WO2017065303A1 - ゴム補強用繊維、ゴム-繊維複合体およびこれを用いた空気入りタイヤ - Google Patents
ゴム補強用繊維、ゴム-繊維複合体およびこれを用いた空気入りタイヤ Download PDFInfo
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- WO2017065303A1 WO2017065303A1 PCT/JP2016/080624 JP2016080624W WO2017065303A1 WO 2017065303 A1 WO2017065303 A1 WO 2017065303A1 JP 2016080624 W JP2016080624 W JP 2016080624W WO 2017065303 A1 WO2017065303 A1 WO 2017065303A1
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- rubber
- fiber
- copolymer
- resin
- olefin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/005—Reinforcements made of different materials, e.g. hybrid or composite cords
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C13/00—Tyre sidewalls; Protecting, decorating, marking, or the like, thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/0042—Reinforcements made of synthetic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/02—Carcasses
- B60C9/0207—Carcasses comprising an interrupted ply, i.e. where the carcass ply does not continuously extend from bead to bead but is interrupted, e.g. at the belt area, into two or more portions of the same ply
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/48—Tyre cords
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C2009/0071—Reinforcements or ply arrangement of pneumatic tyres characterised by special physical properties of the reinforcements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
- B60C15/0628—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead comprising a bead reinforcing layer
- B60C2015/0639—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead comprising a bead reinforcing layer between carcass main portion and bead filler not wrapped around the bead core
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
- D10B2321/022—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polypropylene
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/02—Reinforcing materials; Prepregs
- D10B2505/022—Reinforcing materials; Prepregs for tyres
Definitions
- the present invention relates to a rubber reinforcing fiber, a rubber-fiber composite, and a pneumatic tire using the same (hereinafter, also simply referred to as “tire”), and more particularly, rubber reinforcement useful for reinforcing rubber articles such as tires.
- the present invention relates to industrial fibers, rubber-fiber composites, and pneumatic tires using the same.
- Patent Document 1 discloses that a thermoplastic resin that can be thermally fused to rubber using a resin selected from at least one of polyester, polyamide, polyvinyl alcohol, polyacrylonitrile, rayon, and a heterocyclic ring-containing polymer as a core component.
- a cord / rubber composite is disclosed in which a core / sheath fiber comprising a resin as a sheath component is embedded in unvulcanized rubber and vulcanized and integrated.
- Patent Document 2 discloses a core-sheath type composite fiber that has a core part and a sheath part, the core part includes a thermoplastic resin, and the sheath part includes polyolefin.
- Example 1 of Patent Document 2 two polymers of high density polyethylene and maleic acid-modified high density polyethylene having an acid value of 27 mgKOH / g according to JIS-K-0070 method are mixed in the resin of the sheath portion.
- the olefin polymer composition formed as described above an effect of improving the conformability of the interface with the 6 nylon resin used for the core is obtained.
- the compatibility with the rubber to be deposited is lowered due to the difference in polarity.
- an object of the present invention is to improve the adhesiveness between rubber and fiber, so that when used as a reinforcing material, the durability of the fiber can be further improved as compared with the conventional fiber, rubber-
- the object is to provide a fiber composite and a pneumatic tire using the same.
- the present inventor has used a core-sheath type composite fiber in which the core part is made of a high melting point resin having a melting point of 150 ° C. or more and the sheath part is made of a low melting point resin material containing an olefin polymer.
- the present inventors have found that the above problems can be solved and have completed the present invention.
- the rubber reinforcing fiber of the present invention comprises a high melting point resin (A) having a core part having a melting point of 150 ° C. or higher, and a sheath part comprising a resin material (B) having a lower melting point than the high melting point resin (A).
- A high melting point resin
- B resin material
- the resin material (B) is an olefin copolymer comprising a propylene- ⁇ -olefin copolymer (C1), a propylene-nonconjugated diene copolymer (C2), an unsaturated carboxylic acid or an anhydride monomer thereof.
- olefin copolymer composition (X) containing at least one kind of olefin polymer.
- the resin material (B) is a styrene elastomer (E) containing a single molecular chain in which the olefin copolymer composition (X) and a styrene monomer are mainly continuously arranged. And one or more selected from the group consisting of a vulcanization accelerator (F) and a filler (N).
- the propylene- ⁇ -olefin copolymer (C1) is preferably a random copolymer of propylene and ethylene or 1-butene
- the ionomer (C3) is an ethylene-ethylenic copolymer. It is also preferable to be an ionomer of a saturated carboxylic acid copolymer or an ionomer of an unsaturated carboxylic acid polymer of polyolefin.
- the propylene-nonconjugated diene copolymer (C2) is preferably an ethylene-propylene-diene copolymer, and the olefin homopolymer or olefin copolymer (D) ((C1 ) And (except for C2) are preferably ⁇ -olefins or polyolefin rubbers.
- 20 to 98 parts by mass of the propylene- ⁇ -olefin copolymer (C1) is contained in 100 parts by mass of the olefin copolymer composition (X), and the propylene-nonconjugated diene system.
- 2 to 80 parts by mass of copolymer (C2), 2 to 40 parts by mass of ionomer (C3), excluding olefin homopolymer or olefin copolymer (D) (excluding (C1) and (C2) ) Is preferably 2 to 75 parts by mass, and preferably 2 or more types.
- the rubber-fiber composite of the present invention is characterized in that a reinforcing material made of the rubber reinforcing fiber is coated with rubber.
- the tire of the present invention is characterized by comprising a reinforcing layer made of the rubber-fiber composite.
- the fiber for rubber reinforcement which improved the adhesiveness with respect to rubber
- the fiber for reinforcing rubber according to the present invention has a core sheath made of a high melting point resin (A) having a melting point of 150 ° C. or higher, and a sheath portion made of a resin material (B) having a melting point lower than that of the high melting point resin (A). It consists of a composite fiber of the mold.
- A high melting point resin
- B resin material
- the fiber for rubber reinforcement according to the present invention is characterized in that the resin material (B) constituting the sheath portion comprises the olefin copolymer composition (X), and this olefin copolymer composition (X).
- the resin material (B) constituting the sheath portion comprises the olefin copolymer composition (X), and this olefin copolymer composition (X).
- X olefin copolymer composition
- X olefin copolymer composition
- X olefin copolymer composition
- these two or more olefinic polymers are used in combination, so that the rubber reinforcement that is more excellent in fusion property with the adherend rubber and more preferable in workability, etc. than in the past. It became possible to make the fiber for use.
- the resin material (B) constituting the sheath part has a lower melting point than the high melting point resin (A) constituting the core part.
- the resin material (B) constituting the sheath part has a lower melting point than the high melting point resin (A) constituting the core part.
- the rubber reinforcing fiber of the present invention is coated with rubber to form a rubber-fiber composite.
- a rubber-fiber composite is conventionally used for bonding tire cords when composited with rubber. Since it is not necessary to perform a dip treatment for attaching an adhesive composition such as a resorcin / formalin / latex (RFL) adhesive, it is possible to simplify the bonding process.
- an adhesive composition such as a resorcin / formalin / latex (RFL) adhesive
- RTL formalin / latex
- the organic fibers are coated with a fiber coating rubber (Skim Rubber) in order to ensure adhesion.
- the rubber reinforcing fiber of the present invention it is possible to directly obtain a strong adhesive force without using a fiber coating rubber by heat sealing with a side rubber or a tread rubber. is there.
- organic fibers are coated with rubber for fiber coating, it is necessary to secure a coating thickness that does not break the rubber coating, so the rubber weight increases by this coating thickness and, as a result, generally contributes to economic improvement.
- the present invention since there are no restrictions on such adhesion processing, there is no secondary negative effect of increasing the weight of the fiber coating rubber. It is possible to provide a composite with a rubber type corresponding to a reinforcing part, such as tread rubber.
- the core-sheath type composite fiber can exhibit sufficient reinforcing performance in the use of a reinforcing material for rubber articles such as tires. Therefore, the rubber reinforcing fiber of the present invention can be fused with rubber without dip treatment or rubber coating by the sheath portion while ensuring the reinforcing performance by the core portion.
- the composite When the composite is used for tire reinforcement, it can contribute to weight reduction of the tire by thinning the gauge.
- the cut end surface of the core portion exposed before vulcanization at the cut end portion is made of the resin of the sheath portion. It is known that a strong fusion between the resin and rubber in the sheath can be obtained even in this portion. This is thought to be due to the low melting point olefin polymer forming the sheath flowing due to heating during vulcanization and entering the gap between the cut end face of the core made of high melting point resin and the rubber. Thereby, durability against strain after vulcanization of the rubber-fiber composite can be further improved.
- Organic fibers for reinforcing rubber articles coated with an adhesive composition such as a resorcinol / formalin / latex (RFL) adhesive, which has been conventionally used for bonding tire cords, include rubber and coated cord materials.
- RTL resorcinol / formalin / latex
- the cord is cut by the member size, and therefore the adhesive composition is not treated on the side surface that becomes the end of the cut cord.
- a strain that peels between the cord end and the rubber is input at a high strain, a crack develops from a non-adhered portion between the cord end and the rubber, and the rubber article breaks.
- the cord end and the rubber are not connected to each other by a method in which the cord end is not disposed at a tire portion that is highly strained or the rubber member is thickened.
- There was a restriction to prevent cracks from being generated from the end of the cord such as reducing the strain that would cause a gap between the wires.
- the cut surface of the cord end portion is fused with the rubber, a restriction caused by a crack progressing from a non-adhered portion between the cord end and the rubber due to strain.
- the design is such that the end of the cord is placed in a tire part that is highly strained, which has been difficult in the past, and the gauge near the end of the cord is made thinner so that the cord end and the rubber are separated. Therefore, it is possible to provide a composite with a rubber type that can reduce the weight of the tire.
- the fiber for reinforcing rubber according to the present invention is a resin material (B) having a low sheathing point, and can be directly adhered to the rubber by heat fusion, and at the same time, the melting point of the core is a high melting point of 150 ° C. or higher. It is a composite fiber having a core-sheath structure, which is resin (A).
- resin (A) a composite fiber having a core-sheath structure
- the melting point of the high melting point resin (A) forming the core is 150 ° C. or higher, preferably 160 ° C. or higher.
- the melting point of the high-melting point resin is less than 150 ° C., the core of the composite fiber is melt-deformed and thinned when the rubber article is vulcanized, or the orientation of the fiber resin molecule is lowered. It will not have performance.
- the resin material (B) forming the sheath preferably has a melting point of 80 ° C. or higher, more preferably 120 ° C. or higher, and still more preferably 135 ° C. or higher. Range. If the melting point of the resin material (B) is less than 80 ° C., sufficient adhesion will be obtained due to the formation of fine voids on the surface if the rubber does not adhere to the surface of the olefin polymer sufficiently at the beginning of vulcanization. May not be obtained. Further, when the melting point of the resin material (B) is 120 ° C. or higher, at a temperature of 130 ° C.
- a vulcanization temperature that may be industrially used in a rubber composition containing sulfur and a vulcanization accelerator.
- the rubber and the resin material (B) are preferable because the rubber composition can be subjected to vulcanization and crosslinking reaction at the same time.
- the vulcanization temperature is set to 170 ° C. or more in order to shorten the vulcanization time industrially, when the melting point of the resin material (B) is less than 80 ° C., the viscosity of the molten resin becomes too low.
- the thermal fluidity increases during vulcanization, and a portion where the sheath thickness decreases due to the pressure during vulcanization occurs, and strain stress such as adhesion test concentrates on the portion where the resin material of the sheath portion is thin.
- the resin material (B) has a melting point of 120 ° C. or higher.
- the vulcanization temperature is 175 ° C. or higher, and the resin material (B) is thermally vulcanized with the rubber composition at the initial stage of vulcanization. May be obtained. Further, it is preferable that the melting point of the resin material (B) is 145 ° C.
- the resin material (B) contains an elastomer having rubbery properties
- the resin material (B) softens without clarifying the melting point, but the rubbery properties correspond to a polymer melted state, and It is preferable because the compatibility of the resin material (B) can be obtained at the initial stage of vulcanization.
- a rubber / elastomer having no clear melting point is regarded as substantially lower than the melting point of the high melting point resin in the core unless a material having a melting point or softening point of 150 ° C. or higher is included.
- the high melting point resin having a melting point of 150 ° C. or higher that forms the core is not particularly limited as long as it is a known resin that can be formed into a filament by melt spinning.
- polyester resins such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polyamides such as nylon 6, nylon 66, nylon 12
- polyester resins and polyolefin resins examples include polyester resins and polyolefin resins.
- polyester resins polytrimethylene terephthalate (PTT) resins are particularly preferred.
- the polytrimethylene terephthalate resin forming the core in the rubber reinforcing fiber of the present invention may be a polytrimethylene terephthalate homopolymer, copolymer, or a mixture with other miscible resins.
- Examples of the copolymerizable monomer of polytrimethylene terephthalate copolymer include acid components such as isophthalic acid, succinic acid and adipic acid, glycol components such as 1,4 butanediol and 1,6 hexanediol, and polytetraethylene. Examples include methylene glycol and polyoxymethylene glycol.
- the content of these monomers capable of copolymerization is not particularly limited, but is preferably 10% by mass or less because the bending rigidity of the copolymer is lowered.
- Examples of the polyester resin that can be mixed with the polytrimethylene terephthalate polymer include polyethylene terephthalate, polybutylene terephthalate, and the like, and may be mixed at 50% by mass or less.
- the intrinsic viscosity [ ⁇ ] of the polytrimethylene terephthalate is preferably 0.3 to 1.2, and more preferably 0.6 to 1.1. When the intrinsic viscosity is less than 0.3, the strength and elongation of the fiber is low, and when it exceeds 1.2, the productivity becomes difficult due to yarn breakage caused by spinning.
- the intrinsic viscosity [ ⁇ ] can be measured with an Ostwald viscometer using an o-chlorophenol solution at 35 ° C.
- the melting peak temperature determined by DSC of polytrimethylene terephthalate measured according to JIS-K-7121 is preferably 180 ° C to 240 ° C. More preferably, it is 200 ° C to 235 ° C. When the melting peak temperature is in the range of 180 to 240 ° C., the weather resistance is high, and the flexural modulus of the resulting composite fiber can be increased.
- a plasticizer for example, a plasticizer, a softening agent, an antistatic agent, an extender, a matting agent, a heat stabilizer, a light stabilizer, a flame retardant, an antibacterial agent, a lubricant, Antioxidants, ultraviolet absorbers, crystal nucleating agents and the like can be added as long as the effects of the present invention are not impaired.
- a plasticizer for example, a plasticizer, a softening agent, an antistatic agent, an extender, a matting agent, a heat stabilizer, a light stabilizer, a flame retardant, an antibacterial agent, a lubricant, Antioxidants, ultraviolet absorbers, crystal nucleating agents and the like
- an additive of the mixture composed of the polyester resin for example, a plasticizer, a softening agent, an antistatic agent, an extender, a matting agent, a heat stabilizer, a light stabilizer, a flame retardant, an antibacterial agent, a lubricant, Antioxidants,
- the high melting point resin (A) forming the core is preferably a high melting point polyolefin resin, particularly preferably a polypropylene resin, more preferably a crystalline homopolypropylene polymer, and more preferably an isotactic resin. Mention may be made of tic polypropylene.
- the core part is composed of a high melting point resin (A) having a melting point of 150 ° C. or higher, and the core part can be melted even in the rubber vulcanization process. Absent.
- the inventor conducted vulcanization for 15 minutes at 195 ° C., which is higher than normal industrial vulcanization conditions, and observed the cross-section of the cord embedded in the rubber after vulcanization.
- the resin material (B) the circular cross section was melted and deformed, but the high melting point resin (A) in the core portion was completely melted while maintaining the cross sectional shape of the circular core portion after the core-sheath composite spinning. It was not melted, and the tensile strength at break as a cord was maintained at 150 N / mm 2 or more.
- the melting point of the resin at the core of the cord is 150 ° C. or higher, the inventor will not melt and cut the cord even when subjected to a heat treatment of 195 ° C. during vulcanization of the rubber article.
- the present inventors have found that a rubber reinforcing fiber in the present invention can be obtained.
- the reason why the material strength is maintained and the heat resistance is maintained even at a processing temperature higher than the melting point specific to the resin is that the cord is vulcanized at a constant length by being embedded in the rubber, so that JIS-K7121 or the like Unlike the method of measuring the melting point without constraining the resin shape, it is considered that the melting point is higher than the melting point inherent to the resin because it is a constant length constrained condition in which the fibers do not shrink.
- a polypropylene resin or a PTT resin is used as a resin having a melting point of 150 ° C. or more constituting the core portion, known 66 nylon, polyethylene terephthalate, which has been conventionally used for tire cords, Although the modulus is lower than that of highly elastic cords such as aramid, the elastic modulus is intermediate between these conventional cords and rubber, so the cords should be placed at specific positions in the tire that were not possible with conventional tire cords. It can be mentioned as a feature.
- a rubber balloon-like compression device called a bladder is assembled by assembling members made of rubber or a coated cord material and putting the original shape before vulcanization such as raw tires into a mold. Then, there is a vulcanization process in which it is pressed from the inside toward the mold with high-temperature, high-pressure steam. At this time, if the modulus of the cord is too high, the cord material will be put together with the rubber material in a state where it is pressed against the mold with steam of high temperature and high pressure from the state before being molded in the original shape such as a raw tire.
- the cord becomes so-called “cutting thread (thread that cuts a lump of clay, etc.)” and the rubber material assembled into the original shape before vulcanization is cut off. .
- cutting thread thread that cuts a lump of clay, etc.
- the rubber material assembled into the original shape before vulcanization is cut off.
- the manufacturing measures are taken with the conventional manufacturing method.
- the cord is jointed in an annular shape, so that the cord that is tensioned by pressing high-temperature and high-pressure steam is the rubber material on the bead side in the tire radial direction It is easy to generate manufacturing problems.
- the cord of the present invention is a material in which the cord material is also easily stretched as compared with the conventional high-elasticity cord. Even in the case of a product structure and arrangement position that could not be achieved, it is possible to manufacture the product with the conventional method.
- One of the features of the present invention is that the degree of freedom in designing the tire member can be widened.
- the resin material (B) which comprises a sheath part is characterized by including the olefin type copolymer composition (X), and this olefin type copolymer composition (X) is characterized by the following.
- a known ⁇ -olefin monomer can be used as a comonomer copolymerized with propylene.
- the monomer used as a comonomer is not restricted to 1 type,
- the multi-component copolymer using two or more types of monomers like a terpolymer is also contained as a preferable thing.
- other monomers capable of copolymerization with polypropylene can be included, for example, in a range of 5 mol% or less. In the present invention, these monomers are included.
- the polymer containing is also referred to as a propylene- ⁇ -olefin copolymer (C1).
- a propylene-ethylene random copolymer, a butene-propylene random copolymer, or the like can be used.
- ⁇ -olefins having 2 or 4 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene And linear or branched ⁇ -olefins such as 1,4-methyl-hexene-1,4,4-dimethylpentene-1, and cyclic olefins such as cyclopentene, cyclohexene, and cycloheptene.
- ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and ethylene and 1-butene are particularly preferable.
- the propylene content in the propylene- ⁇ -olefin random copolymer (C1) is preferably 20 to 99.7 mol%, more preferably 75 to 99.5 mol%, and still more preferably 95 to 99.3. Mol%. If the propylene content is less than 20 mol%, the impact strength may be insufficient due to the formation of a polyethylene crystal component. In general, a propylene content of 75 mol% or more is preferable because spinnability is improved. Furthermore, when the propylene content is 99.7 mol% or less, the randomness of the molecular chain increases due to addition polymerization of other monomers such as ethylene copolymerized with polypropylene, and the cord becomes easy to be thermally fused.
- the ethylene content is preferably 0.3 mol% to 80 mol%.
- the fusion resistance between the sheath portion and the adherend rubber is not preferable because the resistance to fracture of the sheath portion is not sufficient, and cracks are easily generated in the sheath portion, which makes it easy to break.
- the ethylene content is 5 mol% or less, the fusion property when the resin materials in the sheath part come into contact with each other at the time of spinning becomes small, and the spinnability becomes preferable.
- the polymer consisting of polypropylene has less disorder of molecular chain orientation due to addition polymerization of the ethylene monomer, and as a result, the crystallinity becomes high. The heat-fusibility of the resin in the sheath portion is reduced.
- the propylene- ⁇ -olefin copolymer (C1) is a random copolymer in which the block amount in NMR measurement of the repeating unit of the same vinyl compound portion is 20% or less of the wholly aromatic vinyl compound portion. preferable. Random copolymerization is preferred because the propylene- ⁇ -olefin copolymer (C1) has low crystallinity, and when it is more non-oriented, the rubber to be applied is a rubber component with low orientation, such as butadiene, natural rubber, and SBR. This is because a rubber composition containing the above is preferable because it is easy to obtain fusion properties due to the compatibility of molecular chains during heating.
- the propylene- ⁇ olefin copolymer (C1) includes a propylene copolymer (C2) containing propylene and a non-conjugated diene, a monomer of an unsaturated carboxylic acid or an anhydride thereof.
- Examples include ionomer (C3), olefin homopolymer or olefin copolymer (D) (excluding (C1) and (C2)) having a degree of neutralization with an olefin copolymer metal salt of 20% or more.
- the propylene- ⁇ -olefin copolymer (C1) is used is that the propylene-containing polymer is an olefin polymer and has a melting point lower than the melting point of 165 ° C. of the propylene homopolymer by containing ⁇ -olefin in the comonomer.
- the melting point is about 90 ° C. to 140 ° C.
- the melting point is suitable for the resin material of the sheath, which is lower than the melting point 150 ° C. or more of the core resin defined in the present invention.
- the crystallinity and orientation are lowered, and the heat-fusibility is improved.
- the adhesiveness is low because it does not contain a diene monomer, and even if the processed cords are overlapped and pressure is applied to each other,
- the blocking property such as adhesion is relatively small with a heat-fusible resin, and can be easily controlled so as to achieve an appropriate spinning workability.
- the resin of the olefin-based copolymer composition (X) is used as a matrix component
- the propylene-based rubber contains propylene and non-conjugated diene that have good adhesion to rubber to be adhered but have strong adhesion to rubber.
- a single olefin polymer is preferable because it can satisfy contradictory physical properties.
- the MFR 190 measured in accordance with JIS-K-7210 of the propylene- ⁇ -olefin copolymer (C1) is preferably 3 to 100 g / 10 min.
- a more preferred MFR 190 is 5 to 40 g / 10 min, even more preferably 5 to 30 g / 10 min. If the MFR 190 exceeds 100 g / 10 min, the fluidity of the resin material in the sheath is too high, and since the MFR 190 is 3 g / 10 min or more, the workability during the spinning process and the stretching process is good and uniform rubber It becomes easy to obtain reinforcing fibers.
- the melting point of the propylene- ⁇ -olefin copolymer (C1) measured according to JIS-K-7121 is preferably not more than the melting point of the high melting point resin (A) in the core.
- the lower limit of the melting point is not particularly limited, but is preferably 90 ° C or higher, particularly preferably 110 ° C or higher, and further 120 ° C or higher.
- a resin having a melting point of less than 90 ° C. and a good fusion property for the resin material (B) of the sheath it is not used as a single resin, but in combination with an olefin polymer having a melting point higher than that.
- the propylene-nonconjugated diene copolymer (C2) according to the present invention can be obtained by polymerizing propylene and a known nonconjugated diene.
- the monomers used as these comonomers are not limited to one type, and multi-component copolymers using two or more types of monomers such as terpolymers are also included as preferable ones.
- other monomers that can be copolymerized with polypropylene can be included, for example, in a range of 5 mol% or less.
- the blend is also a propylene-nonconjugated diene copolymer (C2).
- Preferable examples include 1-butene-propylene copolymer.
- Non-conjugated diene monomers include 5-ethylidene-2-norbornene, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, 5-vinyl-2-norbornene, 4,8-dimethyl-1,4,8- And decatriene, 4-ethylidene-8-methyl-1,7-nonadiene, and the like.
- a non-conjugated diene is introduced as a third component into ethylene and propylene, if an ethylene-propylene-diene copolymer (EPDM) component is included, it is due to sulfur as well as adhesion at the interface with the adherend rubber. Since a component having co-vulcanizability is included, it is preferable.
- EPDM ethylene-propylene-diene copolymer
- the propylene content in the propylene-nonconjugated diene copolymer is preferably 20 to 99.7 mol%, more preferably 30 to 75 mol%, and still more preferably 40 to 60 mol%.
- the propylene content is less than 20 mol%, a blocking phenomenon in which the resin materials in the sheath portion of the cord stick to each other after spinning tends to occur.
- it is less than 30 mol%, the resin material surface of the sheath portion is likely to be disturbed due to the friction of the surface during spinning.
- the propylene content exceeds 99.7 mol% and the amount of other monomers copolymerized with polypropylene is reduced, the randomness of the molecular chain is reduced and the crystallinity of polypropylene is increased. Is a low code.
- the content of the non-conjugated diene monomer exceeds 80 mol%, the fracture resistance of the sheath portion is not sufficient in the fusion between the sheath portion and the adherend rubber, and a crack occurs in the sheath portion. It is not preferable because it is easy to break.
- the ethylene content is less than 0.3 mol%, the compatibility with the adherend rubber and the improvement of adhesion by co-vulcanization are reduced.
- the propylene-nonconjugated diene copolymer (C2) includes another propylene- ⁇ -olefin copolymer (C1), a monomer of an unsaturated carboxylic acid or an anhydride thereof. It is preferable to use in combination with an ionomer (C3) having a degree of neutralization by the metal salt of the olefin copolymer of 20% or more. This is due to the following reasons. When an olefin copolymer (C2) containing a conjugated diene such as EPDM is used as the resin material for the sheath, the adhesiveness is improved by containing a diene capable of sulfur crosslinking.
- a conjugated diene such as EPDM
- a resin constituting the resin material (B) is preferable as one of the preferable methods in order to improve the adhesiveness with the rubber and achieve both the spinnability of the cord and the manufacturability such as the blocking resistance without contradicting them.
- Ingredients include propylene-non-conjugated diene copolymer (C2), and a propylene- ⁇ -olefin copolymer (C1), unsaturated carboxylic acid or anhydride thereof, which is a resinous material with low rubber elasticity.
- An ionomer (C3) having a degree of neutralization with a metal salt of an olefin copolymer containing a polymer of 20% or more, or an olefin homopolymer or olefin copolymer (D) ((C1) and (C2) Except for the above) can be used as a resin matrix phase as a main component of the sheath portion, and the propylene-nonconjugated diene copolymer (C2) can be dispersed and used in combination.
- the MFR 190 of the propylene-nonconjugated diene copolymer (C2) measured according to JIS-K-7210 is preferably 2 to 40 g / 10 min. A more preferred MFR 190 is 3 to 30 g / 10 min. If the MFR190 exceeds 40 g / 10 minutes, the fluidity of the resin material in the sheath is too high, and since the MFR190 is 2 g / 10 minutes or more, the workability during the spinning process and the stretching process is good and uniform rubber It becomes easy to obtain reinforcing fibers.
- the melting point of the propylene-nonconjugated diene copolymer (C2) measured according to JIS-K7121 is preferably not more than the melting point of the core resin (A).
- the lower limit of the melting point is not particularly limited, but is preferably 90 ° C or higher, particularly preferably 110 ° C or higher, and further 120 ° C or higher.
- an ethylene-ethylenically unsaturated carboxylic acid may be used. It is preferably an ionomer of an acid copolymer or an ionomer of an unsaturated carboxylic acid polymer of polyolefin.
- an ethylene-ethylenically unsaturated carboxylic acid copolymer can be obtained by polymerizing ethylene and a known ethylenically unsaturated carboxylic acid.
- the monomers used as these comonomers are not limited to one type, and multi-component copolymers using two or more types of monomers such as terpolymers are also included as preferable ones.
- other monomers that can be copolymerized with polypropylene can be included, for example, in a range of 5 mol% or less, and a polymer including these monomers as long as the intended effect of the present invention is obtained.
- an ethylene-methacrylic acid copolymer is preferable because a core-sheath composite fiber excellent in fusion property can be obtained.
- Ethylenically unsaturated carboxylic acid monomers include vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, nbutyl acrylate, isobutyl acrylate, and isooctyl acrylate.
- Examples include acid esters, methacrylic acid esters such as methyl methacrylate and isobutyl methacrylate, and maleic acid esters such as dimethyl maleate and diethyl maleate. Among these, methyl acrylate and methyl methacrylate are preferable.
- the monomer content of the ethylenically unsaturated carboxylic acid in the ethylene-ethylenically unsaturated carboxylic acid copolymer is preferably 0.5 to 35% by mass, more preferably 1 to 25% by mass, and even more preferably 2%. ⁇ 10% by mass.
- the ethylenically unsaturated carboxylic acid content is less than 0.5% by mass, between the polymers of the olefin copolymer composition (X) by the ethylene-ethylenically unsaturated carboxylic acid copolymer or between the core resin The effect of improving the compatibility is slight, and the fusion property is lowered.
- the polymer of the olefin copolymer composition (X) has a large polarity, such as butadiene rubber and styrene rubber in the rubber composition of the adherend rubber.
- a difference in polarity is produced and compatibility is lowered, so that the fusion property is lowered.
- an ethylene-ethylenically unsaturated carboxylic acid-based ionomer (C3) having a neutralization degree of 20% or more with a metal salt of an olefin-based copolymer containing an unsaturated carboxylic acid or anhydride monomer is used.
- An ionomer obtained by neutralizing a part or all of the carboxyl groups with a metal such as a copolymer or a modified product of an unsaturated carboxylic acid of polyolefin can be used.
- the metal species constituting the ionomer include monovalent metals such as lithium, sodium, and potassium, and polyvalent metals such as magnesium, calcium, zinc, copper, cobalt, manganese, lead, and iron.
- an ionomer obtained by neutralizing an ethylene-ethylenically unsaturated carboxylic acid copolymer with 20% or more of a metal is preferable for use in the resin material (B) of the sheath. This is due to the following reasons.
- the resin material (B) in the sheath becomes a proton H + donating acidic atmosphere due to a functional group such as carboxylic acid
- the sulfur migrates from the rubber to the resin material (B) in the sheath and is activated. Since proton H + reduces the polyvulcanized product, the polyvulcanized product cannot be formed, and therefore, an environment in which the adhesiveness to the adherend rubber cannot be strengthened is easily obtained.
- the ethylene-ethylenically unsaturated carboxylic acid copolymer (C3) is an ionomer, and rubber reinforcement is used so that the composition of the resin material (B) of the sheath portion can maintain a Lewis basic atmosphere.
- the neutralization degree between the carboxylic acid and the metal salt is preferably 100% or more.
- the neutralization degree of the carboxylic acid is preferably 20% to 250%, more preferably 70% to 150%.
- the neutralization degree in this invention is defined by a following formula.
- Degree of neutralization (%) 100 ⁇ [(number of moles of cation component of resin component ⁇ valence of cation component) + (number of moles of metal component of basic inorganic metal compound ⁇ valence of metal component)] / (Mole number of carboxyl group of resin component)
- the amount of the cation component and the amount of the anion component can be determined by a method for examining the degree of neutralization of the ionomer such as neutralization titration.
- the degree of neutralization with a metal salt of an olefin copolymer containing a monomer of an unsaturated carboxylic acid or an anhydride thereof is known from publicly known documents such as Japanese Patent Application Laid-Open Nos. 05-163618 and 07-238420.
- the ionomer (C3) of 20% or more is added, compatibility between the core sheaths of the core-sheath fibers is improved.
- the core portion is particularly a polyester or polyamide resin material, and the sheath portion is an olefin polymer resin. In the case of a material, it is known that the adhesiveness of the interface between core sheaths can be improved.
- the content of the ionomer (C3) having a neutralization degree of 20% or more by the metal salt of the olefin copolymer containing an unsaturated carboxylic acid or anhydride monomer is the olefin copolymer.
- the composition (X) is 100 parts by mass, it is preferably 2 to 40 parts by mass, more preferably 2 to 25 parts by mass, and still more preferably 3 to 15 parts by mass.
- the core sheath of the core sheath fiber When the ionomer (C3) having a neutralization degree of 20% or more by the metal salt of the olefin copolymer containing the unsaturated carboxylic acid or its anhydride monomer is less than 2 parts by mass, the core sheath of the core sheath fiber The compatibility is not improved, and the adhesion is slightly improved. On the other hand, if it exceeds 40 parts by mass, bubbles may enter into the composite during vulcanization to form cavities. In this way, if bubbles are generated at a position where there is a difference in material rigidity between the rubber and the resin of the rubber reinforcing fiber, fatigue due to repeated loads such as when traveling is likely to cause the core fracture of cracking. As a result, the adhesion to rubber is reduced.
- the ionomer (C3) having a neutralization degree of 20% or more by the metal salt of the olefin copolymer containing the unsaturated carboxylic acid or its anhydride monomer is composed of an aliphatic polyester and a polyolefin used for the sheath.
- the MFR 190 measured according to JIS-K-7210 is 0.01 to 200 g / 10 min. More preferred MFR 190 is in the range of 0.1 to 100 g / 10 min, even more preferably in the range of 3 to 60 g / 10 min.
- the melting point of the ethylene-ethylenically unsaturated carboxylic acid copolymer or its ionomer measured in accordance with JIS-K7121 is preferably not more than the melting point of the high melting point resin (A) in the core.
- the lower limit of the melting point is not particularly limited, but is preferably 90 ° C. or higher, particularly preferably 110 ° C. or higher, and further 120 ° C. or higher.
- Examples of the olefin homopolymer or olefin copolymer (D) (excluding (C1) and (C2)) according to the present invention include ethylene such as high-density polyethylene, low-density polyethylene, and linear low-density polyethylene.
- ethylene such as high-density polyethylene, low-density polyethylene, and linear low-density polyethylene.
- ⁇ -olefin homopolymers such as homopolymers, isotactic polypropylene, atactic polypropylene, or propylene homopolymers such as syndiotactic polypropylene, 4-methylpentene-1 homopolymer, 1-butene homopolymer, etc.
- Preferable examples include polymer (D1), or polyolefin rubber (D2) having an unsaturated hydrocarbon bond in the main chain according to JIS-K6397, such as polybutadiene, polyisoprene, and polynorbornene.
- polymer (D1) or polyolefin rubber (D2) having an unsaturated hydrocarbon bond in the main chain according to JIS-K6397, such as polybutadiene, polyisoprene, and polynorbornene.
- ⁇ -olefin homopolymer (D1) or polyolefin rubber (D2) an olefin copolymer (D) containing about 40 or less other monomers for 1000 repeating monomers.
- ⁇ -olefin homopolymer (D1) is particularly preferable in the present invention, and high density polyethylene or polypropylene having a low stereoregularity controlled by a catalyst in propylene polymerization and a low melting point (for example, Idemitsu Kosan Co., Ltd. El Modu, etc.) can be used. These are not used alone but can be used as a mixture.
- the ⁇ -olefin homopolymer (D1) generally often exhibits the characteristics of a thermoplastic material having high crystallinity such as polyethylene and polypropylene. Conventionally, various studies have been conducted on blending such an ⁇ -olefin homopolymer with another olefin polymer in the core-sheath olefin fiber. In the rubber reinforcing fiber of the present invention, the ⁇ -olefin homopolymer (D1) has low rubber-like elasticity and good moldability into a fiber shape during resin spinning.
- propylene- ⁇ -olefin copolymer (C1) propylene-containing copolymer (C2) containing propylene and non-conjugated diene, unsaturated carboxylic acid, which is used as a resin matrix and has low moldability in the form of yarn during spinning
- a polymer such as an ionomer (C3) having a degree of neutralization by the metal salt of an olefin copolymer containing an acid or anhydride monomer thereof to 20% or more
- the resin can be formed into a filament shape during spinning. While ensuring moldability and the like, it is possible to achieve both improvement in adhesion suitable for rubber reinforcement by mixing with other polymers.
- polyethylene examples include linear low-density polyethylene, high-density polyethylene, etc., and a part of ⁇ -olefin such as 1-butene is copolymerized to have a short branched structure to intentionally lower the crystallinity.
- a polymer is mentioned.
- the polypropylene examples include stereotactic polypropylene such as isotactic, syndiotactic, and atactic, but the polypropylene used for the resin material (B) of the sheath is compatible with the rubber to be adhered. Especially preferred is polypropylene with good steric orientation.
- polypropylene examples include propylene having low crystallinity due to a single-site catalyst such as a product El Modu made by Idemitsu Kosan Co., Ltd. It is preferable to use such propylene for the resin material (B) of the sheath when polypropylene is used for the core resin because the bond between the core and the sheath can be strengthened.
- poly 1-butene has high melt miscibility with other olefin components such as polypropylene, and is a preferred example.
- the ⁇ -olefin homopolymer preferably has an MFR190 measured in accordance with JIS-K-7210 of 0.01 to 200 g / 10 min. More preferred MFR 190 is in the range of 0.1 to 100 g / 10 min, even more preferably in the range of 3 to 60 g / 10 min. Moreover, it is preferable that melting
- Examples of the polyolefin rubber (D2) having an unsaturated hydrocarbon bond in the main chain in the olefin homopolymer or olefin copolymer (D) (excluding (C1) and (C2)) include polybutadiene, poly Preferred examples include polymers obtained by polymerizing monomers with low polarity such as isoprene and polynorbornene.
- Examples of the method for producing these olefin polymers include slurry polymerization, gas phase polymerization or liquid phase bulk polymerization using an olefin polymerization catalyst such as a Ziegler catalyst and a metallocene catalyst. Either method of continuous polymerization can be employed.
- the olefin copolymer composition (X) contained in the resin material (B) of the sheath part is composed of a propylene- ⁇ -olefin copolymer (C1), a propylene-nonconjugated diene copolymer (C2).
- the propylene- ⁇ -olefin copolymer (C1) is 20 to 98 parts by mass
- the propylene-nonconjugated diene copolymer (C2) is 2 to 80 parts by mass
- the unsaturated carboxylic acid or anhydride thereof is 20 to 98 parts by mass
- the ionomer (C3) having a degree of neutralization with a metal salt of an olefin copolymer containing a monomer of 20% or more is 2 to 40 parts by mass
- the olefin homopolymer or olefin copolymer (D) (( (Excluding C1) and (C2) preferably contains 2 or more in the range of 2 to 75 parts by mass.
- the resin material (B) constituting the sheath part is a single molecular chain (hereinafter also referred to as “styrene block”) in which styrene monomers are mainly arranged continuously as a compatibilizing component. It is preferable to contain the styrene-type elastomer (E) containing).
- blending a styrene-type elastomer (E) compatibility with a resin material (B) and rubber
- gum can be improved and adhesiveness can be improved.
- the low melting point resin material (B) is mainly a polyolefin resin such as a homopolymer such as polyethylene or polypropylene or an ethylene-propylene random copolymer, which is a resin composition having a melting point range specified in the present invention.
- a resin composition mixed with these components has a phase-separated structure. Therefore, by adding the styrene elastomer (E) as a block copolymer composed of a soft segment and a hard segment, compatibilization of the phase interface can be promoted.
- the styrene elastomer (E) is composed of an adhesive at the interface between the high melting point resin (A) that is the core component and the resin material (B) that is the sheath component, and styrene-butadiene rubber ( Adhesion with adherend rubber is improved by having segments that interact with the molecular structure such as SBR), butadiene rubber (BR), butyl rubber (IIR), and natural rubber (IR) having a polyisoprene structure. Is preferable.
- styrene elastomer (E) specifically, a styrene block copolymer or a styrene graft polymer can be used, and one containing styrene and a conjugated diolefin compound is preferable.
- a polymer comprising a block unit of a styrenic polymer containing a single molecular chain mainly composed of styrene monomers and a conjugated diene compound, a hydride thereof, or a modified product thereof. can be mentioned.
- Styrene monomers constituting the block unit include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, ⁇ -methylstyrene, vinylnaphthalene, vinylanthracene, etc. Can be used singly or in combination of two or more, among which styrene is preferred.
- conjugated diene compounds constituting the styrene elastomer (E) include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1, 3-Butadiene, 1,3-hexadiene and the like can be used alone or in combination of two or more. Among these, 1,3-butadiene is preferred.
- the content of the styrene monomer contained in the styrene elastomer (E) is not particularly limited, but the hard part composed of styrene block units (hard segment) is an olefin contained in the resin material (B) of the sheath part. It is preferably 70% by mass or less so that it can be easily compatibilized by mixing with resins, and is preferably 3% by mass or more so as to obtain the effect of compatibilization with other than olefin resins by introducing a styrene block. . From such a viewpoint, the content of the styrenic monomer is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and further preferably 10 to 50% by mass.
- examples of the styrene elastomer (E) include a styrene-butadiene copolymer, a styrene-isoprene block copolymer, a styrene-ethylenepropylene block copolymer, and a styrene-isobutylene block copolymer.
- styrenic elastomer (E) examples thereof include a polymer obtained by hydrogenation of a heavy bond to complete hydrogenation or partial hydrogenation.
- the styrenic elastomer (E) may be modified with a polar group such as an amino group or maleic acid. Of these, modification with an amino group is preferred.
- Other styrene elastomers include styrene elastomers such as olefin graft copolymers having a polyolefin resin in the main chain and a vinyl polymer in the side chain.
- the graft copolymer is a polymer in which other polymers are arranged like branches in some places in the main copolymer, but in the present invention, a block in which styrene monomers are mainly connected long is arranged.
- the included graft copolymer is a styrene-based graft polymer.
- the hydrogenation rate of the styrene elastomer (E) may be part or all. It is also known that the mechanical properties of a resin composition containing a styrene elastomer is improved by the effect of reducing unsaturated bonds by hydrogenation. From this viewpoint, the hydrogenation rate is 100%. Is also effective. On the other hand, when a conjugated diene capable of addition polymerization is contained in the styrene-based elastomer (E) contained in the resin material (B) of the sheath, sulfur transferred from the rubber is crosslinked during vulcanization with the adherend rubber. Adhesiveness can be improved. From these viewpoints, the hydrogenation rate of the styrene elastomer (E) is preferably 10 to 100% or more, more preferably 15 to 100%, and still more preferably 20 to 60%. .
- styrene-butadiene copolymer examples include styrene-butadiene copolymer (SBS), hydrogenated styrene-butadiene copolymer (HSBR), styrene-ethylene-butadiene copolymer (SEB), and styrene-ethylene.
- SBS styrene-butadiene copolymer
- HSBR hydrogenated styrene-butadiene copolymer
- SEB styrene-ethylene-butadiene copolymer
- SEBS styrene-ethylene-butadiene copolymer
- SEBS styrene-ethylene-butadiene copolymer
- SBBS partially hydrogenated styrene-isoprene-butadiene-styrene copolymer
- Polystyrene-poly (ethylene / propylene) block copolymers include polystyrene-poly (ethylene / propylene) block copolymers (SEP), polystyrene-poly (ethylene / propylene) block-polystyrene (SEPS), polystyrene-poly.
- SEP polystyrene-poly (ethylene / propylene) block copolymers
- SEPS polystyrene-poly (ethylene / propylene) block-polystyrene
- SEEPS Ethylene-ethylene / propylene block-polystyrene
- SEBS polystyrene-poly block-polystyrene
- SEBC polystyrene-poly (ethylene / Butylene) block-crystalline polyolefin
- styrene-isobutylene block copolymer examples include polystyrene-polyisobutylene block copolymer (SIB) and polystyrene-polyisobutylene-polystyrene block copolymer (SIBS).
- styrene-isoprene block copolymer examples include polystyrene-polyisoprene-polystyrene block copolymer (SIS).
- SIS polystyrene-polyisoprene-polystyrene block copolymer
- styrene-based graft polymers include olefin-based graft copolymers (LDPE-g-PS) having low-density polyethylene as the main chain and polystyrene as the side chain, and styrene-acrylonitrile copolymers as the main chain.
- PP-g-AS olefin-based graft copolymer
- styrene-butadiene copolymer styrene-butadiene-butylene-styrene copolymer and styrene-ethylene-butadiene-styrene copolymer are particularly preferred from the viewpoint of adhesion to rubber and compatibility.
- Asahi Kasei Chemicals Co., Ltd. O. E. A partial hydrogenated product of a block copolymer having a styrene block at both ends, such as product number 609, and a random copolymer block of styrene and butadiene in the main chain can be suitably used.
- Styrenic elastomer (E) can be used individually by 1 type or in combination of 2 or more types as appropriate.
- Modification of introducing a polar group into a hydrogenated product of a styrene-butadiene copolymer is not particularly limited. For example, by introducing an amino group, a carboxyl group, or an acid anhydride group into the hydrogenated product. It can be carried out.
- the amount of modification of the styrene elastomer (E) is usually 1.0 ⁇ 10 ⁇ 3 to 1 mmol / g, preferably 5.0 ⁇ 10 ⁇ 3 to 0.5 mmol / g, from the viewpoint of compatibility and workability. More preferably, it is 1.0 ⁇ 10 ⁇ 2 to 0.2 mmol / g, and still more preferably 1.0 ⁇ 10 ⁇ 2 to 0.1 mmol / g.
- the modification for introducing a polar group into these hydrogenated products is preferably modification by introduction of an amino group. This is because, when a compound having an unpaired electron-donating Lewis basic functional group such as an amino group is introduced, it can have an effect as a vulcanization accelerator (F) as described later. It is. On the other hand, when an acidic polar group is introduced, sulfur sulfide is generated in the vulcanization reaction, and when the acidic polar group donates proton H + to the active polyvulcanizate, hydrogen sulfide HS is generated. This may suppress the vulcanization reaction. For this reason, modification with Lewis basic groups is preferred.
- the introduction of the amino group described above includes 3-lithio-1- [N, N-bis (trimethylsilyl)] aminopropane, 2-lithio-1- [N, N-bis (trimethylsilyl) as compounds used for modification.
- unsaturated amines or derivatives thereof include vinylamine.
- examples of the compound used for modification include unsaturated carboxylic acids or derivatives thereof, for example, ⁇ , ⁇ -unsaturated carboxylic acid, ⁇ , ⁇ -unsaturated carboxylic acid anhydrides are preferred, and specific examples include ⁇ , ⁇ -unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; ⁇ , such as maleic acid, succinic acid, itaconic acid, and phthalic acid.
- ⁇ -unsaturated dicarboxylic acid ⁇ -unsaturated dicarboxylic acid
- ⁇ ⁇ -unsaturated monocarboxylic acid ester such as glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxymethyl methacrylate
- Examples include ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides.
- the weight average molecular weight of the styrenic elastomer (E) is not particularly limited, but is preferably 30,000 or more from the viewpoint of heat resistance so that the heat distortion temperature of the resin material (B) in the sheath portion is not lowered. In order to make it easy to obtain fluidity at the time of kneading the resin material of the sheath part, 450,000 or less is preferable. From these viewpoints, the weight average molecular weight of the styrene elastomer (E) is preferably 30,000 to 450,000, more preferably 50,000 to 400,000, and further preferably 80,000 to 300,000.
- the content of the styrene elastomer (E) in the resin material (B) is 1 to 150 parts by weight, particularly 2 to 90 parts by weight with respect to 100 parts by weight of the olefin copolymer composition (X). Further, it can be 3 to 40 parts by mass.
- the resin material (B) constituting the sheath part preferably further contains a vulcanization accelerator (F).
- a vulcanization accelerator (F) By containing the vulcanization accelerator (F), an interaction at the rubber interface is obtained by the effect that the sulfur content in the adherend rubber becomes a transition state between the vulcanization accelerator (F) and the multiple vulcanizate. As a result, the surface distribution of the resin material (B) in the sheath portion from the rubber or the amount of sulfur transferred to the inside of the resin increases.
- vulcanization accelerator (F) examples include basic silica, primary, secondary, and tertiary amines, organic acid salts of these amines or their adducts and salts thereof, aldehyde ammonia type accelerators, and aldehyde amines.
- Lewis basic compounds (F1) such as system accelerators can be mentioned.
- As the other vulcanization accelerator (F2) when the sulfur atom of the vulcanization accelerator approaches the cyclic sulfur in the system, this ring opens and enters a transition state, producing an active vulcanization accelerator-multi-vulcanizate.
- sulfenamide accelerators, guanidine accelerators, thiazole accelerators, thiuram accelerators, dithiocarbamic acid accelerators, etc. which can activate sulfur.
- the Lewis basic compound (F1) is not particularly limited as long as it is a Lewis base in the definition of Lewis acid base and can provide an electron pair.
- These include nitrogen-containing compounds having a lone electron pair on the nitrogen atom, and specifically, basic vulcanization accelerators known in the rubber industry can be used.
- the basic compound (F1) include aliphatic primary, secondary or tertiary amines having 5 to 20 carbon atoms, and alkyls such as n-hexylamine and octylamine.
- Acyclic monoamines and derivatives thereof such as dialkylamines such as amine, dibutylamine and di (2-ethylhexyl) amine, trialkylamines such as tributylamine and trioctylamine, and salts thereof,
- Acyclic polyamines and derivatives thereof such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, polyethyleneimine, and salts thereof;
- Alicyclic polyamines such as cyclohexylamine and derivatives thereof, and salts thereof
- Alicyclic polyamines such as hexamethylenetetramine and derivatives thereof, and salts thereof
- Examples thereof include aromatic polyamine compounds such as phenylenediamine, diaminotoluene, N-alkylphenylenediamine, benzidine, guanidines, n-butyraldehyde aniline and derivatives thereof.
- guanidines include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, dicatechol borate di-o-tolylguanidine salt, 1,3-di- o-Cumenylguanidine, 1,3-di-o-biphenylguanidine, 1,3-di-o-cumenyl-2-propionylguanidine and the like can be mentioned. Of these, 1,3-diphenylguanidine is preferred because of its high reactivity.
- Examples of the organic acid that forms a salt with the amine include carboxylic acid, carbamic acid, 2-mercaptobenzothiazole, dithiophosphoric acid, and the like.
- Examples of the substance that forms an adduct with the amine include alcohols and oximes.
- Specific examples of the organic acid salt or adduct of amine include n-butylamine / acetate, dibutylamine / oleate, hexamethylenediamine / carbamate, dicyclohexylamine salt of 2-mercaptobenzothiazole, and the like.
- nitrogen-containing heterocyclic compound that becomes basic by having a lone electron pair on a nitrogen atom
- monocyclic inclusions such as pyrazole, imidazole, pyrazoline, imidazoline, pyridine, pyrazine, pyrimidine, and triazine are included.
- Nitrogen compounds and derivatives thereof examples thereof include bicyclic nitrogen-containing compounds such as benzimidazole, purine, quinoline, peteridine, acridine, quinoxaline and phthalazine, and derivatives thereof.
- heterocyclic compound having a hetero atom other than a nitrogen atom include heterocyclic compounds containing nitrogen and other hetero atoms such as oxazoline and thiazoline and derivatives thereof.
- Alkali metal salts include monovalent metals such as lithium, sodium and potassium, formates such as polyvalent metals such as magnesium, calcium, zinc, copper, cobalt, manganese, lead and iron, acetates, nitrates and carbonates.
- Examples include basic inorganic metal compounds such as salts, bicarbonates, oxides, hydroxides, and alkoxides.
- metal hydroxides such as magnesium hydroxide, calcium hydroxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, copper hydroxide; magnesium oxide, calcium oxide, zinc oxide (zinc white), copper oxide
- Metal carbonates such as magnesium carbonate, calcium carbonate, sodium carbonate, lithium carbonate, and potassium carbonate.
- a metal hydroxide is preferable, and magnesium hydroxide is particularly preferable.
- These metal salts are sometimes classified as vulcanization aids, but are classified as vulcanization accelerators in the present invention.
- vulcanization accelerator (F2) examples include known vulcanization accelerators such as thioureas, thiazoles, sulfenamides, thiurams, dithiocarbamic acids, and xanthogenic acids.
- thioureas examples include N, N′-diphenylthiourea, trimethylthiourea, N, N′-diethylthiourea, N, N′-dimethylthiourea, N, N′-dibutylthiourea, ethylenethiourea, N, N′-.
- Diisopropylthiourea N, N′-dicyclohexylthiourea, 1,3-di (o-tolyl) thiourea, 1,3-di (p-tolyl) thiourea, 1,1-diphenyl-2-thiourea
- Examples include 2,5-dithiobiurea, guanylthiourea, 1- (1-naphthyl) -2-thiourea, 1-phenyl-2-thiourea, p-tolylthiourea, o-tolylthiourea and the like.
- N, N'-diethylthiourea, trimethylthiourea, N, N'-diphenylthiourea and N, N'-dimethylthiourea are preferred because of their high reactivity.
- Thiazoles include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, zinc salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (N, N-diethylthiocarbamoyl) Thio) benzothiazole, 2- (4′-morpholinodithio) benzothiazole, 4-methyl-2-mercaptobenzothiazole, di- (4-methyl-2-benzothiazolyl) disulfide, 5-chloro-2-mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, 2-mercapto-6-nitrobenzothiazole, 2-mercapto-naphtho [1,2-d] thiazole, 2-mercapto-5-methoxybenzothiazole, 6-amino-2-mercaptobenzothiazole etc And the like.
- 2-mercaptobenzothiazole and di-2-benzothiazolyl disulfide zinc salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (4′-morpholinodithio) benzothiazole Is preferable because of its high reactivity.
- zinc salts of di-2-benzothiazolyl disulfide and 2-mercaptobenzothiazole have high solubility even when added to a relatively non-polar polymer, so that spinnability due to deterioration of surface properties due to precipitation or the like. This is a particularly preferable example because it is difficult for the lowering of the film to occur.
- sulfenamides include N-cyclohexyl-2-benzothiazolylsulfenamide, N, N-dicyclohexyl-2-benzothiazolylsulfenamide, N-tert-butyl-2-benzothiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfenamide, N-methyl-2-benzothiazolylsulfenamide, N-ethyl-2-benzothiazolylsulfenamide, N-propyl-2-benzothiazolylsulfane Fenamide, N-butyl-2-benzothiazolylsulfenamide, N-pentyl-2-benzothiazolylsulfenamide, N-hexyl-2-benzothiazolylsulfenamide, N-pentyl-2-benzothia Zolylsulfenamide, N-octyl-2-benzothiazolyl Phen
- N-cyclohexyl-2-benzothiazolylsulfenamide, N-tert-butyl-2-benzothiazolylsulfenamide, and N-oxydiethylene-2-benzothiazolesulfenamide are highly reactive. Therefore, it is preferable.
- N-cyclohexyl-2-benzothiazolylsulfenamide and N-oxydiethylene-2-benzothiazolylsulfenamide have high solubility even when added to a relatively nonpolar polymer. This is a particularly preferred example because it is difficult for a decrease in spinnability due to deterioration of surface properties due to precipitation or the like.
- Thiurams include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetraisopropylthiuram disulfide, tetrabutylthiuram disulfide, tetrapentylthiuram disulfide, tetrahexylthiuram disulfide, tetraheptylthiuram disulfide, tetraoctylthiuram disulfide, tetra Nonyl thiuram disulfide, tetradecyl thiuram disulfide, tetradodecyl thiuram disulfide, tetrastearyl thiuram disulfide, tetrabenzyl thiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide,
- tetramethylthiuram disulfide tetraethylthiuram disulfide, tetrabutylthiuram disulfide, and tetrakis (2-ethylhexyl) thiuram disulfide are preferred because of their high reactivity.
- Tetrabutyl thiuram disulfide or tetrakis (2-ethylhexyl) thiuram disulfide is a particularly preferred example.
- Dithiocarbamates include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dipropyldithiocarbamate, zinc diisopropyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, zinc dihexyldithiocarbamate, zinc diheptyldithiocarbamate, and dioctyldithiocarbamate.
- Zinc oxide zinc di (2-ethylhexyl) dithiocarbamate, zinc didecyldithiocarbamate, zinc didodecyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dibenzyldithiocarbamate, Copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dipropyldithiocarbamate, Copper isopropyl dithiocarbamate, copper dibutyldithiocarbamate, copper dipentyldithiocarbamate, copper dihexyldithiocarbamate, copper diheptyldithiocarbamate, copper dioctyldithiocarbamate, copper di (2-ethylhexyl) dithiocarbamate, copper didecyldithiocarbamate,
- zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, and zinc dibutyldithiocarbamate are desirable because of their high reactivity.
- the alkyl group contained in the accelerator compound is large, in the case of a relatively non-polar polymer, the solubility tends to increase, and it is difficult to cause a decrease in spinnability due to deterioration of surface properties due to precipitation or the like.
- zinc dibutyldithiocarbamate is a particularly preferable example.
- Xanthates include zinc methylxanthate, zinc ethylxanthate, zinc propylxanthate, zinc isopropylxanthate, zinc butylxanthate, zinc pentylxanthate, zinc hexylxanthate, zinc heptylxanthate, zinc octylxanthate , Zinc 2-ethylhexylxanthate, zinc decylxanthate, zinc dodecylxanthate, potassium methylxanthate, potassium ethylxanthate, potassium propylxanthate, potassium isopropylxanthate, potassium butylxanthate, potassium pentylxanthate, hexylxanthogen Potassium acetate, potassium heptylxanthate, potassium octylxanthate, 2-ethyl Potassium hexylxanthate, potassium de
- the vulcanization accelerator (F) may be preliminarily dispersed in an inorganic filler, oil, polymer or the like, and used for blending the resin material (B) of the sheath portion of the rubber-reinforced core-sheath fiber.
- These vulcanization accelerators and retarders may be used alone or in combination of two or more.
- the content of the vulcanization accelerator (F) in the resin material (B) is 0.05 to 20 parts by mass, particularly 0.2 in relation to 100 parts by mass of the olefin copolymer composition (X). It can be ⁇ 5 parts by mass.
- a polypropylene-based material is used for the low melting point resin material (B).
- thermoplastic rubber examples include acrylonitrile-butadiene rubber, natural rubber, epoxidized natural rubber, butyl rubber, and ethylene / propylene / diene rubber.
- Other thermoplastic elastomers include syndiotactic-1,2-polybutadiene resin or trans-polyisoprene resin.
- the resin material (B) contains a filler (N).
- filler (N) smectite group such as carbon black, alumina, silica alumina, magnesium chloride, calcium carbonate, talc, montmorillonite, zakonite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite
- examples thereof include inorganic particulate carriers such as vermiculite group and mica group, and porous organic carriers such as polypropylene, polyethylene, polystyrene, styrenedivinylbenzene copolymer and acrylic acid copolymer.
- These fillers are blended as fillers to reinforce the sheath part when the sheath part is not sufficiently resistant to fracture in the adhesion between the sheath part and the adherend rubber, and cracks occur in the sheath part. can do.
- One of the fillers (N) is preferably carbon black.
- the carbon black of the present invention has a nitrogen adsorption specific surface area of 20 to 150 m 2 / g according to JIS K6217, an iodine adsorption amount of 15 to 160 mg / g according to JIS K6221, and a DBP oil absorption amount according to (Method A) of JIS K6221 of 25 to 180cm 3/100 g carbon black in the range of is used, preferably a nitrogen adsorption specific surface area of 70 ⁇ 142m 2 / g, iodine adsorption amount 50 ⁇ 139mg / g, DBP oil absorption amount (a method) 70 ⁇ 140cm it is a carbon black in the range of 3 / 100g.
- the average particle size of the carbon black of the present invention is preferably in the range of 10 to 70 nm, more preferably in the range of 10 to 25 nm.
- a general-purpose carbon black having a relatively small particle size, good dispersibility, high nitrogen specific surface area and high iodine adsorption, and good surface properties such as adsorption to the pores of the polymer is preferable.
- Particularly preferred carbon blacks of the present invention include furnace blacks such as SAF carbon black, SAF-HS carbon black, ISAF carbon black, ISAF-HS carbon black, ISAF-LS carbon black, and the like. It can also be used in combination of two or more.
- the blending amount of carbon black is preferably 0.1 to 100 parts by weight, particularly preferably 1 to 30 parts by weight per 100 parts by weight of the olefin copolymer composition (X) contained in the resin material (B) of the sheath part. Part.
- the blending amount of carbon black is 0.1 parts by mass or more, the cord of the present invention is colored black, and the color of the tire or the like matches the color of the black rubber, which is preferable because there is no color unevenness when the cord is exposed.
- the blending amount of carbon black is 1 part by mass or more, a polymer reinforcing effect by carbon black is obtained, which is preferable.
- the carbon black compound resin becomes difficult to fluidize when melted, and thread breakage may occur during spinning processing.
- it exceeds 100 parts by mass it becomes difficult to stretch the polymer stretch in the formation of the filament during fiber spinning, so that the surface of the resin material in the sheath is likely to be uneven.
- additives that are usually added to resins can also be blended.
- this additional component conventionally known nucleating agents, antioxidants, neutralizing agents, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, metal deactivators, used as polyolefin resin compounding agents, etc.
- additives such as peroxides, antibacterial and antifungal agents, and fluorescent brighteners, and other additives can be used.
- additives include 2,2-methylene-bis (4,6-di-t-butylphenyl) phosphate, talc, 1,3,2,4-di (p-methylbenzylidene) as a nucleating agent.
- Sorbitol compounds such as sorbitol, hydroxy-di (aluminum t-butylbenzoate), and the like.
- antioxidants examples include, for example, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,1,3-tris (2-methyl-4) as a phenolic antioxidant.
- -Hydroxy-5-t-butylphenyl) butane octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis ⁇ 3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate ⁇ , 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [ 2- ⁇ 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ -1,1-dimethylethyl] -2,4,8,10-tetrao
- Phosphorus antioxidants include tris (mixed, mono and dinonylphenyl phosphite), tris (2,4-di-t-butylphenyl) phosphite, 4,4′-butylidenebis (3-methyl-6) -T-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, bis (2,4-di -T-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl- 5-methylphenyl) -4,4′-biphenylenediphosphonite, bis (2
- sulfur-based antioxidants include di-stearyl-thio-di-propionate, di-myristyl-thio-di-propionate, and pentaerythritol-tetrakis- (3-lauryl-thio-propionate).
- neutralizing agent examples include calcium stearate, zinc stearate, hydrotalcite and the like.
- Hindered amine stabilizers include polycondensates of dimethyl oxalate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, tetrakis (1,2,2, 6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, N, N-bis (3 -Aminopropyl) ethylenediamine and 2,4-bis ⁇ N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino ⁇ -6-chloro-1,3,5-triazine condensation Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2 , 4 Diyl ⁇ ⁇ (2,2,6,6-te
- stearic acid As the lubricant, stearic acid, oleic acid amide, stearic acid amide, behenic acid amide, ethylene bis stearoid and other higher fatty acid amides, silicon oil, higher fatty acid esters, or magnesium stearate, calcium stearate, zinc stearate, 12 -Magnesium hydroxystearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate, magnesium arachidate, calcium arachidate, zinc arachidate, magnesium behenate, calcium behenate, zinc behenate, magnesium lignocerate, calcium lignocerate And zinc lignocerate, especially magnesium stearate, calcium stearate, zinc stearate, arachidic acid mug Siumu, calcium arachidate, zinc arachidate, magnesium behenate, calcium behenate, behenic acid, zinc, mention may be made of magnesium lignoceric acid, calcium lignoceric acid, and metal soap such as zinc lignocerate. *
- antistatic agent examples include higher fatty acid glycerin ester, alkyl diethanolamine, alkyl diethanolamide, alkyl diethanolamide fatty acid monoester and the like. *
- ultraviolet absorbers examples include 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole and the like. *
- Examples of the light stabilizer include n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4 ′.
- a high melting point polyolefin resin is used for the core part, and the compatibility between the core part and the sheath part is good. From the point of view, it is preferable. Unlike the case where different types of resins are used for the core and the sheath by using an olefin resin for both the core and the sheath, the bonding force at the core-sheath polymer interface is high, and the core / sheath. Since it has sufficient peeling resistance against interfacial peeling between the parts, the characteristics as a composite fiber can be sufficiently exhibited over a long period of time.
- a crystalline propylene homopolymer having a melting point of 150 ° C. or higher is used as the high melting point resin (A) in the core, and an ethylene-propylene copolymer is used as the low melting point resin material (B) in the sheath.
- Polypropylene copolymer resin by copolymerization of polypropylene and a component capable of copolymerization with polypropylene, such as a copolymer or an ethylene-butene-propylene terpolymer, and in particular, an ethylene-propylene random copolymer may be used.
- the high melting point polyolefin-based resin in the core is isotactic polypropylene because of good fiber forming properties during spinning.
- melt flow index (melt flow rate, MFR) (MFR1) of the high-melting polyolefin resin and the melt flow index (MFR2) of the low-melting polyolefin resin are particularly limited as long as they can be spun. However, 0.3 to 100 g / 10 min is preferable. The same applies to the melt flow index of the high melting point resin (A) used for the core other than the high melting point polyolefin resin.
- the melt flow index (MFR1) of the high melting point resin (A) containing the high melting point polyolefin resin is preferably 0.3 to 15 g / 10 min, particularly preferably 0.5 to 10 g / 10 min, more preferably 1 to 1. It can be selected from a range of 5 g / 10 min.
- MFR of the high-melting point resin is within the above range, the spinning take-out property and stretchability are improved, and the melt of the high-melting point resin in the core part is heated under the vulcanization process for producing the rubber article. This is because the form of the cord can be maintained without flowing.
- the melt flow index (MFR2) of the low melting point resin material (B) is preferably 3 g / 10 min or more, particularly preferably 5 to 70 g / 10 min, and further preferably 5 to 30 g / 10 min.
- a resin having a large MFR is preferable because the resin easily flows and fills in the gap with the rubber to be deposited.
- the molten material of the resin material (B) may wet and spread on the surface of the cord or bead core fiber material, it is particularly preferably 70 g / 10 min or less. More preferably, it is 30 g / 10 min or less. In this case, when the composite fibers are in contact with each other, the melt of the molten resin material (B) spreads between each other to form a lump-like fiber bonded body. This is preferable because the occurrence of the phenomenon of fusion is reduced. Further, if it is 20 g / 10 min or less, since the fracture resistance of the resin in the sheath portion is increased when the rubber to be fused is peeled off, it is more preferable that the rubber adheres firmly to the rubber.
- the MFR value (g / 10 min) is in accordance with JIS-K-7210.
- the melt flow rate of the polypropylene resin material is 230 ° C. and the load of 21.18 N (2160 g) under the load of the polyethylene resin material.
- the rate is the melt flow rate measured at a temperature of 190 ° C. and a load of 21.18 N (2160 g), respectively.
- the ratio of the core part to the sheath part in the composite fiber of the present invention is preferably 10 to 95% by mass, more preferably 30 to 80% by mass.
- the ratio of the core portion is preferably 10 to 95% by mass, more preferably 30 to 80% by mass.
- the core portion ratio of 50% by mass or more is preferable because the reinforcing performance can be enhanced.
- the ratio of the core part is too large, the ratio of the sheath part is too small, and the core part is likely to be exposed in the composite fiber, and there is a possibility that sufficient adhesion with the rubber cannot be obtained.
- the production method of the composite fiber (monofilament) of the present invention can be carried out by a wet heating drawing method using a core-sheath type composite spinneret with two single-screw extruders for a core material and a sheath material.
- the spinning temperature can be 140 to 330 ° C., preferably 160 to 220 ° C. for the sheath component, and 200 to 330 ° C., preferably 210 to 300 ° C. for the core component.
- the wet heating can be carried out, for example, at a wet heating apparatus 100 ° C. and a hot water bath 95-100 ° C., preferably 95-98 ° C. If it is once cooled and then reheated and stretched, the crystallization of the sheath proceeds, which is not preferable from the viewpoint of heat-fusibility.
- the draw ratio is preferably 1.5 times or more from the viewpoint of crystallization of the core.
- the fineness of the reinforcing material comprising the rubber reinforcing fiber of the present invention is preferably in the range of 100 dtex or more and 5000 dtex or less.
- the fiber thickness of the reinforcing material is less than 100 dtex, the strength is lowered and the cord is easily broken.
- the fiber thickness of the reinforcing material is more preferably 500 dtex or more in order to suppress cord breakage during processing in various processes during manufacture.
- the fiber thickness of the reinforcing material is not particularly limited as long as it can be disposed on each member of a rubber article such as a tire, but is preferably 5000 dtex or less, particularly 4000 dtex or less.
- the fiber thickness in the present invention means a fiber size (conforming to JIS L 0101) measured with a monofilament alone in the case of a monofilament and with a cord bundled with a monofilament in the case of a bundled monofilament.
- the monofilament cord of the present invention is characterized by high adhesion to rubber even when the thickness of the single fiber of the reinforcing material is 50 dtex or more.
- the fiber thickness of the reinforcing material is less than 50 dtex, even when the fiber is not bonded by the adhesive composition or the fiber resin and the rubber are not fused, the problem of the adhesion with the rubber is less likely to occur. This is because when the diameter of a single fiber is reduced, the stress that the cord cuts is smaller than the force at which the bonded portion peels. Therefore, when the adhesion is evaluated by peeling or the like, the interface between the cord and the rubber is peeled off. This is because the cord is cut before it is cut.
- fluff fluff
- the monofilament of the present invention is characterized by high adhesion to rubber even when the thickness of the single fiber of the reinforcing material is 50 dtex or more, and the cord end can be fused.
- the rubber-fiber composite of the present invention is formed by rubber coating the reinforcing material made of the rubber reinforcing fiber.
- a rubber article to be reinforced and a rubber type corresponding to the application site can be appropriately selected and used, and are not particularly limited.
- a rubber composition containing a diene such as a diene rubber is preferred, and a rubber composition further containing a sulfur vulcanizing agent is particularly preferred.
- the diene rubber include natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, and chloroprene rubber, and a rubber composition containing natural rubber and butadiene rubber is preferable.
- the olefin-based random polymer or olefin-based homopolymer of the resin material (B) of the sheath part contains a styrene elastomer (E) containing a styrene block
- the compatibility with a diene rubber containing a styrene component Therefore, the adhesiveness in the rubber composition containing styrene butadiene rubber can be improved.
- the length of the reinforcing material made of the composite fiber is preferably 10 mm or more, and is preferably as long as possible.
- the length of the reinforcing material made of the composite fiber is as short as less than 10 mm, it is necessary to use a method such as kneading into the rubber and extruding when integrating with the rubber, and the rubber coating may be oriented in one direction. It becomes difficult.
- the difference between the short fiber and the long fiber is a difference in whether the end of the fiber acts as a free end or a fixed end. The longer the fibers, the higher the tension bearing ability that is characteristic of the long fibers. Therefore, by appropriately arranging the rubber-fiber composite, it becomes easy to obtain the desired performance in rubber articles such as tires.
- the form when the reinforcing material of the core-sheath composite fiber becomes a fiber assembly is not particularly limited, but is preferably a monofilament or a cord formed by bundling 10 or less monofilaments, more preferably, It is a monofilament cord.
- the core-sheath fiber assembly in the present invention is a fiber form of cord, twist cord, non-woven fabric or woven fabric in which more than 10 monofilaments are bundled, and the fiber assembly is vulcanized in rubber.
- the filaments are welded to each other and the melt penetrates each other, thereby forming a lump of foreign matter in the rubber article. is there. If such foreign matter is generated, cracks may develop from the bulky foreign matter in the rubber article due to rolling distortion during use of the tire, and separation may occur. For this reason, when the core-sheath fiber becomes a fiber assembly in the rubber article, the larger the number of filaments bundled, the more difficult the rubber penetrates between the cords and the easier it is to form a lump of foreign matter. In order to use it as a typical rubber article, there is a problem in durability, and in a twisted cord, non-woven fabric, or woven fiber structure, the number of filaments in which the cord is bundled is generally 10 or less. Is preferred.
- the fibers in the rubber article are arranged such that the monofilament cords of the core-sheath composite fiber do not substantially cross each other inside the composite, that is, there are few points of contact with each other. Further, when the cords are arranged in parallel so that the cords are aligned, the sheath resin does not melt and a plurality of cords do not penetrate each other, so that the rubber article can be reinforced without causing a shape change such as a fiber coagulated mass. Therefore, it is preferable.
- the core-sheath conjugate fiber according to the present invention is disposed in a rubber article, it is preferable that the core-sheath conjugate fiber is not brought into contact with the other surface of the cord subjected to the adhesion treatment. More preferably, rubber is interposed between them.
- the reason for this is that even when the melt flow index of the low melting point olefin polymer as in the present invention is used, if the melt melt spreads on the surface of the cord that has been subjected to the adhesion treatment on the surface, the adhesion treatment is performed. This is because a melt is interposed between the cord and the rubber, thereby causing a problem of preventing the adhesion between the cord surface subjected to the adhesion treatment and the rubber.
- examples of the cord subjected to the adhesion treatment on the surface include carcass plies, belts, beads, etc., and rubber is used between the cord and the core-sheath composite fiber according to the present invention. It is preferable to arrange such that the outer periphery of the cord whose surface is subjected to an adhesive treatment and the core-sheath composite fiber according to the present invention are not brought into contact with each other by interposing them.
- the reinforcing material made of the core-sheath fiber can be covered with rubber in a state of being oriented in one direction.
- the tension applied to the rubber can be borne by the reinforcing material, and the effect of improving the cut-resistant strength when applied to tire reinforcement applications, The effect etc. which disperse
- the amount of rubber used can be reduced by taking advantage of the strength in the fiber axis direction. The effect of improving the fuel consumption can be obtained.
- the number of reinforcements driven in the composite of the present invention is preferably 5 to 75 per 50 mm width. If the number of driving is too small, a sufficient reinforcing effect may not be obtained.
- the composite of the present invention may be arranged in one layer per reinforcing part or in two or more layers as long as there is no problem in the production of the rubber article to be reinforced. There are no particular restrictions on the number of layers provided.
- the rubber-fiber composite of the present invention can be suitably used for reinforcement of various rubber articles such as tires, and has the desired reinforcement performance while suppressing an increase in the thickness of the rubber article. It can be achieved.
- the composite of the present invention when used for tire reinforcement, it is used with a skeleton material rather than a skeleton material that maintains the tire internal pressure and bears the strength of the tire. It is useful as an insert, flipper, chipper, chafer (canvas chafer) member, etc. used for the purpose of improving the steering stability of the tire by improving the effect of reducing the distortion at the time of tire deformation or improving the tire .
- the tensile strength at break after vulcanization of the reinforcing material in the rubber-fiber composite according to the present invention is preferably 29 N / mm 2 or more, more preferably 40 N / mm 2 or more, and even more preferably 90 N / mm. mm 2 or more, particularly preferably 150 N / mm 2 or more, and the higher the value.
- the composite fiber according to the present invention is thermally deformed at the vulcanization temperature at the time of rubber processing so that the sheath part is fused with rubber, but the core part is hardly thermally deformed, and fusing in the fiber axis direction of the composite fiber. It will not be done.
- the resin portion is continuously arranged along the fiber axis direction, a strength of 29 N / mm 2 or higher, which is higher than the rubber breaking strength, can be obtained.
- a strength of 29 N / mm 2 or higher which is higher than the rubber breaking strength, can be obtained.
- such a composite becomes an anisotropic material having sufficient rubber breaking strength in the fiber axis direction. Therefore, in a rubber article provided with this composite, the strain load in such a specific direction is borne. A function can be obtained. If the tensile strength at break of the reinforcing material is less than 29 N / mm 2 , sufficient reinforcing performance may not be obtained in the rubber article after vulcanization.
- the rubber-fiber composite according to the present invention has sufficient reinforcement performance even when vulcanized at a general vulcanization temperature of 150 ° C.
- FIG. 1 is a schematic cross-sectional view showing an example of the pneumatic tire of the present invention.
- the illustrated tire includes a pair of bead portions 11, a pair of sidewall portions 12 that extend from the pair of bead portions 11 to the outside in the tire radial direction, and a tread that extends between the pair of sidewall portions 12 to form a ground contact portion.
- Part 13 The illustrated tire has a carcass layer 2 composed of at least one carcass ply extending across a toroid between bead cores 1 embedded in a pair of bead portions 11, and the crown portion of the tire in the radial direction.
- a belt layer 3 composed of at least two belts arranged outside is provided.
- an inner liner is disposed inside the carcass layer 2 in the tire radial direction.
- symbol 5 in a figure shows a bead filler.
- the pneumatic tire of the present invention is provided with a reinforcing layer using the rubber-fiber composite of the present invention, and thereby has excellent durability as compared with the conventional tire.
- the arrangement position of the reinforcing layer is not particularly limited.
- at least a part of the bead portion 11 and the sidewall portion 12 includes the composite of the present invention.
- a reinforcing layer 4 made of can be disposed.
- the reinforcing layer 4 In the tire during running, the greater the amplitude of vibration of the tire wall, the greater the air vibration generated on the tire side surface, that is, the running noise.
- the reinforcing layer 4 the tensile tension of the composite fiber Therefore, the vibration of the tire side surface can be suppressed, so that the sound generated from the tire side surface can be reduced and noise such as passing noise can be reduced.
- the reinforcing layer 4 made of the composite of the present invention is thinner than the reinforcing layer made of the conventional rubberized cord layer, so there is no demerit due to the increase in the thickness of the side portion. Furthermore, since the tire side portion has a temperature of up to about 60 ° C.
- the melting point of the low melting point polyolefin polymer in the sheath portion is 80 ° C. or more, the composite of the present invention is tired. It can be used by applying to rubber articles such as. Further, even during high strain running such as tire puncture running, since the tire temperature is about 110 ° C., the melting point of the low melting point olefin polymer in the sheath according to the present invention is 120 ° C. or higher.
- the temperature level is equivalent to the softening point of the adhesive composition consisting of resorcin / formalin / latex, which is conventionally used for the adhesion treatment of the tire cord surface, the temperature in the general market where the conventional tire cord is used Since it is considered that durability can be secured, it can be used as a cord member for reinforcing a general tire even under severe temperature durability conditions when traveling in the market, which is particularly preferable. Moreover, if the melting point is 135 ° C. or higher, it may be applicable to racing tires and the like that require higher durability at higher strains and higher temperatures than ordinary tires.
- the reinforcing layer 4 only needs to be disposed on at least a part of the bead portion 11 and the sidewall portion 12, and thereby, due to the tension load caused by the composite fiber in the reinforcing layer 4,
- the carcass ply main body portion 2A extending between the pair of bead portions 11 and the bead filler 5 are preferably used. Between the tire radial direction outer side end 1a of the bead core 1 and the tire shoulder side to the position P on the tire shoulder side.
- the position P is the case where the tire is assembled to the applicable rim, filled with the prescribed internal pressure, and loaded with the prescribed load, with the tire cross-sectional height from the lower end of the bead core 1 to the upper end of the belt layer 3 in the tread portion. Further, it may be present at a position of 65% to 85% of the tire cross-section height.
- “Applicable rim” is an industrial standard effective in the area where tires are produced and used. In Japan, JATMA (Japan Automobile Tire Association) YEAR BOOK is used. In Europe, ETRTO (European Tire and Rim Technical Organization) is used.
- STANDARD MANUAL in the US, refers to the rim specified in TRA (THE TIRE and RIM ASSOCATION INC.) YEAR BOOK, etc.
- the “specified internal pressure” refers to the standard of JATMA etc. for tires of the applicable size when the tire is mounted on the applicable rim
- the internal pressure (maximum air pressure) corresponding to the tire maximum load capacity is defined, and the “specified load” refers to the maximum mass allowed to be applied to the tire in the above-mentioned standard.
- the end portion of the reinforcing layer 4 in the present invention since the cut surface of the end portion of the cord is fused to the rubber, there is no restriction due to a crack developing from a non-adhered portion between the cord end and the rubber due to strain. Therefore, it can be disposed in a tire portion that has a high strain, which has been difficult in the past.
- an example in which the end portion of the reinforcing layer 4 can be arranged at the position P on the tire shoulder side from the end portion 2B in the tire width direction of the carcass ply is given.
- the reinforcing layer 4 and the carcass ply are formed.
- the crossed layers intersect with each other with different cord length directions.
- the reinforcing layer 4 so as to be a crossing layer with the carcass ply in this way, when repeated strain stress such as shear deformation is input between the reinforcing layer 4 crossing the carcass ply with traveling, Since cracks develop from the end face of the non-adhered portion of the end portion of the reinforcing layer 4, the durability of the bead portion cannot be increased from the tire side.
- tires with the end portion of the reinforcing layer 4 arranged in the same range except for tires with special structures that are reinforced with rubber or other members so that cracks do not progress from the end face of the non-adhered portion, It has hardly been put to practical use until now.
- there is a concern due to cracks in the end face of the non-adhered part of the cord end not limited to such a tire structure, so in a pneumatic tire that is becoming increasingly lighter in the future, the end is closely attached It is particularly desirable to become.
- the reinforcing layer 4 may be disposed so that the fiber axis direction of the reinforcing material is any direction.
- the orientation direction of the reinforcing material is substantially the tire circumferential direction.
- the reinforcing material is preferably disposed so that the orientation direction of the reinforcing material is substantially 30 ° to 90 ° from the tire radial direction.
- the vibration of the tire side part in the lateral direction of the tire is applied to the reinforcing material in any direction from 30 ° to 90 ° from the tire circumferential direction or the tire radial direction. Since it can be suppressed by the tensile tension, a high effect can be obtained.
- the angle direction in which the members are arranged is 30 ° or more from the tire radial direction because the effect of suppressing displacement due to the opening between the carcass ply cords is increased. Particularly preferably, it is 45 ° or more from the tire radial direction, and more preferably 90 ° from the tire radial direction.
- the tire cord is more preferable as the angle with respect to the tire radial direction is increased because the melting temperature of the tire cord at a high temperature is increased and the heat resistance of the tire is improved.
- Tm ⁇ Hm / ⁇ Sm.
- ⁇ Sm increases due to disturbance of the orientation in the cord direction, and the melting point decreases. This is because the melting point increases when tension is applied.
- Tension is applied to the cord in the tire with the internal pressure applied, but when it is attached to the vehicle, the cord near the tread surface of the tire is compressed in the tire radial direction.
- the closer the cord arrangement is to 90 ° with respect to the tire radial direction the smaller the compression input, so the tire cord is more likely to be tensioned and the temperature at which the cord actually melts increases.
- the effect of suppressing the displacement between the carcass ply cords is particularly preferable when the reinforcing layer 4 is arranged in the tire circumferential direction because it becomes effective.
- the composite of the present invention when the green tire is molded, is disposed in a desired reinforcing region in the bead portion 11 or the sidewall portion 12 and then 140 ° C. to 190 ° C. according to a conventional method. It can be produced by vulcanizing at a vulcanization temperature of 3 to 50 minutes. Specifically, for example, when the reinforcing layer 4 is disposed so that the fiber axis direction of the reinforcing material is the tire circumferential direction, the composite is formed in a spiral winding structure in the tire radial direction. It can be arranged.
- thermoplastic resin used as a raw material core and sheath resins described in Tables 6 and 7 below, which were dried using a vacuum dryer, were used.
- An ionomer obtained by neutralizing an olefin copolymer containing an unsaturated carboxylic acid or its anhydride monomer with a metal (ion) was prepared by the following methods i) to iii).
- Examples 1 to 16, Comparative Examples 1 to 14 2) Production of rubber reinforcing cord Using the materials shown in the following Tables 1 to 7 as the core component and sheath component, two ⁇ 50 mm single-screw extruders for the core material and the sheath material, Using the core-sheath type composite spinneret with a diameter of 1.25 mm at the spinning temperature shown, the discharge rate was adjusted so that the sheath-core ratio was 4: 6 by mass, and the spinning speed was 100 m / min. The mixture was melt-spun and stretched in a hot water bath at 98 ° C. so as to be 1.7 times to obtain a core-sheath type composite monofilament having a fineness of 550 dtex.
- Table 10 shows that each core-sheath type composite monofilament obtained has a width of 50 mm with a total of 60 shots per 50 mm in width.
- a rubber-fiber composite was produced by coating with an unvulcanized rubber compounded for the sidewall. Further, the surface properties at the time of spinning were determined according to Table 9, and Tables 1 to 5 described the rough appearance of the cord.
- test tires The rubber-fiber composites prepared in 3) above were applied to a reinforcing layer, and test tires of each example and comparative example were manufactured at a tire size of 195 / 65R14.
- This test tire had a carcass layer made of one carcass ply as a skeleton, and a belt layer made up of two belts arranged on the outer side of the crown portion of the carcass in the radial direction of the tire.
- a reinforcing material is provided in a region of a width of 50 mm from the outer end in the tire radial direction of the bead core to the maximum tire width position in the sidewall portion.
- the core-sheath type composite monofilament was disposed so that the orientation direction of the core was substantially the tire circumferential direction. Further, the vulcanization conditions at the time of tire production were 23 minutes at a vulcanization temperature of 180 ° C.
- test piece was prepared by cutting out the rubber so that a certain amount of rubber remained.
- the fiber cord dug up was peeled off from the test piece with a tensile tester, and the rubber adhesion state of the peeled cord was observed.
- any test sample can be used as long as it is a method in which one cord can be peeled off from the rubber with a tire after running and the state of rubber adhesion on the tensile peeled surface can be observed.
- the form of the piece and the manufacturing method are not particularly limited.
- the comparative example 1 which consists only of core part resin is an example which shows that adhesiveness is lower than each Example, and the resin material (B) of a sheath part is required.
- the adhesion (with rubber) after running is C level or higher, the adhesive strength is 1.56 N / piece or less, surface roughness is 0 or more, no air is entered when vulcanizing the resin material of the sheath, Are compatible.
- Comparative Example 2, Comparative Example 3, and Examples 1 to 4 are examples in which (C2) is preferably 2 to 80 parts by mass and (C1) is preferably 2 to 98 parts by mass. When the amount is 100 parts by mass and exceeds 80 parts by mass, the adhesive strength is very rough.
- Example 3 is an example in which the compatibilizer (E), the vulcanization accelerator (F), and the filler (N) other than the olefin copolymer composition (X) are in a preferred range. .
- Comparative Example 4 Examples 5 to 6, and Comparative Example 5 are cases where the olefin polymer is (D1), (D) is in the range of 2 to 75 parts by mass, and (C2) is in the range of 2 to 80 parts by mass. It is an example which shows that the range of is preferable.
- Example 7 is an example in which the homopolymer (D) is a diene type (D2).
- Example 8 is an example in which the homopolymer (D) is a polypropylene polymer in which the stereoregularity is controlled to be low using a catalyst, and is compatible with crystalline propylene (CA-1) in the core. Good, but because the sheath softens, the surface becomes rough. 8) In Example 9, when the homopolymer (D) is a poly 1-butene resin, this also has good compatibility with the crystalline propylene (CA-1) of the core, but is diene and has a soft sheath. As a result, surface roughness increases.
- Comparative Example 6 is an example of a single cord of aliphatic polyester, and it can be seen that the adhesiveness is low when the olefin copolymer composition (X) is not included in the sheath.
- Comparative Example 7 the interface peeled between the core and the sheath.
- Examples 10 to 11 are the same amount of ethylene-unsaturated carboxylic acid as in Comparative Example 8, and the degree of neutralization is 40 and the degree of neutralization is 130, and the adhesion is improved.
- Comparative Examples 10 to 14 and Examples 13 to 16 are examples in which the core resin is 6 nylon.
- Comparative Example 10 is an example in which neither the core nor the sheath is welded with 6 nylon.
- Comparative Example 11 is an example close to the composition of Patent Document 2, and after tire running fatigue, the compatibility between rubber and resin is low, so the adhesion of rubber is low.
- Comparative Examples 13 to 14 are examples that are not ionomers, and the adhesion to rubber is low after running.
- Examples 13 to 16 are examples using the ionomer (C3) according to the present invention, and the performance is obtained at 2 to 35 parts by mass.
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Abstract
Description
前記樹脂材料(B)が、プロピレン-αオレフィン系共重合体(C1)、プロピレン‐非共役ジエン系共重合体(C2)、不飽和カルボン酸またはその無水物の単量体を含むオレフィン系共重合体の金属塩による中和度が20%以上のアイオノマー(C3)、および、オレフィン系ホモ重合体またはオレフィン系共重合体(D)((C1)および(C2)を除く)から選ばれる2種以上のオレフィン系重合体を含むオレフィン系共重合体組成物(X)を含んでなることを特徴とするものである。
本発明のゴム補強用繊維は、芯部が融点150℃以上の高融点樹脂(A)からなり、鞘部が、高融点樹脂(A)よりも融点の低い樹脂材料(B)からなる芯鞘型の複合繊維よりなるものである。
また、芯部と鞘部材料の樹脂界面における相溶性を向上するため、本発明における、前記の「不飽和カルボン酸またはその無水物の単量体を含むオレフィン系共重合体の金属塩による中和度が20%以上のアイオノマー(C3)」を、2~40質量部の範囲で混合することができる。
これらの中でも、エチレン、1-ブテン、4-メチル-1-ペンテン、1-ヘキセンおよび1-オクテンが好ましく、特に好ましいのはエチレン、1-ブテンである。
また、前記プロピレン-αオレフィン系共重合体(C1)のJIS-K-7121に準じて測定した融点は、芯部の高融点樹脂(A)の融点以下が好ましい。なお、融点の下限は特に制限しないが、90℃以上が好ましく、特に好ましくは110℃以上であり、さらには120℃以上である。融点が90℃未満で融着性の良い樹脂を鞘部の樹脂材料(B)に使用するときは、単体の樹脂での適用でなく、それ以上の融点であるオレフィン系重合体と併用して、含有率を例えば25質量%以下で混合すると、加硫の加工時に鞘部の樹脂材料(B)に気泡が入り難くなるため、走行時の歪などにより気泡からの亀裂進展が起こり難くなり、接着の耐疲労耐久性の低下が少なくなるのでより好ましい。
好ましい例としては、1-ブテン-プロピレン共重合体などを挙げることができる。
特に、エチレンとプロピレンに第三成分として非共役ジエンを導入する場合は、エチレン-プロピレン-ジエン系共重合体(EPDM)の成分が含まれると、被着ゴムとの界面の密着性とともに硫黄による共加硫性をもつ成分が含まれるので、好ましい。
これは、以下のような理由による。鞘部の樹脂材料にEPDMなどの共役ジエンを含むオレフィン系共重合体(C2)を用いると、硫黄架橋が可能なジエンを含有することにより、接着性が向上する。しかし、ゴム状重合体の特徴である、無定形かつ軟質の高分子に由来した性状を有するため、通常は繊維材料に用いると、紡糸応力で無定形に伸びて断糸するなどで紡糸し難い樹脂である。但し、芯鞘繊維の鞘部に使用すると、芯部の樹脂が紡糸応力を負担するため、鞘部の表面に付着していれば紡糸が可能となる。しかし、紡糸時のコード表面性状については、ゴム状重合体の成分が多い場合、例えば、紡糸加工で表面が荒れないように紡糸速度を遅くすると、加工時の生産性が低くなり、紡糸加工されたコード同士を重ねて圧をかけると、互いにくっつき合うブロッキング現象が発生し、また、例えば、ボビン巻取り後にコード間が貼り付いたり、巻出しでコード表面が傷ついてしまうことがある。
好ましい例としては、エチレン-メタクリル酸共重合体が、融着性に優れる芯鞘複合繊維が得られるので好ましい。
これらの中でも、アクリル酸メチル、メタクリル酸メチルが好ましい。
なお、本発明者の検討では、鞘部の樹脂材料(B)への使用においては、エチレン-エチレン性不飽和カルボン酸系共重合体を金属で20%以上中和したアイオノマーが好ましい。これは、以下のような理由による。鞘部の樹脂材料(B)が、カルボン酸などの官能基によりプロトンH+供与性の酸性雰囲気になると、被着ゴムから鞘部の樹脂材料(B)に硫黄が移行して活性化しても、プロトンH+が多加硫物を還元するので、多加硫物が形成できないため、被着ゴムとの接着性を強固にできない環境となり易い。このためエチレン‐エチレン性不飽和カルボン酸系共重合体(C3)をアイオノマーにすることが好ましく、鞘部の樹脂材料(B)の組成物がルイス塩基性の雰囲気が保たれるよう、ゴム補強用繊維の鞘部の樹脂材料(B)においては含有量を限定するか、あるいは本発明における加硫促進剤などを添加する必要があるが、このような知見は従来知られていなかった。なお、カルボン酸と金属塩の中和度は、100%以上であることが好ましいが、カルボン酸は弱酸であるため、カルボン酸の中和度が20%でも、本発明の効果が得られる。好ましいカルボン酸の中和度は20%~250%であり、さらに好ましくは、70%~150%である。
中和度(%)=100×[(樹脂成分の陽イオン成分のモル数×陽イオン成分の価数)+(塩基性無機金属化合物の金属成分のモル数×金属成分の価数)]/(樹脂成分のカルボキシル基のモル数)
これら、陽イオン成分量および陰イオン成分量は、中和滴定などのアイオノマーの中和度の検討方法により求めることができる。
前記ポリプロピレンとしては、アイソタクチック、シンジオタチック、アタチックなどの立体規則性のあるポリプロピレンが挙げられるが、鞘部の樹脂材料(B)に使用するポリプロピレンとしては、被着ゴムとの相容性が良い立体配向性が低いポリプロピレンが特に好ましい。このようなポリプロピレンとしては出光興産社製の商品エルモーデュなどのシングルサイトの触媒により低結晶性であるプロピレンが挙げられる。このようなプロピレンを鞘部の樹脂材料(B)に用いると、芯部樹脂にポリプロピレンを用いたときには、芯鞘間の結合を強くすることができるので好ましい。
また、ポリエチレン、ポリプロピレン以外にも、ポリ1-ブテンについても、ポリプロピレンなど他のオレフィン成分との溶融状態の混和性が高く、好ましい例として挙げられる。
スチレン系エラストマー(E)を構成する、その他の共役ジエン化合物としては、1,3-ブタジエン、イソプレン、1,3-ペンタジエン、2,3-ジメチル-1,3-ブタジエン、2-フェニル-1,3-ブタジエン、1,3-ヘキサジエンなどを、単独でまたは2種以上を組み合わせて用いることができるが、これらの中では、1,3-ブタジエンが好ましい。
また、他のスチレン系エラストマーとしては、ポリオレフィン樹脂を主鎖、ビニル系ポリマーを側鎖に持つオレフィン系グラフト共重合体などのスチレン系エラストマーが挙げられる。グラフト共重合体は、幹となる共重合にところどころに枝のように他の重合体が配列した重合体であるが、本発明においては、スチレン単量体を主として長く連結して配列したブロックを含むグラフト共重合体をスチレン系グラフトポリマーとする。
スチレン系グラフトポリマーとしては、低密度ポリエチレンを主鎖としてポリスチレンを側鎖に持つオレフィン系グラフト共重合体(LDPE-g-PS)や、ポリプロピレンを主鎖としてスチレン-アクリロニトリル共重合体を側鎖に持つオレフィン系グラフト共重合体(PP-g-AS)などが挙げられる。
本発明においては、これらの中でも特に、ゴムとの接着性および相容性の観点から、スチレン-ブタジエン共重合体、スチレン-ブタジエン-ブチレン-スチレン共重合体およびスチレン-エチレン-ブタジエン-スチレン共重合体あるいは、旭化成ケミカルズ(株)商品S.O.E.品番609などの両末端にスチレンブロックを、主鎖にスチレン及びブタジエンのランダム共重合体のブロックを有するブロック共重合体の部分水素添加物を、好適に用いることができる。スチレン系エラストマー(E)は、1種を単独で、または、2種以上を適宜組合わせて用いることができる。
スチレン系エラストマー(E)の変性量は、相溶性及び作業性の観点から、通常1.0×10-3~1ミリモル/g、好ましくは5.0×10-3~0.5ミリモル/g、より好ましくは1.0×10-2~0.2ミリモル/g、更に好ましくは1.0×10-2~0.1ミリモル/gである。
エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサメチレンジアミン、ポリエチレンイミン等に挙げられる非環式ポリアミン及びその誘導体並びにその塩、
シクロヘキシルアミンなどの脂環式ポリアミン及びその誘導体並びにこれらの塩、
ヘキサメチレンテトラミンなどの脂環式ポリアミン及びその誘導体並びにこれらの塩、
アニリン、アルキルアニリン、ジフェニルアニリン、1-ナフチルアニリン、N-フェニル-1-ナフチルアミン等に挙げられる芳香族モノアミン及びその誘導体ならびにこれらの塩、
フェニレンジアミン、ジアミノトルエン、N‐アルキルフェニレンジアミン、ベンジジン、グアニジン類、n-ブチルアルデヒドアニリン、などの芳香族ポリアミン化合物及びその誘導体、などが挙げられる。
なお、グアニジン類としては、1,3-ジフェニルグアニジン、1,3-ジ-o-トリルグアニジン、1-o-トリルビグアニド、ジカテコールボレートのジ-o-トリルグアニジン塩、1,3-ジ-o-クメニルグアニジン、1,3-ジ-o-ビフェニルグアニジン、1,3-ジ-o-クメニル-2-プロピオニルグアニジン等が挙げられる。これらのうちで1,3-ジフェニルグアニジンが反応性が高いので好ましい。
ベンズイミダゾ-ル、プリン、キノリン、ペテリジン、アクリジン、キノキサリン、フタラジンなどの複環式の含窒素化合物及びその誘導体、等を挙げることができる。
また、例えば、窒素原子以外のヘテロ原子を有する複素環式化合物としては、オキサゾリン、チアゾリン等の窒素およびその他のヘテロ原子を含有する複素環式化合物およびその誘導体が挙げられる。
具体的には、水酸化マグネシウム、水酸化カルシウム、水酸化ナトリウム、水酸化リチウム、水酸化カリウム、水酸化銅などの金属水酸化物;酸化マグネシウム、酸化カルシウム、酸化亜鉛(亜鉛華)、酸化銅などの金属酸化物;炭酸マグネシウム、炭酸カルシウム、炭酸ナトリウム、炭酸リチウム、炭酸カリウムなどの金属炭酸化物が挙げられる。
これらの中でも、アルカリ金属塩としては、金属水酸化物が好ましく、特に水酸化マグネシウムが好適である。
なお、これら金属塩は、加硫助剤に分類されることもあるが、本発明においては、加硫促進剤に分類する。
これらのうち、N-エチル-N-フェニルジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジブチルジチオカルバミン酸亜鉛は、反応性が高いため望ましい。また、促進剤化合物に含まれるアルキル基が大きくなると比較的に無極性であるポリマーの場合では溶解度が高くなる傾向があり、析出などによる表面性状の悪化による紡糸性の低下などが発生しにくいため、ジブチルジチオカルバミン酸亜鉛などは、特に好ましい例である。
本発明のカーボンブラックについては、JIS K6217による窒素吸着比表面積が20~150m2/g、JIS K6221によるヨウ素吸着量が15~160mg/g、JIS K6221の(A法)によるDBP吸油量が25~180cm3/100gの範囲にあるカーボンブラックが用いられ、好ましくは、窒素吸着比表面積が70~142m2/g、ヨウ素吸着量が50~139mg/g、DBP吸油量(A法)が70~140cm3/100gの範囲にあるカーボンブラックである。
また、本発明のカーボンブラックの平均粒子径は、10~70nmの範囲であることが好ましく、さらに好ましくは10~25nmの範囲である。比較的小さい粒径で分散性が良く、かつ窒素吸着の比表面積やヨウ素吸着量が高めであり、ポリマーの細孔への吸着などの表面性状が良好な汎用カーボンブラックであると、好ましい。本発明の特に好ましいカーボンブラックとしては、SAFカーボンブラック、SAF-HSカーボンブラック、ISAFカーボンブラック、ISAF-HSカーボンブラック、ISAF-LSカーボンブラック等のファーネスブラック等が挙げられ、これらのカーボンブラックを単独で用いることも、2種以上を組み合わせて用いることもできる。
また、鞘部の樹脂材料(B)の、オレフィン系ランダム重合体あるいはオレフィン系ホモ重合体に、スチレンブロックを含むスチレン系エラストマー(E)を含めると、スチレン成分を含むジエン系ゴムへの相溶性が向上するため、スチレンブタジエンゴムを含むゴム組成物での接着性を向上させることができる。
また、タイヤコードは、タイヤ半径方向に対し角度が付くほど、タイヤコードの高温での融解温度は高くなり、タイヤの耐熱性が向上するために好ましくなる。この理由は前出の通り、物質の融点はTm=ΔHm/ΔSmの式で表されるため、コード方向に圧縮をかけると、コード方向に配向を乱すことでΔSmが大きくなり融点が下がるが、引張りをかけると融点が上がることによる。内圧を張った状態のタイヤ内のコードには張力がかかるが、車両に装着するとタイヤの踏面付近のコードで、タイヤ半径方向に圧縮がかかる。しかし、タイヤ半径方向に対し90°のコード配置に近いほど圧縮の入力が少なくなるため、タイヤコードには張力がかかりやすくなり、コードが実際に融解する温度が上昇するためである。
素材となる熱可塑性樹脂としては、真空乾燥機を用いて乾燥させた、下記表6,7に記載された芯材および鞘材の樹脂を用いた。
なお、不飽和カルボン酸またはその無水物の単量体を含むオレフィン系共重合体を金属(イオン)で中和されてなるアイオノマーは、以下のi)~iii)の方法によって、調製した。
i)SC-1化合物の調製
エチレン・メタクリル酸共重合体の酸基の40%が中和されてなるアイオノマーの調製については、表6に示す樹脂材料(HC-1)の100質量部と水酸化ナトリウム(市販JIS一級)2.8質量部を、溶融押出機にて200℃で混練りして、溶融押出機の先端のダイスから押出した溶融ストランドを断片化して、真空乾燥機で乾燥を行い、ポリマーペレットを得た。
ii)SC-2化合物の調製
エチレン・メタクリル酸共重合体の酸基の130%が中和されてなるアイオノマーの調製については、表6に示す樹脂材料(HC-1)の100質量部と水酸化ナトリウム(市販JIS一級)9.0質量部を、溶融押出機にて200℃で混練りして、溶融押出機の先端のダイスから押出した溶融ストランドを断片化して、真空乾燥機で乾燥して調製した。なお、水酸化ナトリウムは市販のJIS一級試薬を用いて中和した。
iii)SC-3化合物の調製
無水マレイン酸変性ポリブタジエンの酸基の100%が中和されてなるアイオノマーの調製については、表6に示す樹脂材料(HC-2)の100質量部と酸化亜鉛9.0質量部を、溶融押出機にて200℃で混練りして、溶融押出機の先端のダイスから押出した溶融ストランドを断片化して、真空乾燥機で乾燥して調製した。
2)ゴム補強用コードの作製
芯成分および鞘成分として、下記表1~7に示す材料を用いて、芯材用および鞘材用の2台のφ50mmの単軸押出機で、各表中に示す紡糸温度にて、口径が1.25mmの芯鞘型複合紡糸口金を用いて、鞘芯比率が質量比率で4:6となるように吐出量を調整して、紡糸速度100m/分にて溶融紡糸し、98℃の熱水浴で1.7倍となるように延伸して、繊度550dtexの芯鞘型複合モノフィラメントを得た。
得られた各芯鞘型複合モノフィラメントを、幅50mmあたり計60本の打込み数で50mmの幅となるよう、表10に示すサイドウォール用配合の未加硫状態のゴムにより被覆して、ゴム-繊維複合体を作製した。
また、紡糸時の表面の性状を表9に従い判定して、表1~5にコードの外観の荒れの状況を記載した。
上記3)で作製した、このゴム-繊維複合体を補強層に適用して、タイヤサイズ195/65R14にて、各実施例および比較例の供試タイヤを作製した。この供試タイヤは、1枚のカーカスプライからなるカーカス層を骨格とし、カーカス層のクラウン部タイヤ半径方向外側に配置された2枚のベルトからなるベルト層を備えていた。また、この供試タイヤのカーカスプライの本体部とビードフィラーとの間には、サイドウォール部のうち、ビードコアのタイヤ半径方向外側端部からタイヤ最大幅位置までの幅50mmの領域に、補強材の配向方向が実質的にタイヤ周方向になるように、上記芯鞘型複合モノフィラメントを、配設した。また、タイヤ製造時の加硫条件としては、加硫温度180℃で23分とした。
各比較例および実施例の供試タイヤを、JATMA YEAR BOOK-2015規格の適用リム(標準リム)にリム組みし、25±2℃の室内にて内圧を220kPaに調整してから、24時間放置した後、タイヤの空気圧の再調整を行い、JATMA規格の130%の荷重(荷重676kgf、空気圧200kPa)をタイヤに付加し、速度80km/時で4万kmの距離を直径約3mのドラム上にて連続走行させることで、比較例および実施例の供試タイヤに「一般的な市街地走行に近い走行条件であるがより高い荷重負荷の条件」で、走行時の熱劣化と疲労を入力した。
各比較例および実施例の供試タイヤのビード部のリムラインの高さ位置から取り出した複合体からテスト用のサンプルピースを切り出して、このサンプルピースから掘り起こした繊維コードについて30cm/分の速度でコードを加硫物から剥離させ、剥離後のコードについて、ゴム付着状況を観察して、下記表8に従いランク付けを行って、ゴム付着率(ゴム付)を確認し、下記表1~5に表示した。
ここで、本発明のタイヤからのサンプルピースの切り出しは、図2に示すように、まず繊維コードのコード軸方向に沿って切り出しを行い、次に、コード表面から約0.1~0.7mm程度のゴムが残るようにゴムを切り出して試験片を作製し、掘り起こした繊維コードを、引張試験機で試験片から剥離し、この剥離後のコードのゴム付着状態を観察した。なお、本発明においては、上記の方法以外でも、走行後のタイヤで、ゴムからコード1本を引張剥離して、その引張剥離面のゴム付着状態を観察できる方法であれば、テスト用のサンプルピースの形態や作製方法は、特に制限されない。
実施例および比較例で作製したコードを、図3に示すようにパッキングした後、面圧50gf/cm2となるように荷重をかけて5時間静置した。このとき、荷重がかかったときにパッキングが崩れないよう、モールドのような成型容器に前記パッキングを入れて荷重をかけた。その後、コードを堀り起こし、30cm/分の速度でコード同士を剥離するときの抗力を25±1℃の室内雰囲気温度で測定し、モノフィラメントコード間の粘着力とした。この結果を表1~5に示した。
2)BR:ポリブタジエンゴム、宇部興産(株)製、商品名:BR150L
3)カーボンブラック、東海カーボン(株)製、商品名:シーストF
4)ワックス:日本精蝋製(株)製、商品名:マイクロクリスタリンワックス「オゾエース0701」
5)加硫助剤(ステアリン酸)、新日本理化(株)製、商品名:50S
6)加硫促進助剤(酸化亜鉛)、ハクスイテック(株)製、酸化亜鉛華
7)老化防止剤:N-(1,3-ジメチルブチル)-N’-p-フェニレンジアミン、大内新興化学工業(株)製、ノックラック6C
8)加硫促進剤:ジフェニルグアニジン、大内新興化学工業(株)製、ノクセラーD
9)加硫促進剤:ジベンゾチアジルジスルフィド、三新化学工業(株)製、サンセラーDM
10)加硫促進剤:N-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド、三新化学工業(株)製、サンセラーCM
11)硫黄:鶴見化学工業(株)製、5%油処理粉末硫黄
1)芯部樹脂のみからなる比較例1は、各実施例より接着性が低く、鞘部の樹脂材料(B)が必要であることが分かる例となっている。
2)実施例では、走行後の接着性(ゴム付)がCレベル以上、粘着力が1.56N/本以下、表面の荒れ〇以上、鞘部の樹脂材料の加硫時のエアー入りなし、が両立されている。
3)比較例2、比較例3、実施例1~4は、(C2)が2~80質量部で、(C1)が2~98質量部が好適なことが分かる例であり、(C2)が100質量部で80質量部を超過すると粘着力が表面の荒れが大きい。
4)実施例3は、オレフィン系共重合体組成物(X)以外の、相容化剤(E)、加硫促進剤(F)、充填剤(N)が、好ましい範囲内の例である。
5)比較例4、実施例5~6、比較例5は、オレフィン系重合体が(D1)の場合で、(D)が2~75質量部の範囲、(C2)が2~80質量部の範囲が好ましいことを示す例である。
6)実施例7は、ホモ重合体(D)がジエン系の(D2)の場合の例である。
7)実施例8は、ホモ重合体(D)が触媒を用い立体規則性を低く制御したポリプロピレン重合体の場合の例であり、芯部の結晶性プロピレン(CA-1)とはなじみ性が良いが、鞘が軟化するので、表面の荒れが大きくなる。
8)実施例9は、ホモ重合体(D)がポリ1-ブテン樹脂のとき、これも、芯部の結晶性プロピレン(CA-1)とはなじみ性が良いが、ジエンで鞘が軟かくなるので、表面の荒れが大きくなる。
9)比較例6は、脂肪族ポリエステルの単一コードの例であり、鞘部にオレフィン系共重合体組成物(X)を含まないと、接着性が低いことが分かる。
10)比較例7では、芯と鞘の間で界面が剥離した。
11)比較例8は、エチレン-不飽和カルボン酸であって中和度=0の例であり、ゴムとの相容性が低くなり、比較例7より接着が低下している。
12)実施例10~11は、比較例8と同量のエチレン-不飽和カルボン酸であって中和度=40、中和度=130の場合であり、接着性が向上している。
13)実施例11、実施例12、比較例9と、アイオノマーの比率が高くなるにつれて、樹脂組成物としては極性が高くなり、無極性の被着ゴムとは接着性が低くなっている。また、エチレン系重合体、ブテンを含む共重合体なので、軟化点が低いために、表面が荒れている。
14)比較例10~14、実施例13~16は、芯部樹脂が6ナイロンの例である。
15)比較例10は、芯部も鞘部も6ナイロンでは溶着しない例である。
16)比較例11は、特許文献2の組成に近い例であり、タイヤ走行疲労後では、ゴムと樹脂との間の相溶性が低いために、ゴムの接着が低いものになっている。
17)比較例13~14は、アイオノマーでない例であり、ゴムとの接着が走行後に低くなっている。
18)実施例13~16は、本発明に係るアイオノマー(C3)を用いた例であり、2~35質量部で性能が得られている。
1a ビードコア1のタイヤ半径方向外側端部
2 カーカス層
2A カーカスプライの本体部
2B カーカスプライのタイヤ幅方向端部
3 ベルト層
4 補強層
5 ビードフィラー
11 ビード部
12 サイドウォール部
13 トレッド部
Claims (9)
- 芯部が融点150℃以上の高融点樹脂(A)からなり、鞘部が、該高融点樹脂(A)よりも融点の低い樹脂材料(B)からなる芯鞘型の複合繊維よりなるゴム補強用繊維であって、
前記樹脂材料(B)が、プロピレン-αオレフィン系共重合体(C1)、プロピレン‐非共役ジエン系共重合体(C2)、不飽和カルボン酸またはその無水物の単量体を含むオレフィン系共重合体の金属塩による中和度が20%以上のアイオノマー(C3)、および、オレフィン系ホモ重合体またはオレフィン系共重合体(D)((C1)および(C2)を除く)から選ばれる2種以上のオレフィン系重合体を含むオレフィン系共重合体組成物(X)を含んでなることを特徴とするゴム補強用繊維。 - 前記樹脂材料(B)が、前記オレフィン系共重合体組成物(X)と、スチレン単量体を主として連続して配列してなる単独分子鎖を含むスチレン系エラストマー(E)、加硫促進剤(F)および充填剤(N)からなる群から選ばれる1種以上と、を含んでなる請求項1記載のゴム補強用繊維。
- 前記プロピレン-αオレフィン系共重合体(C1)が、プロピレンとエチレンまたは1-ブテンとのランダム共重合体である請求項1記載のゴム補強用繊維。
- 前記アイオノマー(C3)が、エチレン‐エチレン性不飽和カルボン酸系共重合体のアイオノマー、または、ポリオレフィンの不飽和カルボン酸重合体のアイオノマーである請求項1記載のゴム用補強繊維。
- 前記プロピレン‐非共役ジエン系共重合体(C2)が、エチレン-プロピレン-ジエン系共重合体である請求項1記載のゴム補強用繊維。
- 前記オレフィン系ホモ重合体またはオレフィン系共重合体(D)((C1)および(C2)を除く)が、α‐オレフィン、または、ポリオレフィンゴムである請求項1記載のゴム補強用繊維。
- 前記オレフィン系共重合体組成物(X)100質量部中に、前記プロピレン-αオレフィン系共重合体(C1)が20~98質量部、前記プロピレン-非共役ジエン系共重合体(C2)が2~80質量部、前記アイオノマー(C3)が2~40質量部、前記オレフィン系ホモ重合体またはオレフィン系共重合体(D)((C1)および(C2)を除く)が2~75質量部で、2種以上含まれる請求項1記載のゴム補強用繊維。
- 請求項1記載のゴム補強用繊維よりなる補強材が、ゴム被覆されてなることを特徴とするゴム-繊維複合体。
- 請求項8記載のゴム-繊維複合体からなる補強層を備えることを特徴とする空気入りタイヤ。
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EP16855555.5A EP3363934B1 (en) | 2015-10-14 | 2016-10-14 | Fiber for rubber reinforcement, rubber-fiber composite, and pneumatic tire using same |
US15/767,397 US20180297407A1 (en) | 2015-10-14 | 2016-10-14 | Fiber for rubber reinforcement, rubber-fiber composite, and pneumatic tire using same |
CN201680060585.3A CN108138376A (zh) | 2015-10-14 | 2016-10-14 | 橡胶加强用纤维、橡胶-纤维复合体和使用其的充气轮胎 |
JP2017545504A JPWO2017065303A1 (ja) | 2015-10-14 | 2016-10-14 | ゴム補強用繊維、ゴム−繊維複合体およびこれを用いた空気入りタイヤ |
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JPWO2017065304A1 (ja) * | 2015-10-14 | 2018-08-02 | 株式会社ブリヂストン | ゴム補強用繊維、ゴム−繊維複合体およびこれを用いた空気入りタイヤ |
JPWO2017065305A1 (ja) * | 2015-10-14 | 2018-08-02 | 株式会社ブリヂストン | ゴム補強用繊維、ゴム−繊維複合体およびこれを用いた空気入りタイヤ |
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EP3901361A4 (en) * | 2018-12-20 | 2022-03-02 | Teijin Frontier Co., Ltd. | PROCESS FOR PRODUCTION OF RUBBER REINFORCING FIBERS |
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EP3363934A4 (en) | 2018-08-22 |
WO2017065303A8 (ja) | 2018-05-11 |
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