic elastomer composition as described in said (1) or (2) which is at least 1 sort (s) chosen from an additive.

(4) The thermoplastic elastomer composition according to any one of (1) to (3), wherein the durometer E hardness according to JIS K6253 is 80 or less.

(5) The sum total of all the monomeric units containing content of the ethylene monomeric unit which comprises the said ethylene-alpha-olefin type copolymer [A] and [A1] including the ethylene monomeric unit and the monomeric unit of an alpha-olefin compound is 100 The thermoplastic elastomer composition as described in any one of said (1)-(4) which is 35 to 95 mol% when it is set to mol%.

(6) The thermoplastic elastomer composition according to any one of (1) to (5), wherein the mineral oil softener [C], [C1] and [C2] are paraffinic mineral oil.

(7) The crosslinking agent is 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl- 2,5-di (t-butylperoxy) hexane, α, α-bis (t-butylperoxy) diisopropylbenzene, dicumylperoxide and di-t-butylperoxide, wherein the organic peroxide is selected from ( The thermoplastic elastomer composition according to any one of 1) to (6).

(8) The thermoplastic elastomer composition according to any one of the above (1) to (7), wherein a cyclohexane insoluble content at 23 ° C. of the ethylene-α-olefin copolymer in the thermoplastic elastomer composition is 60% by mass or more.

(9) A molded article prepared from the thermoplastic elastomer composition according to any one of (1) to (8).

(10) The low hardness sealing material manufactured using the thermoplastic elastomer composition as described in any one of said (1)-(8).

The low hardness sealing material as described in said (10) whose durometer A hardness based on JISK6253 is 40 or less.

(12) The low hardness sealing material as described in said (10) or (11) formed in any shape chosen from O-ring shape, a sheet shape, and a rod shape.

(13) A container comprising the low hardness sealing material according to any one of (10) to (12) as a component.

(14) A container molded by injection molding from a composite composed of a seal portion and a case portion made from the low hardness seal material according to any one of (10) to (12).

(15) The container according to the above (14), wherein the case portion is made from a thermoplastic resin and / or a thermoplastic elastomer composition and is recyclable.

(16) A toner case comprising the low hardness sealing material according to any one of (10) to (12) as a component.

The thermoplastic elastomer composition of the present invention is 5 to 60 mass% of an ethylene-α-olefin-based copolymer having an intrinsic viscosity measured at 135 ° C. at 135 ° C. or higher in [A] decalin solvent, and [B] polyolefin resin 1 to [D] With respect to a total of 100 parts by mass of 20% by mass and 30 to 94% by mass of the [C] mineral oil softener (the total of [A], [B] and [C] is 100% by mass). 0.1 to 50 parts by mass of the hydrogenated diene polymer, wherein at least the [A] ethylene-α-olefin copolymer and the [B] polyolefin resin are heat-treated dynamically in the presence of a crosslinking agent, whereby injection molding, extrusion molding, Excellent molding processability by blow molding, compression molding, vacuum molding, lamination molding, calender molding, etc., low hardness, mineral oil-based softeners do not bleed out, flexibility, and excellent rubber elasticity (rebound elasticity, compression set).

Another thermoplastic elastomer composition of the present invention comprises 20 to 80% by mass of an ethylene-α-olefin-based copolymer having an intrinsic viscosity measured at 135 ° C. or higher in [X] [A1] decarin solvent at 135 ° C./g or higher and [C1]. 5 to 60 mass% of dielectric rubber containing 20 to 80 mass% of mineral oil softener (but the sum of [A1] and [C1] is 100 mass%), 1 to 20 mass% of [B1] polyolefin resin, And [D1] hydrogenated diene polymer to 100 parts by mass of [C2] mineral oil softener 30 to 94% by mass (the total of [X], [B1], and [C2] is 100% by mass). 0.1 to 50 parts by mass, wherein at least the [A1] ethylene-α-olefin copolymer and the [B1] polyolefin resin are thermally treated in the presence of a crosslinking agent, thereby injection molding, extrusion molding, blow molding and compression. Excellent moldability by forming, vacuum forming, additive forming, calender forming, etc. Excellent hardness, low hardness, mineral oil-based softener does not bleed out, it is flexible, and excellent rubber elasticity (rebound elasticity, compression set).

The hydrogenated diene polymer [D] is at least one selected from a hydrogenated product of a polymer containing a monomer unit of a conjugated diene compound, and a hydrogenated product of a polymer containing a monomer unit of a conjugated diene compound and a monomer unit of a vinyl aromatic compound. In the case of a species, the durometer hardness prescribed | regulated to JISK6253 can be 80 or less, and it can be set as a soft composition.

Moreover, when cyclohexane insoluble content at 23 degreeC of the ethylene-alpha-olefin type copolymer in this thermoplastic elastomer composition is 60 mass% or more, it is excellent in rubber elasticity and mechanical strength.

The molded article of the present invention has a low hardness, does not bleed out of the mineral oil softener, has flexibility, and is excellent in rubber elasticity (rebound elasticity, compression set). Moreover, since the sealing material of this invention is comprised by the thermoplastic elastomer composition, it becomes possible to recycle and it is extremely excellent in resource saving.

The container using this low hardness sealing material as a component can be integrally molded in a short time by the injection molding of the sealing part and the case part manufactured from this sealing material, and can provide the container which is labor saving and excellent in recyclability.

BRIEF DESCRIPTION OF THE DRAWINGS It is a photograph which shows the container with a sealing part which uses the low hardness sealing material of this invention as a component.

It is a photograph which shows the state which separated the container with a sealing part of FIG. 1 into the sealing part and the case part.

It is explanatory drawing which shows the leak fall test.

<Explanation of symbols for the main parts of the drawings>

1: seal

2: case

10: Container

11: lid

12: double clip

13: corrugated cardboard

14: Packing

15: water

Hereinafter, the present invention will be described in detail.

The thermoplastic elastomer composition of the first aspect of the present invention is a 5- to 60 mass% ethylene-α-olefin-based copolymer having an intrinsic viscosity measured at 135 ° C in a [A] decalin solvent at 3.5 dl / g or more, and a [B] polyolefin system. With respect to 100 mass parts in total of 1-20 mass% of resins, and 30-94 mass% of [C] mineral oil type softeners (However, the sum total of [A], [B], and [C] is 100 mass%.), [D] The hydrogenated diene polymer contains 0.1 to 50 parts by mass, and at least the [A] ethylene-α-olefin copolymer and the [B] polyolefin resin are heat treated dynamically in the presence of a crosslinking agent.

The thermoplastic elastomer composition of the second aspect of the present invention comprises 20 to 80% by mass of an ethylene-α-olefin-based copolymer having an intrinsic viscosity measured at 135 ° C. or higher at 135 ° C. in [X] [A1] decarin solvent, and [ C1] 5 to 60 mass% of dielectric rubber containing 20 to 80 mass% of mineral oil softener (but the sum of [A1] and [C1] is 100 mass%), and 1 to 20 mass of [B1] polyolefin resin [D1] hydrogenated diene to 100 parts by mass of 30% to 94% by mass of [C2] mineral oil-based softener (the sum of [X], [B1], and [C2] is 100% by mass)). It contains 0.1-50 mass parts of system type polymers, and at least the said [A1] ethylene-alpha-olefin type copolymer and the said [B1] polyolefin type resin are heat-processed dynamically in presence of a crosslinking agent.

Hereinafter, each component is demonstrated in more detail.

1. Ethylene-α-olefin copolymer ([A] and [A1])

This ethylene-alpha-olefin type copolymer (henceforth simply a "EAO type copolymer") contains an ethylene monomer unit (a1) and the monomer unit (a2) of the alpha olefin which has 3 or more carbons except ethylene. It is a copolymer.

The amount of ethylene monomer unit (a1) is preferably 35 to 95 mol%, more preferably 40 to 90 mol%, particularly when the total amount of monomer units constituting the EAO copolymer is 100 mol%. Preferably it is 45-85 mol%. If the amount of the ethylene monomer unit (a1) is too large, the flexibility of the thermoplastic elastomer composition obtained tends to be insufficient, while if too small, the mechanical strength may not be sufficient.

As an alpha olefin which forms the said monomeric unit (a2), it is preferable that carbon number is three or more, and it is propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-methyl-1- butene, 2- Methyl-2-butene, 3-methylbutene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene and the like Can be. These can be used individually by 1 type or in combination of 2 or more types. Among these, those having 3 to 10 carbon atoms are more preferable, and by using such α-olefin, it is possible to easily copolymerize other monomers when the EAO copolymer contains other monomer units. Particularly preferred α-olefins are propylene, 1-butene, 1-hexene and 1-octene, and propylene and 1-butene are more preferable.

When content of the said monomeric unit (a2) makes 100 mol% whole quantity of the monomeric unit which comprises an EAO copolymer, Preferably it is 5-65 mol%, More preferably, it is 10-45 mol%, Especially preferably, Is 15 to 40 mol%. When the amount of the monomer unit (a2) is too small, the thermoplastic elastomer composition obtained may not exhibit the desired rubber elasticity. On the other hand, when too much, the durability of the composition obtained may fall.

The EAO copolymer may be a binary copolymer composed of the monomer units (a1) and (a2), and a polymer (three member) composed of these monomer units (a1) and (a2) and another monomer unit (a3). Copolymer, quaternary copolymer, etc.) may be sufficient. As this other monomeric unit, the monomeric unit of a non-conjugated diene compound, etc. are mentioned.

As a non-conjugated diene compound, linear acyclic diene compounds, such as 1, 4- hexadiene, 1, 5- hexadiene, and 1, 6- hexadiene, 5-methyl- 1, 4- hexadiene, 3, 7- dimethyl -1,6-octadiene, 5,7-dimethylocta-1,6-diene, 3,7-dimethyl-1,7-octadiene, 7-methylocta-1,6-diene, dihydromirsen Branched chain acyclic diene compound, tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo [2.2.1] -hepta-2,5-diene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl Alicyclic diene compounds, such as 2-norbornene, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types. Among them, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and the like are preferable.

When using the EAO copolymer containing the said monomeric unit (a3), when the structural amount of the said monomeric unit (a3) makes 100 mol% whole quantity of the monomeric unit which comprises an EAO copolymer, Preferably it is 10 mol. % Or less, More preferably, it is 1-8 mol%. When there is too much structural quantity of the said monomer unit (a3), the durability of the composition obtained may fall.

The intrinsic viscosity (measured at 135 ° C. in decalin solvent) of the EAO copolymer is at least 3.5 Pa / g, preferably at least 3.8 Pa / g, more preferably at 4.0 to 7.O Pa / g. If this intrinsic viscosity is less than 3.5 Pa / g, the mineral oil type softener may bleed out from the thermoplastic elastomer composition obtained or rubber elasticity may fall.

As the EAO-based copolymer, a halogenated copolymer in which a part of the hydrogen atoms in the molecule is substituted with halogen atoms such as chlorine atom and bromine atom can be used. Furthermore, in the presence of these copolymers, vinyl chloride, vinyl acetate, (meth) acrylic acid, derivatives of (meth) acrylic acid [methyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, etc.], male The graft polymer obtained by superposing | polymerizing unsaturated monomers, such as an acid and a derivative of maleic acid (maleic anhydride, maleimide, dimethyl maleate, etc.), and a conjugated diene compound (butadiene, isoprene, chloroprene etc.) can also be used.

The said EAO type copolymer can be used individually by 1 type or in combination of 2 or more types.

Content of EAO type copolymer [A] contained in the thermoplastic elastomer composition of 1st aspect of this invention is 100 in total of this EAO type copolymer [A], polyolefin resin [B], and mineral oil type softener [C]. When it is mass%, it is 5-60 mass%, Preferably it is 10-58 mass%, More preferably, it is 15-55 mass%. When there is too much content of the said EAO type copolymer [A], the flexibility of the thermoplastic elastomer composition obtained may become inadequate, and when too small, mineral oil type softener [C] may bleed out.

The ethylene-alpha-olefin copolymer [A1] which comprises the dielectric rubber [X] for making the thermoplastic elastomer composition of the second aspect of the present invention can be used as it is. The proportion of the EAO copolymer [A1] and the mineral oil softener [C1] constituting the dielectric rubber [X] are 20 to 80 mass% and 20 to 80 mass%, respectively, when the total is 100 mass%. Preferably it is 25-75 mass% and 25-75 mass%, More preferably, it is 30-70 mass% and 30-70 mass%.

Content of the dielectric rubber [X] contained in the thermoplastic elastomer composition of the second aspect of the present invention was 100% by mass of the total of the dielectric rubber [X], the polyolefin resin [B] and the mineral oil softener [C2]. In this case, it is 5-60 mass%, Preferably it is 10-58 mass%, More preferably, it is 15-55 mass%. When the content of the dielectric rubber [X] is too large, the flexibility of the obtained thermoplastic elastomer composition may not be sufficient, while when too small, the mineral oil softener [C1] and / or [C2] bleeds out. There is.

The EAO copolymer ([A] or [A1]) is, for example, ethylene, in the presence of a catalyst comprising a Ziegler-Natta catalyst, a soluble vanadium compound and a solvent containing an organoaluminum compound. (alpha) -olefin and nonconjugated diene can be obtained by the polymerization method by the medium-low pressure method, such as the method of superposing | polymerizing, supplying hydrogen as a molecular weight regulator as needed. The polymerization can be carried out by a gas phase method (fluid phase or stirring phase) or a liquid phase method (slurry method or solution method).

As said soluble vanadium compound, for example, VOCl ₃ and VCl ₄ It is preferable to use the reaction product of at least one of and alcohol. Alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, n-hexanol, n-octanol, 2-ethylhexanol, n-decanol and n-dodecanol Although etc. can be used, Among these, a C3-C8 alcohol is used preferably.

Examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquechloride and butylaluminum sesque Chloride, ethyl aluminum dichloride, butyl aluminum dichloride, methyl aluminoxane which is a reaction product of trimethyl aluminum and water, etc. are mentioned. Among them, in particular, ethyl aluminum cesyl chloride, butyl aluminum cesyl chloride, a mixture of ethyl aluminum cesyl chloride and triisobutyl aluminum, and a mixture of triisobutyl aluminum and butyl aluminum cesyl chloride are preferably used. As the solvent, hydrocarbons are preferably used, and among these, n-pentane, n-hexane, n-heptane, n-octane, isooctane and cyclohexane are preferably used. These can be used individually by 1 type or in combination of 2 or more types.

As a form of the dielectric ethylene-alpha-olefin type copolymer which is a non-dielectric ethylene-alpha-olefin type copolymer [A] and dielectric rubber [X], a bale, a crumb, a pellet, and a powder (a bale pulverized product is included) ) May be in any form. You may use together a non-dielectric ethylene-alpha-olefin type copolymer [A] and a dielectric ethylene-alpha-olefin type copolymer [X].

2. Polyolefin resin ([B] and [B1])

As said polyolefin resin, a homopolymer may be sufficient and a copolymer may be sufficient as the sum total of the monomeric units of 1 or more types of alpha-olefins exceeding 50 mol%. In the case of a copolymer, the copolymer of alpha-olefins may be sufficient, and the copolymer of alpha-olefin and the other monomer copolymerizable with this alpha-olefin may be sufficient. As this polyolefin resin, crystalline resin and / or amorphous resin can be used.

When crystalline polyolefin resin (B-a) is used as said polyolefin resin, this crystallinity is 50% or more, Preferably it is 53% or more, More preferably, 55% or more by the crystallinity degree by X-ray diffraction. This degree of crystallinity is closely related to the density. For example, in the case of polypropylene, the density of the α-type crystal (monocrystalline) is 0.936 g / cm 3, and the density of the smectica-type microcrystal (the hexagonal crystal) is 0.886 g. / Cm 3, the density of the amorphous (atactic) component is 0.850 g / cm 3. In the case of poly-1-butene, the density of the isotactic crystal component is 0.91 g / cm 3 and the density of the amorphous (atactic) component is 0.87 g / cm 3.

Therefore, the density of the crystalline polyolefin-based resin (B-a) is preferably 0.89 g / cm 3 or more, more preferably 0.90 to 0.94 g / cm 3, and the crystallinity can be made 50% or more by using this range. When the crystallinity of the crystalline polyolefin resin (B-a) is less than 50% and the density is less than 0.89 g / cm 3, the heat resistance, strength, and the like of the thermoplastic elastomer composition to be obtained tend to decrease.

Preferable alpha-olefin which forms said crystalline polyolefin resin (B-a) is a C2 or more thing, More preferably, it is a C2-C12 thing. Of these, propylene and 1-butene are preferred.

Content of the monomeric unit (b1) of the alpha olefin which comprises the said crystalline polyolefin type resin (Ba) is preferable when the whole quantity of the monomeric unit which comprises this crystalline polyolefin type resin (Ba) is 100 mol%. Preferably it is 80 mol% or more, More preferably, it is 90-100 mol%.

When the said crystalline polyolefin resin (B-a) is a copolymer, this copolymer may be any of a block copolymer and a random copolymer. However, in order to set it as the block copolymer of said crystallinity degree, when the total amount of the structural unit except the monomeric unit (b1) of (alpha) -olefin makes the whole quantity of the monomeric unit which comprises a block copolymer 100 mol%, Is 40 mol% or less, More preferably, it is 20 mol% or less. The block copolymer can be obtained by living polymerization using a Ziegler-Natta catalyst.

In order to set it as the random copolymer of said crystallinity degree, when the total amount of the structural unit except the monomeric unit (b1) of (alpha) -olefin makes the whole quantity of the monomeric unit which comprises a random copolymer 100 mol%, Preferably it is 15 It is mol% or less, More preferably, it is 10 mol% or less.

The random copolymer can be obtained by polymerizing α-olefin or the like in the presence of a catalyst component containing, for example, a Ziegler-Natta catalyst, a soluble vanadium compound, an organoaluminum compound, and a solvent. As a polymerization method, a medium and low pressure method etc. are mentioned, It can carry out by a gas phase method (fluid phase or stirring phase), a liquid phase method (slurry method or a solution method), etc. In the case of superposition | polymerization, you may use molecular weight regulators, such as hydrogen gas, as needed.

Examples of the soluble vanadium compound, VOCl _3, and (or) it is preferred to use a reaction product of VCl ₄ with an alcohol. Alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, n-dodecanol Etc. can be mentioned. Among these, alcohols having 3 to 8 carbon atoms are preferable.

Examples of the organoaluminum compound include trityl aluminum, triisobutylaluminum, tri-n-hexyl aluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquechloride, butylaluminum sesquechloride and ethyl Aluminum dichloride, butyl aluminum dichloride, methylaluminoxane, which is a reaction product of trimethylaluminum and water, and the like. Among these, ethyl aluminum sesquichloride, butyl aluminum sesquilide, a mixture of ethyl aluminum sesquichloride and triisobutyl aluminum, and a mixture of triisobutyl aluminum and butyl aluminum sesquichloride are preferable.

As said solvent, a hydrocarbon is preferable and especially n-pentane, n-hexane, n-heptane, n-octane, isooctane, and cyclohexane are preferable. These can be used individually by 1 type or in combination of 2 or more types.

Melting | fusing point of the said crystalline polyolefin resin (B-a), ie, the maximum peak temperature according to the differential scanning calorimetry, becomes like this. Preferably it is 100 degreeC or more, More preferably, it is 120 degreeC or more. If this melting | fusing point is less than 100 degreeC, there exists a tendency for sufficient heat resistance and strength not to be exhibited.

The melt flow rate (temperature 230 ° C., load 2.16 kg) (hereinafter simply referred to as “MFR”) of the crystalline polyolefin resin (Ba) is preferably 0.1 to 1,000 g / 10 minutes, more preferably 0.5 To 500 g / 10 min, more preferably 1 to 100 g / 10 min. If this MFR is less than 0.1 g / 10 minutes, there exists a tendency for the kneading processability, extrusion processability, etc. of a raw material composition to become inadequate. On the other hand, when it exceeds 1,000 g / 10min, there exists a tendency for the intensity | strength of the thermoplastic elastomer composition obtained to fall.

Therefore, as said crystalline polyolefin resin (Ba), crystallinity degree is 50% or more, density is 0.89 g / cm <3> or more, content of the ethylene monomeric unit is 20 mol% or less, melting | fusing point is 100 degreeC or more, MFR is 0.1-100 g / It is preferable that it is 10 minutes, and it is especially preferable to use the copolymer of polypropylene and / or propylene and ethylene whose melting | fusing point is 140-170 degreeC.

The said crystalline polyolefin resin (B-a) can be used individually by 1 type or in combination of 2 or more types.

When using amorphous polyolefin resin (Bb) (henceforth also called "amorphous polyolefin resin (Bb)") as said polyolefin resin, this crystallinity is less than 50% of the crystallinity by X-ray diffraction, and is preferable. Preferably it is 30% or less, More preferably, it is 20% or less. When viewed from the density, the density of the amorphous polyolefin resin (B2) is preferably 0.85 to 0.89 g / cm 3, more preferably 0.85 to 0.88 g / cm 3.

The preferable alpha-olefin which forms said amorphous polyolefin resin (B-b) is a C3 or more thing, More preferably, it is 3-12.

When content of the monomer unit (b2) of the alpha olefin which comprises the said amorphous polyolefin resin (Bb) makes the whole quantity of the monomer unit which comprises this amorphous polyolefin resin (Bb) 100 mol%, Preferably 60 mol% or more.

Examples of the amorphous polyolefin resin (Bb) include homopolymers such as atactic polypropylene and atactic poly1-butene, propylene exceeding 50 mol%, and other α-olefins (ethylene, 1-butene, 1-pentene, 1). Copolymers of -hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc., more than 50 mol% of 1-butene and other α-olefins (ethylene, propylene, 1-pentene, 1-hexene , 4-methyl-1-pentene, 1-octene, 1-decene and the like).

Atactic polypropylene and atactic poly-1-butene can be obtained by polymerization using a zirconocene compound-methylaluminoxane catalyst.

The atactic polypropylene can be obtained as a by-product of the polypropylene exemplified as the crystalline polyolefin-based polymer (B-a).

When said amorphous polyolefin resin (B-b) is a copolymer, this copolymer may be any of a block copolymer and a random copolymer. However, in the case of a block copolymer, the monomeric unit (b2) of the alpha olefin comprised more than 50 mol% needs to be bonded by the atactic structure. This block copolymer can be obtained by living polymerization using a Ziegler-Natta catalyst. A random copolymer can be obtained by the method similar to the said crystalline polyolefin type polymer (B-a).

When the amorphous polyolefin resin (Bb) is a copolymer of α-olefin having 3 or more carbon atoms and ethylene, when the total amount of the monomer units constituting the amorphous polyolefin resin (Bb) is 100 mol%, the α-olefin Content of the monomeric unit (b2) of becomes like this. Preferably it is 60-100 mol%.

As the amorphous polyolefin resin (B-b), atactic polypropylene, a copolymer containing more than 50 mol% of propylene monomer units and ethylene monomer units, and a copolymer of propylene and 1-butene are particularly preferable.

The polystyrene reduced number average molecular weight (Mn) by GPC of the amorphous polyolefin resin (B-b) is preferably 1,000 to 20,00O, more preferably 1,500 to 15,00O.

The amorphous polyolefin resin (B-b) may be used alone or in combination of two or more thereof.

The said polyolefin resin may be used independently of the said crystalline polyolefin resin (B-a) and amorphous polyolefin resin (B-b), respectively, and may be used combining it according to the objective, a use, etc.

Content of the polyolefin resin [B] contained in the thermoplastic elastomer composition of the 1st aspect of this invention is 100 mass% of the sum total of EAO copolymer [A], polyolefin resin [B], and mineral oil type softener [C]. When it is set as 1-20 mass%, Preferably it is 3-18 mass%, More preferably, it is 5-15 mass%. When there is too much content of the said polyolefin resin [B], there exists a tendency for the flexibility of the thermoplastic elastomer composition obtained to become insufficient, and when too small, there exists a tendency for kneading workability to fall.

Content of polyolefin resin [B1] contained in the thermoplastic elastomer composition of 2nd aspect of this invention made 100 mass% the sum total of dielectric rubber [X], polyolefin resin [B1], and mineral oil type softener [C2]. In this case, it is 1-20 mass%, Preferably it is 3-18 mass%, More preferably, it is 5-15 mass%. When there is too much content of the said polyolefin resin [B1], there exists a tendency for the flexibility of the thermoplastic elastomer composition obtained to become insufficient, and when too small, there exists a tendency for kneading workability to fall.

3. Mineral oil-based softeners ([C], [C1] and [C2])

The mineral oil-based softener is not particularly limited as long as it is conventionally used in rubber products and the like, and paraffinic, naphthenic and aromatic mineral oils can be given.

The softener for rubber which consists of mineral oil type hydrocarbon is generally a mixture of the three of an aromatic ring, a naphthenic ring, and a paraffin chain. Paraffinic mineral oil accounts for 50% or more of the total carbon number of the paraffin chain, and naphthenic mineral oil of 30 to 45% of the carbon number of the naphthenic ring, and aromatic mineral oil of 30% or more of the total carbon number of the aromatic ring Each is classified as

The paraffinic, naphthenic and aromatic mineral oils may be used in combination of these, and furthermore, each may be used alone or in combination of two or more thereof. Among these, in any of [C], [C1], and [C2], paraffinic mineral oil is preferable, and hydrogenated paraffinic mineral oil is particularly preferable. As paraffinic mineral oil, "Dia process oil PW90", "Diana process oil PW380", etc. made by Idemitsu Corporation are mentioned, for example.

Polystyrene reduced weight average molecular weight (Mw) by GPC of the said mineral oil type softener becomes like this. Preferably it is 300-2,00O, More preferably, it is 500-1,500. Kinetic viscosity in 40 degreeC becomes like this. Preferably it is 20-800 cSt, More preferably, it is 50-600 cSt. The pour point is preferably -40 to 0 ° C, more preferably -30 to 0 ° C.

The mineral oil softener may be used in combination with low molecular weight hydrocarbons such as polybutene and polybutadiene.

The content of the mineral oil softener [C] contained in the thermoplastic elastomer composition of the first aspect of the present invention is 100% by mass of the total of the EAO copolymer [A], the polyolefin resin [B] and the mineral oil softener [C]. When it sets to 30-94 mass%, Preferably it is 32-87 mass%, More preferably, it is 35-80 mass%. When there is too much content of the said mineral oil type softener [C], there exists a tendency for the intensity | strength of the thermoplastic thermoplastic elastomer composition obtained to become insufficient, and the mineral oil type softener [C] may bleed out. On the other hand, when too small, there exists a tendency for the flexibility of the thermoplastic elastomer composition obtained to become insufficient.

The mineral oil softener [C2] contained in the thermoplastic elastomer composition of the second aspect of the present invention may be the same as or different from the mineral oil softener [C1] constituting the dielectric rubber [X]. Content of this mineral oil type softener [C2] is 30-94 mass%, when the sum total of dielectric rubber [X], polyolefin resin [B], and mineral oil type softener [C2] is 100 mass%, Preferably it is It is 32-87 mass%, More preferably, it is 35-80 mass%. When there is too much content of the said mineral oil type softener [C2], there exists a tendency for the strength of the thermoplastic elastomer composition obtained to become insufficient, and the mineral oil type softener [C2] may bleed out. On the other hand, when too small, there exists a tendency for the flexibility of the thermoplastic elastomer composition obtained to become insufficient.

The total amount of the mineral oil softener contained in the thermoplastic elastomer composition of the second aspect of the present invention is less than the total amount of the mineral oil softener contained in the thermoplastic elastomer composition of the first aspect. This is because the mineral oil-based softener [C1] is already contained in the dielectric rubber [X].

4. Hydrogenated diene polymer ([D] and [D1])

The hydrogenated diene polymer is not particularly limited as long as it is a hydrogenated product of a diene polymer including a monomer unit of a conjugated diene compound, and (I) a hydrogenated product of a (co) polymer containing only monomer units of a conjugated diene compound, (II ) Hydrogenates, such as a polymer containing the monomeric unit of a conjugated diene compound, and the monomeric unit of a compound (for example, a vinyl aromatic compound) which can superpose | polymerize with this conjugated diene compound, etc. are mentioned.

1 type may be sufficient as said hydrogenated diene type polymer with respect to said (I), said (II), etc., and 2 or more types of combination may be sufficient as it. Moreover, the combination of said (I) and said (II) may be sufficient. This hydrogenated diene polymer may or may not be crosslinked by this thermoplastic elastomer composition.

As said (I), a hydrogenated butadiene block copolymer etc. are mentioned.

As said (II), (i) block copolymer containing the polymer block of a vinyl aromatic compound, and the polymer block of a conjugated diene compound (for example, hydrogenated styrene butadiene block copolymer, hydrogenated styrene isoprene block copolymer, hydrogenation) Styrene butadiene isoprene block copolymers, etc.), (ii) a block copolymer comprising a polymer block of a vinyl aromatic compound and a random copolymer block of a conjugated diene compound and a vinyl aromatic compound, and (iii) a polymer block of a conjugated diene compound; Block copolymer comprising a copolymer block of a conjugated diene compound and a vinyl aromatic compound, (iv) a tapered phase block of a vinyl aromatic compound and a conjugated diene compound in which a polymer block of the conjugated diene compound and a monomer unit of the vinyl aromatic compound increase Block copolymer comprising a, (v) random air of the conjugated diene compound and vinyl aromatic compound There may be mentioned the block body and, for the monomer unit of the vinyl aromatic compound incrementally, vinyl aromatic compounds and conjugated block copolymer containing a tapered block of the diene compound and the like.

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types. Of these, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable.

As a vinyl aromatic compound, styrene, tert- butyl styrene, (alpha) -methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1, 1- diphenyl styrene, vinyl naphthalene, vinyl anthracene, N, N-di Ethyl-p-aminoethylstyrene, vinylpyridine and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, styrene is preferable.

As the hydrogenated diene polymer, a halogenated hydrogenated diene polymer in which a part of hydrogen atoms in a molecule is substituted with a halogen atom such as a chlorine atom or a bromine atom can be used.

Furthermore, in the presence of these polymers, vinyl chloride, vinyl acetate, (meth) acrylic acid, derivatives of (meth) acrylic acid [methyl (meth) acrylate, (meth) acrylic acid glycidyl, (meth) acrylamide, etc.], maleic acid And graft polymers obtained by polymerizing unsaturated monomers such as derivatives of maleic acid (maleic anhydride, maleimide, dimethyl maleate, etc.) and conjugated diene compounds (butadiene, isoprene, chloroprene and the like).

The hydrogenation rate of the said hydrogenated diene polymer becomes like this. Preferably it is 70% or more, More preferably, it is 90% or more, More preferably, it is 95% or more. In addition, this "hydrogenation rate" means the ratio of the number of the olefinic unsaturated bonds in a hydrogenated side chain or main chain with respect to the number of the olefinic unsaturated bonds in the side chain or main chain of the conjugated diene unit which comprises the diene polymer before hydrogenation. The value to indicate.

As the hydrogenated diene polymer, an uncrosslinked polymer may be used, or a crosslinked polymer may be used. Moreover, you may use combining these. The crosslinked hydrogenated diene polymer can be obtained by a conventionally known method such as a method described later.

When the said hydrogenated diene type polymer is a 5 mass% toluene solution, the solution viscosity in 30 degreeC becomes like this. Preferably it is 5 mPa * s or more, More preferably, it is 10 mPa * s or more. This toluene solution viscosity is a surrogate index of molecular weight, and when it is less than 5 mPa * s, there exists a tendency for the mechanical strength of the thermoplastic elastomer composition obtained to fall.

As said hydrogenated diene type polymer, a hydrogenated styrene butadiene block copolymer and a hydrogenated styrene butadiene isoprene block copolymer are preferable.

The hydrogenated diene-based polymer can be easily produced according to a known method, for example, the method disclosed in Japanese Patent Application Laid-Open No. 2-36244, that is, a method of living anion polymerization of conjugated diene compound and vinyl aromatic compound. This is followed by a method for producing a polymer before hydrogenation and then hydrogenating the polymer before hydrogenation in the presence of a catalyst.

In living anion polymerization, initiators, such as an organolithium compound and an organic sodium compound, are used normally. As this organolithium compound, alkyl lithium, such as n-butyl lithium, sec-butyl lithium, t-butyl lithium, is mentioned, It is used preferably. As a solvent used at the time of superposition | polymerization, hydrocarbon solvents, such as hexane, heptane, methylcyclopentane, cyclohexane, benzene, toluene, xylene, 2-methylbutene-1,2-methylbutene-2, are used. The method of living anion polymerization may be batch type or continuous type, and polymerization temperature is the range of 0-120 degreeC normally.

In the living anionic polymerization, the hydrogenated block copolymer obtained by using together an ether, a tertiary amine, an alkoxide of an alkali metal (sodium, potassium, etc.), phenoxide, sulfonic acid salt, etc., and selecting the kind, the amount of use, etc. appropriately. The ratio with respect to the number of all conjugated diene units of the number of conjugated diene units which have an olefinic unsaturated bond in the side chain in can be controlled easily.

The molecular weight of a polymer can also be enlarged by adding a polyfunctional coupling agent or a crosslinking agent, and carrying out a coupling reaction or crosslinking immediately before completion | finish of living anion polymerization.

As the coupling agent, divinylbenzene, 1,2,4-trivinylbenzene, epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, benzene-1,2,4-triisocyanate, diethyl oxalate , Diethyl malonate, diethyl adipic acid, dioctyl adipic acid, dimethyl phthalate, diethyl phthalate, diethyl terephthalate, diethyl carbonate, 1,1,2,2-tetrachloroethane, 1,4-bis (trichloro Methyl) benzene, trichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, (dichloromethyl) trichlorosilane, hexachlorodisilane, tetraethoxysilane, tetrachlorotin, 1,3-dichloro- 2-propanol etc. are mentioned. Of these, divinylbenzene, epoxidized 1,2-polybutadiene, trichlorosilane, methyltrichlorosilane and tetrachlorosilane are preferable.

Examples of the crosslinking agent include divinylbenzene, adipic diester, epoxidized liquid butadiene, epoxidized soybean oil, epoxidized linseed oil, triylene diisocyanate, diphenylmethane diisocyanate, 1,2,4-benzenetriisocyanate and the like.

The pre-hydrogenated polymer obtained as described above is reacted at a hydrogen pressure of 1 to 100 kg / cm 2, at a temperature in the range of -10 to 150 ° C., in the presence of a hydrogenated catalyst, in a hydrocarbon solvent to give a desired hydrogenated diene polymer. can do.

Examples of the hydrogenation catalyst include metal elements selected from periodic table Ib, IVb, Vb, VIb, VIIb, and group VIII elements such as Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, and Pt. Compounds are used. As this compound, metals, such as a metallocene type compound containing elements, such as Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, Re, Pd, Ni, Pt, Rh, Ru, are carbon, silica Supported heterogeneous catalysts supported on a carrier such as alumina, diatomaceous earth, organic salts of elements such as Ni and Co, or homogeneous Ziegler catalysts in which acetylacetone salts and reducing agents such as organic aluminum are combined, and organic such as Ru and Rh Metal compounds or complexes; fullerenes containing hydrogen; carbon nanotubes; and the like. These hydrogenated catalysts can be used individually by 1 type or in combination of 2 or more types. Among them, a metallocene compound containing an element selected from Ti, Zr, Hf, Co, and Ni, or a metal containing an element selected from Ti, Zr, and Hf, which can be hydrogenated in a homogeneous system in an inert organic solvent. Sen compounds are preferred. In addition, an inexpensive and industrially useful hydrogenation catalyst obtained by reacting a titanocene compound with an alkyl lithium is also preferable.

After hydrogenation, the hydrogenated diene polymer produced | generated from the reaction solution is isolate | separated by removing the residue of a catalyst as needed, or adding an phenolic or amine antioxidant. Isolation of the hydrogenated diene polymer can be carried out by, for example, adding acetone, alcohol or the like to the reaction solution and precipitating it, adding the reaction solution into a boiling water under stirring, and then distilling off the solvent.

As said hydrogenated diene type polymer, the following commercial items can be used. For example, the grades which are preferable as "Sefton" made from Kuraray Co., Ltd. (hydrogenated styrene butadiene isoprene block copolymer are 4044, 4055, 4077, etc., and are hydrogenated styrene butadiene block copolymers, such as 8007, 8004, 8006, etc.). JTB Co., Ltd., etc. made by Asahi Kasei Co., Ltd. (preferred grades are H1052, H1031, H1041, H1051, H1062, H1943, H1913, H1043, H1075, JT-90P, etc.) "Crayton" made by Creton Polymers (as hydrogenated styrene-butadiene block copolymer), such as "dynaron" (as hydrogenated styrene-butadiene block copolymer, and the like grade) are preferable grades G1650, G1651, G1652, G1657, etc.) etc. can be used.

Content of the hydrogenated diene polymer [D] contained in the thermoplastic elastomer composition of 1st aspect of this invention is 100 mass in total of EAO copolymer [A], polyolefin resin [B], and mineral oil type softener [C]. When it is negative, it is 0.1-50 mass parts, Preferably it is 0.5-45 mass parts, More preferably, it is 1-40 mass parts. When there is too much content of the said hydrogenated diene type polymer [D], the fluidity | liquidity of the thermoplastic elastomer composition obtained may deteriorate. On the other hand, when too little, mineral oil type softener [C] may bleed out.

In this case, the combination of the contents of the ethylene-α-olefin copolymer [A], the polyolefin resin [B] and the mineral oil softener [C] is 5 to 60 mass%, respectively, when these totals are 100 mass%. , 1 to 20% by mass and 30 to 94% by mass, preferably 10 to 58% by mass, 3 to 18% by mass and 32 to 87% by mass, more preferably 15 to 55% by mass, 5 to 15% by mass. And 35 to 80 mass%.

Content of the hydrogenated diene type polymer [D1] contained in the thermoplastic elastomer composition of 2nd aspect of this invention made 100 mass parts the sum total of dielectric rubber [X], polyolefin resin [B1], and mineral oil type softener [C2]. In this case, it is 0.1-50 mass parts, Preferably it is 0.5-45 mass parts, More preferably, it is 1-40 mass parts. When there is too much content of the said hydrogenated diene type polymer [D1], the fluidity | liquidity of the thermoplastic elastomer composition obtained may deteriorate. On the other hand, when too little, mineral oil type softener [C2] may bleed out.

The thermoplastic elastomer compositions of the first and second aspects of the present invention may contain other polymer components in addition to the ethylene-α-olefin copolymer, polyolefin resin, and hydrogenated diene polymer. The other polymer component is not particularly limited as long as it does not impair mechanical strength, flexibility, or the like of the thermoplastic elastomer composition to be obtained.

Such polymer components include ionomer resins, aminoacrylamide polymers, polyethylene maleic anhydride graft polymers, polyisobutylenes, ethylene vinyl chloride copolymers, ethylene vinyl alcohol copolymers, ethylene vinyl acetate copolymers, and polyethylene oxides. , Ethylene-acrylic acid copolymer, polypropylene maleic anhydride graft polymer, polyisobutylene and maleic anhydride graft polymer thereof, chlorinated polypropylene, 4-methylpentene-1 resin, polystyrene, ABS resin, ACS resin, AS Resin, AES resin, ASA resin, MBS resin, acrylic resin, methacryl resin, vinyl chloride resin, vinylidene chloride resin, polyamide resin, polycarbonate, vinyl alcohol resin, vinyl acetal resin, fluorine resin, polyether resin , Polyethylene terephthalate, nitrile rubber and its hydrogenated substances, acrylic rubber, silicone rubber, fluorine Radish, butyl rubber, natural rubber, chlorinated polyethylene thermoplastic elastomer, syndiotactic 1,2-polybutadiene, simple blended olefin thermoplastic elastomer, implant type olefin thermoplastic elastomer, polyvinyl chloride thermoplastic elastomer, polyurethane thermoplastic elastomer And polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and fluorine-based thermoplastic elastomers. These polymer components can be used individually by 1 type or in combination of 2 or more types.

5. Additive

In the thermoplastic elastomer composition of the present invention, in addition to the above components, antioxidants, antistatic agents, blocking agents, sealant improvers, lubricants, anti-aging agents, heat stabilizers, weathering agents, metal inerts, ultraviolet absorbers, light stabilizers, antifreeze agents, etc. Stabilizers, antibacterial and antifungal agents, dispersants, plasticizers, crystal nucleating agents, flame retardants, tackifiers, foaming aids, dyes, pigments (such as titanium oxide), colorants such as carbon black, metal powders such as ferrite, glass fibers and metal fibers Inorganic fibers such as inorganic fibers, carbon fibers, aramid fibers, composite fibers, inorganic whiskers such as potassium titanate whiskers, glass beads, glass balloons, glass flakes, asbestos, mica, calcium carbonate, talc, wet silica, dry silica , Alumina, alumina silica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice, evo powder, cotton floc, cork powder, sulfate bar , Or may have a fluorine resin, a polymer of a filler, various additives, or a mixture thereof, such as beads, a polyolefin wax, cellulose powder, rubber powder, fillers such as wood powder, and low molecular weight polymer is contained.

6. Thermoplastic Elastomer Composition

In the thermoplastic elastomer composition of the present invention, at least the ethylene-α-olefin-based copolymer and the polyolefin-based resin are dynamically heat treated in the presence of a crosslinking agent. That is, the crosslinked ethylene-α-olefin copolymer and the crosslinked polyolefin resin are included. When the hydrogenated diene type polymer used at the time of manufacture was an uncrosslinked substance, it may be bridge | crosslinked by dynamic heat processing. In addition, "dynamically heat-processing" means performing both a shearing force and heating.

Although it does not specifically limit as said crosslinking agent, It can bridge | crosslink each of EAO copolymer and polyolefin resin, or both EAO copolymer and polyolefin resin by dynamic heat treatment at the temperature more than melting | fusing point of polyolefin resin. Preferred compounds are preferred.

Examples of the crosslinking agent include organic peroxides, phenolic crosslinking agents, sulfur, sulfur compounds, p-quinones, derivatives of p-quinone dioximes, bismaleimide compounds, epoxy compounds, silane compounds, amino resins, polyol crosslinking agents, polyamines, and triazine compounds. And metal soaps. These can be used individually by 1 type or in combination of 2 or more types. Among these, organic peroxides and phenol resin crosslinking agents are preferable.

Examples of the organic peroxide include 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3,2,5-dimethyl-2, 5-bis (tbutylperoxy) hexene-3,2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,2'-bis (t-butylperoxy) -p-iso Propylbenzenes, dicumylperoxide, di-t-butylperoxide, t-butylperoxide, p-mentaneperoxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane , Dilauroyl peroxide, diacetyl peroxide, t-butylperoxybenzoate, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, benzoyl peroxide, di (t-butylperoxy) per Benzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, t-butylperoxy isopropyl carbonate and the like. These can be used individually by 1 type or in combination of 2 or more types. Among them, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-3,2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane and α, α-bis (t-butylperoxy) diisopropylbenzene, dicumylperoxide, di-t-butylperoxide are preferred.

As a phenol type crosslinking agent, the p-substituted phenol type compound represented by following formula (I), o-substituted phenol aldehyde condensate, m-substituted phenol aldehyde condensate, brominated alkylphenol aldehyde condensate, etc. are mentioned, for example. Can be. These can be used individually by 1 type or in combination of 2 or more types. Among these, p-substituted phenolic compounds are preferable.

In the formula (I), X is a hydroxyl group, a halogenated alkyl group or a halogen atom, R is a saturated hydrocarbon group of 1 to 15 carbon atoms, n is an integer of 0 to 10.

A p-substituted phenol type compound can be obtained by condensation reaction of p-substituted phenol and an aldehyde (preferably formaldehyde) in presence of an alkali catalyst.

The amount of the crosslinking agent used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, still more preferably 1 part by mass based on 100 parts by mass of the total amount of the polymer component used in the production of the thermoplastic elastomer composition of the present invention. To 10 parts by mass.

When using an organic peroxide as said crosslinking agent, Preferably it is 0.05-10 mass parts, More preferably, it is 0.1-5 mass parts. When the usage-amount of this organic peroxide is too large, the crosslinking degree will become high too much and it exists in the tendency for moldability to deteriorate or mechanical property to fall. On the other hand, when too small, a crosslinking degree will run short and the rubber elasticity and mechanical strength of the thermoplastic elastomer composition obtained may fall.

When using a phenolic crosslinking agent as said crosslinking agent, Preferably it is 0.2-10 mass parts, More preferably, it is 0.5-5 mass parts. When the usage-amount of this phenolic crosslinking agent is too large, there exists a tendency for moldability to deteriorate. On the other hand, when too small, a crosslinking degree will run short and the rubber elasticity and mechanical strength of the thermoplastic elastomer composition obtained may fall.

By using together with a crosslinking adjuvant or a crosslinking promoter, the said crosslinking agent can carry out a crosslinking reaction calmly, and can form especially uniform crosslinking. In particular, in the case of using the organic peroxide as the crosslinking agent, sulfur, sulfur compounds (powder sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur, dipentamethylenethiuram tetrasulfide, etc.), oxime compounds (p-quinone Oxime, p, p'-dibenzoylquinone oxime, etc.), polyfunctional monomers (ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, N, N'-m-phenyl It is preferable to use crosslinking adjuvant, such as lenbismaleimide, N, N'-toluylene bismaleimide, maleic anhydride, divinylbenzene, di (meth) acrylic acid, etc.). These can be used individually by 1 type or in combination of 2 or more types. Of these, p, p'-dibenzoylquinone oxime, N, N'-m-phenylenebismaleimide and divinylbenzene are preferable.

Since N, N'-m-phenylene bismaleimide has a function as a crosslinking agent in the said crosslinking adjuvant, it can also be used as a crosslinking agent.

The amount of the crosslinking aid used in the case of using the organic peroxide as the crosslinking agent is preferably 10 parts by mass or less, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymer component used in the production of the thermoplastic elastomer composition. to be. When the usage-amount of this crosslinking adjuvant is too large, the crosslinking degree will become high too much and it exists in the tendency for molding processability to fall or mechanical property to fall.

When the phenolic crosslinking agent is used as the crosslinking agent, a crosslinking accelerator such as a metal halide (tin tin chloride, ferric chloride, etc.), an organic halide (chlorinated polypropylene, brominated butyl rubber, chloroprene rubber, etc.) is used in combination. The crosslinking rate can be controlled. Moreover, it is more preferable to use dispersing agents, such as metal oxides, such as zinc oxide, and a stearic acid, in addition to a crosslinking promoter.

Although the thermoplastic elastomer composition of the present invention contains a crosslinked ethylene-α-olefin-based copolymer, the content of the crosslinked ethylene-α-olefin-based copolymer can be evaluated as an insoluble content in cyclohexane. That is, the cyclohexane insoluble content at 23 degrees C of the ethylene-alpha-olefin type copolymer contained in this thermoplastic elastomer composition becomes like this. Preferably it is 60 mass% or more, More preferably, it is 65 mass% or more, More preferably, 70 It is mass% or more. When the said cyclohexane insoluble content is less than 60 mass%, rubber elasticity and mechanical strength may fall. The measuring method of the said cyclohexane insoluble content is as follows.

<Measurement method of insoluble cyclohexane content>

About 200 mg of the thermoplastic elastomer composition is weighed and chopped. Thereafter, the obtained three pieces are immersed in 100 ml of cyclohexane in a sealed container at 23 ° C. for 48 hours. Then, this cyclohexane solution is filtered, and the residue on a filter paper is dried for 1 hour with a vacuum dryer (105 degreeC). From the mass of the thermoplastic elastomer composition before immersion, the value obtained by subtracting the mass of the dry residue and the amount of the theoretical mineral oil softener in the thermoplastic elastomer composition (the dissolved non-crosslinked ethylene-α-olefin copolymer in [A] and [A1]) was obtained. Corrected final mass p ”.

On the other hand, the mass of the ethylene-alpha-olefin type copolymer (total amount of [A] and [A1]) is calculated | required from the mass of the thermoplastic elastomer composition before immersion, and is called "corrected initial mass (q)."

Here, a cyclohexane insoluble content is (the insoluble content / EAO copolymer whole quantity in an EAO copolymer), and is calculated | required by following Formula.

Cyclohexane insoluble content [mass%] = [{corrected final mass (p)} ÷ {corrected initial mass (q)}] x 100

The durometer E hardness (by JIS K6253) of the thermoplastic elastomer composition of the present invention is preferably 80 or less, more preferably 75 or less, still more preferably 70 or less.

7. Manufacturing Method of Thermoplastic Elastomer Composition

The manufacturing method of the thermoplastic elastomer composition of this invention will not be specifically limited if it is a method containing the ethylene-alpha-olefin type copolymer and polyolefin resin dynamically heat-treated in presence of a crosslinking agent.

As a general method, the raw material composition containing an ethylene-alpha-olefin type copolymer, a polyolefin resin, a mineral oil type softener, a hydrogenated diene type polymer, and a crosslinking agent is prepared, and the dynamic heat processing of this raw material composition is performed.

As another method, (i) the raw material composition containing an ethylene-alpha-olefin type copolymer (or dielectric rubber), a polyolefin resin, and a crosslinking agent is prepared, and after performing the dynamic heat treatment of this raw material composition, Method of adding, (ii) preparing a raw material composition comprising an ethylene-α-olefin copolymer (or dielectric rubber), a polyolefin resin, a hydrogenated diene polymer, and a crosslinking agent, and performing dynamic heat treatment of the raw material composition. And other raw material components.

The ethylene-alpha-olefin type copolymer, polyolefin resin, and hydrogenated diene type polymer used when preparing a raw material composition may be used as it is, and may be used as a composition containing the same or another additive, respectively. As a shape when using an ethylene-alpha-olefin type copolymer, any of a veil, a crumb, a pellet, and a powder (including the base or the crushed product of a crumb) may be sufficient, and the ethylene-alpha-olefin type copolymer from which a shape differs You may use in combination.

The combination of content of ethylene-alpha-olefin copolymer [A], polyolefin resin [B], and mineral oil type softener [C] in all the raw material components (I) used in order to make it as a thermoplastic elastomer composition of a 1st aspect, When these sum totals are 100 mass%, they are 5-60 mass%, 1-20 mass%, and 30-94 mass%, respectively, Preferably they are 10-58 mass%, 3-18 mass%, and 32-87 mass% More preferably, they are 15-55 mass%, 5-15 mass%, and 35-80 mass%.

In order to make the thermoplastic elastomer composition of a 2nd aspect, the dielectric rubber [X] which consists of an ethylene-alpha-olefin type copolymer [A1] and a mineral oil type softener [C1] is prepared previously, and this dielectric rubber [X] is made into a crosslinking agent, etc. Use with other raw ingredients.

The combination of content of dielectric rubber [X], polyolefin resin [B1], and mineral oil type softener [C2] in all the raw material components (II) used in order to make the thermoplastic elastomer composition of a 1st aspect adds 100 mass% of these sum totals. When it is set to 5 to 60% by mass, 1 to 20% by mass and 30 to 94% by mass, respectively, preferably 10 to 58% by mass, 3 to 18% by mass and 32 to 87% by mass, more preferably 15 To 55 mass%, 5 to 15 mass%, and 35 to 80 mass%.

Melt-kneading apparatus etc. are mentioned as an apparatus used for "dynamically heat-processing" at the time of manufacturing a thermoplastic elastomer composition. The treatment by the melt kneading apparatus may be continuous or batch.

As this melt-kneading apparatus, an open type mixing roll, a non-open type | mold nozzle mixer, a single screw extruder, a twin screw extruder, a continuous kneader, a pressurized kneader, etc. are mentioned, for example. Among these, it is preferable to use continuous melt kneading apparatuses, such as a single screw extruder, a twin screw extruder, and a continuous kneader, from a viewpoint of economy, processing efficiency, etc. The continuous melt kneading apparatus may be used in combination of two or more of the same or different apparatuses.

When using the said twin screw extruder, it is preferable that L / D (ratio of screw effective length L and outer diameter D) is 30 or more, More preferably, it is 36-60. As this twin screw extruder, arbitrary twin screw extruders, such as two screws meshing with each other and not meshing with each other, can be used, for example, the rotation direction of two screws is the same direction, and a screw is meshed with each other. It is more preferable.

Examples of such a twin screw extruder include "PCM" manufactured by Ikegai Co., Ltd. "KTX" manufactured by Kobe Steel Co., Ltd., "TEX" manufactured by Nippon Steel Co., Ltd., "TEM" manufactured by Toshiba Machine Co., Ltd., "ZSK" manufactured by Warner.

When using the said continuous kneader, it is preferable that L / D (ratio of screw effective length L and outer diameter D) is 5 or more, More preferably, L / D is 10.

Examples of such continuous kneaders include "Mixtron KTX, LCM, NCM" manufactured by Kobe Steel Co., Ltd., "CIM CMP", manufactured by Nippon Steel Co., Ltd., and the like.

The treatment temperature at the time of dynamic heat treatment is 120-350 degreeC normally, Preferably it is 150-290 degreeC. The treatment time is usually 20 seconds to 320 minutes, and preferably 30 seconds to 25 minutes. The shear force applied to the mixture is 10 to 20, 000 / sec at a shear rate, preferably 100 to 10,000 / sec.

The thermoplastic elastomer composition obtained as mentioned above is low in hardness, especially the durometer E and the durometer A, has flexibility, and is excellent in rubber elasticity. Therefore, according to the purpose and a use, even when it is set as the molded article which consists only of this thermoplastic elastomer composition, the said outstanding characteristic can be utilized. As a manufacturing method of the molded article which consists of the thermoplastic elastomer composition of this invention, an extrusion molding method, the calender molding method, the solvent casting method, the injection molding method, the vacuum molding method, the powder slash molding method, the heat press method, etc. are mentioned, for example.

8. Molded product

The molded article of the present invention is characterized in that it is formed from the thermoplastic elastomer composition.

The molded article of the present invention can be a product composited by lamination, joining, or the like, manufactured from other materials.

As another material, rubber, resin, thermoplastic elastomer composition other than this invention, a metal (alloy), glass, a textile, a wood, etc. are mentioned, for example.

As rubber | gum and resin, what was illustrated as another polymer component which can be mix | blended with the thermoplastic elastomer composition of this invention can be used.

Examples of the metal (alloy) include stainless steel, aluminum, iron, copper, nickel, zinc, lead, tin, nickel and zinc alloys used in automobiles, ships, and home appliances, iron and zinc alloys, and lead and tin alloys. have.

9. Sealants Made from Thermoplastic Elastomer Compositions:

Among the thermoplastic elastomer compositions of the present invention, a durometer A hardness in accordance with JIS K6253 is preferably 40 or less, preferably 35 or less, more preferably 30 or less, particularly preferably 22 or less, as a sealing material. The thermoplastic elastomer composition has a compression set (measurement condition: 70 ° C, 22 hours) in accordance with JIS K6262, preferably 40% or less, more preferably 38% or less, even more preferably 35% or less. . The sealing material manufactured by using the thermoplastic elastomer composition having such characteristics is extremely excellent in sealing property, and since the mineral oil softener does not bleed out and is made of the thermoplastic elastomer composition, it is possible to recycle at the same time and easily, thereby saving resources. Extremely good.

As a manufacturing method of the sealing material manufactured from the thermoplastic elastomer composition of this invention, the extrusion molding method, the calender molding method, the solvent casting method, the injection molding method, the vacuum molding method, the powder slash molding method, the heat press method, etc. can be used, for example.

Although the shape of the sealing material obtained is not specifically limited, For example, O-ring form, a sheet form, or a rod form etc. are mentioned. A sealing material can also be used as a stopper.

The sealing material of this invention forms this in a sealing part, and is compounded by lamination | stacking, joining, etc., such as components, such as a case part manufactured from other materials, For example, products, such as a container, such as a toner case for copiers and printers, etc. You can do Here, as another material, rubber, resin, thermoplastic elastomer compositions other than this invention, a metal (alloy), glass, a textile, a wood, etc. are mentioned, for example.

In the case of using a product such as a container, the case part may use various materials as described above. However, the case part is preferably composed of a material that can be recycled. Among them, it is preferable that the case portion is made from the thermoplastic resin and / or the thermoplastic elastomer composition because it can be recycled and is easy.

As a thermoplastic resin, a thermoplastic elastomer, and a thermoplastic elastomer composition for a recycleable case part, what has thermoplasticity among what was illustrated as another polymer component in description of the raw material composition used for forming a thermoplastic elastomer composition is used suitably. For example, ionomer resin, aminoacrylamide polymer, polyethylene and maleic anhydride graft polymer, polyisobutylene, ethylene vinyl chloride copolymer, ethylene vinyl alcohol copolymer, ethylene vinyl acetate copolymer, polyethylene Oxide, ethylene-acrylic acid copolymer, polypropylene and maleic anhydride graft polymer thereof, polyisobutylene and maleic anhydride graft polymer thereof, chlorinated polypropylene, 4-methylpentene-1 resin, polystyrene, ABS resin, ACS Resin, AS resin, AES resin, ASA resin, MBS resin, acrylic resin, methacryl resin, vinyl chloride resin, vinylidene chloride resin, polyamide resin, polycarbonate, vinyl alcohol resin, vinyl acetal resin, fluorine resin, Polyether resin, polyethylene terephthalate, chlorinated polyethylene thermoplastic elastomer, syndiotactic 1,2-polybutadi , Simple blended olefin thermoplastic elastomer, implant type olefin thermoplastic elastomer, dynamic crosslinked olefin thermoplastic elastomer, polyvinyl chloride thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, And fluorine-based thermoplastic elastomers. These polymer components can be used individually by 1 type or in combination of 2 or more types.

Moreover, when the olefin type material compatible with a sealing material is selected as a material of a case side, the container by which the case part and the sealing part were heat-sealed can be obtained. On the other hand, when a material (for example, a thermoplastic resin containing a functional group) incompatible with the sealing material is selected as the material of the case part, the sealing part and the case part can be compounded without being fused.

Specifically, polypropylene or polyethylene can be cited as the case-side material compatible with the sealing material, and ABS resin, polycarbonate, and polystyrene can be cited as the case-side material incompatible with the sealing material.

As the container of the present invention, metals (alloys), glass, textiles, wood, etc., which are materials other than thermoplastic resins and thermoplastic elastomer compositions, can also be used. For example, as metals (alloys), stainless steel, aluminum, iron, copper, nickel And zinc, lead, tin, nickel and zinc alloys used in automobiles, ships, and home appliances, iron and zinc alloys, and lead and tin alloys.

The sealing material of this invention can be formed in a container (case part with a sealing part) by forming this in a sealing part, Preferably, it is compounded by injection molding with a case part. In the container, the sealing portion made of the sealing material of the present invention can exhibit extremely excellent sealing performance in housing contents such as powder or liquid such as toner.

As a compounding method by injection molding, two or two or more kinds of resins such as a core back method, a die slide method, a rotary method, and the like are sequentially injected and filled into a mold from separate injection cylinders to form molded articles of different materials or different materials. The shaping | molding method to make is mentioned. It is also possible to obtain a multilayer or multicolor molded article by injecting a plurality of times.

The rotary method is injection molding a material of the first color (first material) from the first cylinder, opening the mold once, and rotating the mold rotating plate by 180 ° with the primary molded product attached to the core side to close the mold. It is a method of manufacturing a composite injection molded article by injection molding a material of the second color (second material) from the second cylinder, opening the mold again, and taking the molded article out of the mold.

The core backing method consists of primary molding and secondary molding, and during the primary molding, a part of the cavity is sealed with a moving core, injection molding of molten resin into an empty cavity to mold the primary semi-molded product, At the time of secondary shaping | molding, the moving core is evacuated and molten resin is injected into the evacuated space, and the molded article integrated with the primary semi-molded article is obtained.

As a manufacturing method of the container using the sealing material of this invention, the die slide method [DSI (Die Slide Injection)] is mentioned as a preferable shaping | molding method among injection molding. The DSI method is briefly described as follows.

First, in a state in which the mold is closed, the primary molded article (half-part of the hollow article) is molded by primary injection, and the mold is opened while the primary molded article is left in the cavity. The metal mold | die has a structure which can move with the die slide mechanism provided in the injection molding machine. This mechanism moves the mold to the position where the primary parts face each other. The mold is closed again, and the resin is secondly injected in the form of a headband so as to surround the joint portion back to the primary molded product, and then integrated. Said hollow article molding method is described, for example in plastic age "development of the hollow injection molding technique by DSI" (Aug. 2002), p74-84, and Unexamined-Japanese-Patent No. 62-87315.

Hereinafter, an Example is given and this invention is demonstrated concretely. The invention is not at all limited by these examples. "%" And "part" in an Example are a mass reference | standard unless there is particular notice.

Example 1

1. Preparation of Thermoplastic Elastomer Compositions

The dielectric rubber (I) which contains the ethylene-alpha-olefin type copolymer and mineral oil type softener (hydrogenated paraffinic mineral oil by Idemitsu Corporation), brand name "Diana process oil PW380" shown below in the ratio shown in Table 1 was prepared. . Thereafter, the dielectric rubber (I), the polyolefin-based resin shown below, the mineral oil-based softener, the hydrogenated diene-based polymer, and various additives except the crosslinking agent and the crosslinking aid were mixed in the blending ratios of Table 2 to obtain a raw material composition. . The raw material composition was put into a pressurized kneader (capacity 10 liters, manufactured by Moriyama Co., Ltd.) heated to 150 ° C in advance, and the polyolefin resin was melted at 40 rpm (shearing speed 200 / sec) until the components were uniformly dispersed. After kneading for 15 minutes, the obtained kneaded material in a molten state was pelletized by a feeder ruder (manufactured by Moriyama Co., Ltd.).

Then, the pellet, the crosslinking agent and the crosslinking aid were added to a Henschel mixer at a ratio shown in Table 2 and mixed for 30 seconds. Then, 200 degreeC, using a twin screw extruder (ratio of full-engagement type screw in the same direction, ratio L / D = 33.5 of the screw flight part and screw diameter (D), the Ikegai Corporation make, PCM45 type), Extrusion was carried out while performing a dynamic heat treatment at a treatment time of a residence time of 1 minute 30 seconds, 300 rpm, and a shear rate of 400 / sec to obtain a pellet-like thermoplastic elastomer composition.

(1) Ethylene-α-olefin Copolymer

(I) Ethylene propylene 5-ethylidene-2-norbornene terpolymer

The ethylene monomer unit amount is 66 mol%, the 5-ethylidene-2-norbornene monomer unit amount is 4.5 mol%, and the intrinsic viscosity measured at 135 degreeC in decalin solvent is 5.5 dl / g.

(II) Ethylene propylene 5-ethylidene-2-norbornene terpolymer

The ethylene monomer unit amount is 66 mol%, the 5-ethylidene-2-norbornene monomer unit amount is 4.5 mol%, and the intrinsic viscosity measured at 135 degreeC in decalin solvent is 2.7 dl / g.

(2) polyolefin resin

(I) crystalline polypropylene

The brand name "Novatec FL25R" (density; 0.90 g / cm <3>, MFR (temperature 230 degreeC, load 2.16 kg); 23g / 10min) made from Nippon Polychem Co., Ltd. was used.

(II) Propylene 1-butene amorphous copolymer

Product name "UBETAC APAO UT 2780" made by Ube Rexen Corporation (Amount of propylene monomer; 71 mol%, melt viscosity; 8,000 cPs, density; 0.87 g / cm 3, crystallinity by X-ray diffraction; 0%, polystyrene equivalent number by GPC) Average molecular weight (Mn): 6,500) was used.

(3) hydrogenated diene polymer

(I) Styrene butadiene isoprene hydrogenated diene polymer

Product made by Kuraray Co., Ltd., brand name "Sefton 4077" (styrene monomer unit amount; 30 mol%, specific gravity; 0.91, hydrogenation rate; 98%, toluene solution viscosity (30 degreeC, concentration 5 mass%); 300 mPa * s, melt flow rate (230 degreeC, 21.2N) did not flow, and it was impossible to measure).

(II) Styrene butadiene hydrogenated diene polymer

Product made by Kuraray Co., Ltd., brand name "Sefton 8006" (styrene monomer unit amount; 30 mol%, specific gravity; 0.91, hydrogenation rate; 98%, toluene solution viscosity (30 degreeC, concentration 5 mass%); 42 mPa * s, melt flow rate (230 degreeC, 21.2N) did not flow, and it was impossible to measure).

(III) Styrene butadiene hydrogenated diene polymer

Creton Polymers, brand name "G1651" (styrene monomer unit amount; 33 mol%, specific gravity; 0.91, hydrogenation rate; 99%, toluene solution viscosity (30 ° C, concentration 5 mass%); 50 mPa s, melt flow rate (230 degreeC, 21.2N) did not flow, and it was impossible to measure).

(4) additive

(i) crosslinking agent

The brand name "perhexa 25B-40" (5-dimethyl-2,5-di (t-butylperoxy) hexane) by the Japan Oil Corporation was used.

(ii) crosslinking aid

Divinylbenzene (purity; 96%) manufactured by Shinil Iron Chemical Co., Ltd. was used.

(iii) anti-aging agents

The brand name "Irganox 1010" (tetrakis [methylene 3- (3,5-di-tert- butyl-4-hydroxyphenyl) propionate] methane) by Ciba Specialty Chemicals Co., Ltd. was used.

Oilfield rubber (I) (II)  Ingredients (parts)  Ethylene-α-olefin Copolymer Ultimate viscosity (점도 / g) (I) 5.5 50 (II) 2.7 60   Mineral oil softener 50 40

2. Evaluation of Thermoplastic Elastomer Compositions

The pellet of the thermoplastic elastomer composition obtained above was processed by the injection molding machine ("N-100" made by Nippon Steel Works, Ltd.), and the sheet (test piece) of length 120mm, width 120mm, and thickness 2mm was produced. This sheet was used for various evaluations. The result was written together in Table 2.

(1) melt flow rate (MFR)

According to JIS K7210, it measured at 190 degreeC and load 21N.

(2) cyclohexane insoluble

It measured at 23 degreeC by the method described in this text.

(3) Hardness (durometer E)

In accordance with JIS K6253, the hardness after 5 seconds from the start of the measurement was measured to set the index of flexibility.

(4) hardness (durometer A)

In accordance with JIS K6253, the hardness 5 seconds after the start of measurement in the durometer A hardness was measured, and the index of flexibility was taken.

(5) tensile breaking strength and tensile breaking elongation

It measured according to JIS K6251.

(6) compression permanent deformation

According to JIS K6262, it measured on 70 degreeC and the conditions of 22 hours, and made it into the index of rubber elasticity.

(7) resilience

According to JIS K6255, it measured at 23 degreeC using the Lubke-type repulsion elastic tester, and set it as the index of rubber elasticity.

(8) Appearance of molding (bleed test of mineral oil softener)

From the said sheet, the test piece of 40 mm length and 30 mm width was punched out, and after leaving a test piece for 168 hours in a 5 degreeC thermostat, the external appearance was visually observed and it was set as the following evaluation.

○; No bleed of mineral oil softener

×; With bleed of mineral oil softener

Example Comparative example One 2 3 One 2 3   Raw material component (part) Oilfield rubber (I) 47 47 35 47 47 (II) 47 Polyolefin resin (I) 4 4 3 4 4 4 (II) 4 4 3 4 4 4 Mineral oil softener 45 45 59 45 45 45  Hydrogenated diene polymer (I) 5 5 (II) 5 (III) 25 Crosslinking agent 0.8 0.8 0.8 0.8 0.8 Crosslinking aid 0.6 0.6 0.6 0.6 0.6 Anti-aging 0.1 0.1 0.1 0.1 0.1 0.1 Total amount of mineral oil softener in the composition 68.5 68.5 76.5 44 68 68.5 With or without dynamic crosslinking U U U U U radish   Properties MFR (190 ° C, 21N) [g / 10min] 8 10 8 16 5 One Cyclohexane Insoluble [%] 87 85 86 81 84 29 Hardness (durometer E) 55 54 55 53 59 53 Hardness (durometer A) 26 22 24 19 22 19 Tensile Break Strength [MPa] 2.1 2 2.7 1.9 1.4 0.8 Tensile Elongation at Break [%] 770 750 780 720 740 930 Compression set [%] 29 33 19 37 37 90 Resilience [%] 57 57 68 57 56 55 Molding appearance ○ ○ ○ × × ×

Examples 2-3 and Comparative Examples 1-2

Except having used each raw material component in the compounding ratio of Table 2, it carried out similarly to Example 1, and obtained each thermoplastic elastomer composition, and the evaluation was performed. The result was written together in Table 2.

About the comparative example 2, it carried out similarly to the said Example 1, and prepares dielectric rubber (II) of Table 1, mixes by the mixing ratio of Table 2 using this dielectric rubber (II) and another raw material component, A raw material composition was obtained.

Comparative Example 3

Dielectric rubber (I) and another raw material component were mixed by the compounding ratio of Table 2, and the raw material composition was obtained. The raw material composition was charged into a pressurized kneader (capacity 10 liters, manufactured by Moriyama Co., Ltd.) heated at 150 ° C in advance, and the polyolefin resin was melted at 40 rpm (shearing speed 200 / sec) until the components were uniformly dispersed. After kneading for 15 minutes, the obtained kneaded material in a molten state was pelletized by a feeder luder (manufactured by Moriyama Co., Ltd.) to obtain a thermoplastic elastomer composition and evaluated. The result was written together in Table 2.

From the result of Table 2, the comparative example 1 is an example which does not contain a hydrogenated diene type polymer, the mineral oil type softener bleeded out from the surface of a molded article, and was poor in appearance. Although the comparative example 2 contained the hydrogenated diene type polymer, since the intrinsic viscosity of an ethylene-alpha-olefin type copolymer was less than 3.5 dl / g, the mineral oil type softener bleeded out and was bad in appearance. Comparative Example 3 is an example of no dynamic crosslinking, and has poor mechanical strength because of poor tensile properties, large compression set, large bleeding-out of mineral oil softener, and poor appearance.

On the other hand, it can be seen that the thermoplastic elastomer compositions of Examples 1 to 3 are 54 to 55 in hardness (durometer E) and 22 to 26 in hardness (durometer A), which is very low in hardness and excellent in flexibility. In addition, the compression set is very small at 29 to 33%, the rebound elasticity is sufficiently high at 57 to 68%, and the rubber elasticity is excellent. Moreover, neither of the bleed-out phenomenon was recognized and the external appearance was favorable.

Examples 4-5, Comparative Examples 4-5

1. Preparation of Thermoplastic Elastomer Compositions

Dielectric rubber (X), polyolefin resin, mineral oil softener, hydrogenated diene polymer and additives (excluding crosslinking agent and crosslinking aid) shown below were mixed at the blending ratio of Table 3 and pelletized in the same manner as in Example 1. .

Then, the pellet, the crosslinking agent and the crosslinking aid were added to the Henschel mixer at the ratio shown in Table 3, mixed for 30 seconds, and then extruded while performing a dynamic heat treatment using a twin screw extruder as in Example 1 And three types (A, B, C) of pellet-like thermoplastic elastomer compositions were obtained.

(1) oilfield rubber (X)

Dielectric copolymer rubber 1: Ethylene / propylene / 5-ethylidene-2-norbornene terpolymer (66 mol% ethylene content, 4.5 mol% 5-ethylidene-2-norbornene content, intrinsic viscosity 5.5 kPa / g) 50 mass%, paraffin softener 50 mass%

(2) polyolefin resin

(I) crystalline polypropylene

The brand name "Novatec FL25R" (density; 0.90 g / cm <3>, MFR (temperature 230 degreeC, load 2.16 kg); 23g / 10min) made from Nippon Polychem Co., Ltd. was used.

(II) Propylene 1-butene amorphous copolymer

Product name "UBETAC APAO UT 2780" by Ube Rexen Corporation (Amount of propylene monomer; 71 mol%, melt viscosity; 8,000 cPs, density; 0.87 g / cm 3, crystallinity by X-ray diffraction; O%, polystyrene equivalent number by GPC) Average molecular weight (Mn): 6,500) was used.

(3) mineral oil softener

The brand name "Diana process oil PW90" (paraffinic mineral oil) made from Idemitsu Chemical Co., Ltd. was used.

(4) hydrogenated diene polymer

(I) Styrene butadiene isoprene hydrogenated diene polymer

Product made by Kuraray Co., Ltd., brand name "Sefton 4077" (styrene monomer unit amount; 30 mol%, specific gravity; 0.91, hydrogenation rate; 98%, toluene solution viscosity (30 degreeC, concentration 5 mass%); 300 mPa * s, melt flow rate (230 degreeC, 21.2N) did not flow, and it was impossible to measure).

(5) additive

(i) crosslinking agent

The brand name "perhexa 25B-40" (5-dimethyl-2,5-di (t-butylperoxy) hexane) by the Japan Oil Corporation was used.

(ii) crosslinking aid

Divinylbenzene (purity; 96%) manufactured by Shinil Iron Chemical Co., Ltd. was used.

(iii) anti-aging agents

Ciba Specialty Chemicals Co., Ltd. brand name "Irganox 1010" (tetrakis [methylene 3- (3,5-di-tert- butyl-4-hydroxyphenyl) propionate] methane) was used.

A B C   (Part) Oilfield rubber (I) 45 47 75 Polyolefin resin (I) 5 4 6 (II) 5 4 6 Mineral oil softener 40 45 13 Hydrogenated diene polymer (I) 5 Crosslinking agent 0.8 0.8 0.8 Crosslinking aid 0.6 0.6 0.6 Anti aging agents 0.1 0.1 0.1   Properties Cyclohexane Insoluble [%] 85 87 86 MFR (190 ° C, 21N) [g / 10min] 6 22 MFR (230 ° C, 49N) [g / 10min] 41 Hardness (durometer A) 20 22 42 Tensile breaking strength [MPa] 2.7 2.8 4.2 Tensile Break Elongation [%] 700 650 740 Compression permanent deformation [%] 33 34 38 Oil bleed ○ ○ ○

2. Evaluation of Thermoplastic Elastomer Compositions

The pellets of the three types of thermoplastic elastomer compositions obtained above were processed by an injection molding machine (manufactured by Nippon Steel Mill, "N-100" type) to prepare a sheet (test piece) having a length of 120 mm, a width of 120 mm, and a thickness of 2 mm. . This sheet was used for various evaluations. The result was written together in Table 3.

(1) oil bleed

The oil bleedability after leaving to stand on 80 degreeC and 72 hours conditions was visually evaluated.

○; No bleed of mineral oil softener

×; With bleed of mineral oil softener

3. Production of container with seal

Production of the container with a seal was made of polystyrene (grade H230 made by Japan Polystyrene Co., Ltd.) by the die slide injection molding method (M-DSI ^® method) using 220 EII-P2M (injection molding machine for two-color molding) manufactured by Nippon Steel Mill. After molding (cylinder temperature 210 degreeC, mold temperature 50 degreeC), the sealing part side was shape | molded continuously (cylinder temperature 210 degreeC, mold temperature 50 degreeC) from the thermoplastic elastomer composition, and the container with a sealing part was obtained. Fig. 1 shows the obtained container with seal 10, and Fig. 2 separates the seal 1 and the case 2 made from the low hardness seal of the present invention constituting the container 10 with seal. It is a photograph showing a state.

4. Sealing performance evaluation method

(Test Methods)

As shown in FIG. 3, 90% of water 15 was filled in the container with a sealing material (two-color molded article) 10 produced by said 3. Next, this container 10 was covered with a lid 11, and the end was fixed with a double clip (Kuri 34 manufactured by Kokuyo Co., 25 mm inlet width) 12 (8 pieces). 14 represents packing. The container 10 was dropped on the cardboard 13 from a height of 1 m to confirm leakage of water in the container 10. The test was performed five times (n = 5) by changing the drop direction with one sample. The results are shown in Table 4.

Example 4 Example 5 Comparative Example 4 Comparative Example 5 Thermoplastic Elastomer Composition A B C No sealing material n One 2 One 2 One 2 One One ○ ○ ○ ○ ○ ○ × 2 ○ ○ ○ ○ ○ × × 3 ○ ○ ○ ○ × ○ × 4 ○ ○ ○ ○ ○ × × 5 ○ ○ ○ ○ × ○ × Toner Leak Rate (%) 0 0 80 100

○: no leak ×: leak

(Evaluation results)

As is apparent from the results shown in Table 4, the low hardness sealing material (thermoplastic elastomer composition = A, B) according to the present invention did not leak, and the sealing property was good. On the other hand, the sealing material using the thermoplastic elastomer composition whose hardness exceeds 40 was bad sealing property.

Since the thermoplastic elastomer composition of the present invention is excellent in flexibility and rubber elasticity (rebound elasticity, compression set), automobile bumpers, exterior malls, wind sealing gaskets, door sealing gaskets, trunk sealing gaskets, roof side rails, emblems Interior and exterior skins such as inner panels, door trims, console boxes, weather strips, etc. Leisure seats requiring weather resistance, sealing materials for aircrafts and ships, interior and exterior skins, etc. Pharmacopoeia parts and water supply packings, such as seals for general machinery and equipment, such as ash or waterproof sheet materials, sealants in fuel cell stacks, skin materials or housings, railway track pads, rolls for information equipment, cleaning braids, electronic components Image protective film such as a protective film, a sealing material, a photograph, a protective film in a flat panel display (FPD) manufacturing process such as a film for film, a semiconductor and a liquid crystal display device, a cosmetic film for building materials, Ryoyong machine parts, it can be used widely in general foods such as wires, sundry goods products, sports goods.

In addition, the low hardness sealing material of the present invention can be molded by injection molding, extrusion molding, blow molding, compression molding, vacuum molding, lamination molding, calender molding, etc., has an extremely low hardness, excellent sealing property, and a mineral oil softener. Since it does not bleed out and is excellent in the characteristics that compression set is small, it can be used suitably as a sealing material for general machines and apparatuses. In addition, this sealing material is comprised by the thermoplastic elastomer composition and can be recycled, and is extremely excellent in global environmental and resource saving.

The container in which the low hardness sealing material and the case are integrally molded by two-color injection molding can contain various contents and reliably eliminate leaks, and can be used safely during transportation and use.

Claims (16)

[A] 5 to 60 mass% of ethylene-α-olefin-based copolymers having an intrinsic viscosity measured at 135 ° C. at 135 ° C. or higher in [A] decalin solvent, [B] 1 to 20% by mass of polyolefin resin, and [C] With respect to 100 parts by mass in total of 30 to 94% by mass of mineral oil softener (the total of [A], [B] and [C] is 100% by mass), (D) 0.1-50 mass parts of hydrogenated diene type polymers are included, The thermoplastic elastomer composition in which at least the said [A] ethylene-alpha-olefin type copolymer and the said [B] polyolefin type resin are heat-processed dynamically in presence of a crosslinking agent. [X] 20 to 80 mass% of ethylene-α-olefin copolymer having an intrinsic viscosity measured at 135 ° C. at 135 ° C. or higher in [A1] decarin solvent, and 20 to 80 mass% of [C1] mineral oil softener ( However, the sum total of [A1] and [C1] is 100 mass%.) 5-60 mass% of oil-extended rubbers, [B1] 1 to 20 mass% of polyolefin resin, and With respect to 100 mass parts in total of 30-94 mass% of [C2] mineral oil type softeners (However, the sum total of [X], [B1], and [C2] is 100 mass%.), [D1] Contains 0.1 to 50 parts by mass of a hydrogenated diene polymer, The thermoplastic elastomer composition in which at least the said [A1] ethylene-alpha-olefin type copolymer and said [B1] polyolefin type resin are heat-processed dynamically in presence of a crosslinking agent. The hydrogenated substance of the polymer containing the monomeric unit of a conjugated diene compound, the monomer unit of a conjugated diene compound, and the monomer of a vinyl aromatic compound of Claim 1 or 2 in which the said hydrogenated diene type polymer [D] is a monomer unit of a conjugated diene compound. At least one thermoplastic elastomer composition selected from hydrogenated polymers containing units. The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the durometer E hardness according to JIS K6253 is 80 or less. The monomer of the ethylene monomer unit and the alpha olefin compound as described in any one of Claims 1-4 whose content of the ethylene monomeric unit which comprises the said ethylene-alpha-olefin type copolymer [A] and [A1] is an ethylene monomer unit. The thermoplastic elastomer composition which is 35-95 mol%, when the sum total of all the monomer units containing a unit is 100 mol%. The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the mineral oil softener [C], [C1], and [C2] are paraffinic mineral oil. The crosslinking agent according to any one of claims 1 to 6, wherein the crosslinking agent is 1,3-bis (t-butyl peroxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tbutylperoxy Hexine-3, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α-bis (t-butylperoxy) diisopropylbenzene, dicumylperoxide and di-t- A thermoplastic elastomer composition, which is an organic peroxide selected from butyl peroxide. The thermoplastic elastomer composition according to any one of claims 1 to 7, wherein a cyclohexane insoluble content is at least 60 mass% at 23 ° C of the ethylene-α-olefin-based copolymer in the thermoplastic elastomer composition. A molded article prepared from the thermoplastic elastomer composition according to any one of claims 1 to 8. The low hardness sealing material formed using the thermoplastic elastomer composition of any one of Claims 1-8. The low hardness sealing material according to claim 10, wherein the durometer A hardness in accordance with JIS K6253 is 40 or less. The low hardness sealing material according to claim 10 or 11 formed in an O-ring shape, a sheet shape or a rod shape. The container which uses the low hardness sealing material of any one of Claims 10-12 as a component. A container formed by injection molding from a composite composed of a seal and a case made from the low hardness seal of any one of claims 10 to 12. 15. The container of claim 14, wherein the case portion is made from a thermoplastic resin and / or a thermoplastic elastomer composition and is recyclable. A toner case comprising the low hardness sealing material according to any one of claims 10 to 12 as a component.

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