CN108690273A - Curing bag rubber composition and curing bag - Google Patents
Curing bag rubber composition and curing bag Download PDFInfo
- Publication number
- CN108690273A CN108690273A CN201810230918.3A CN201810230918A CN108690273A CN 108690273 A CN108690273 A CN 108690273A CN 201810230918 A CN201810230918 A CN 201810230918A CN 108690273 A CN108690273 A CN 108690273A
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- Prior art keywords
- rubber
- curing bag
- rubber composition
- mass parts
- butyl
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- YOEWQQVKRJEPAE-UHFFFAOYSA-L succinylcholine chloride (anhydrous) Chemical class [Cl-].[Cl-].C[N+](C)(C)CCOC(=O)CCC(=O)OCC[N+](C)(C)C YOEWQQVKRJEPAE-UHFFFAOYSA-L 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N β-pinene Chemical compound C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
A kind of fraction defective for the curing bag for reducing and being generated in sulfidization molding (especially bubble fraction defective), excellent in te pins of durability and the good curing bag rubber composition and curing bag of pyroconductivity are provided.A kind of curing bag rubber composition, it contains, including the rubber constituent of the above butyl system rubber of 81 mass parts, comprising carbon black and relative to 100 mass parts of rubber constituent and containing fillers more than 45 mass parts, and include the hydrocarbon compound for the structural unit for coming from ethylene and the structural unit for coming from propylene for adding up to 85mol% or more.
Description
Technical field
The present invention relates to curing bag rubber composition and curing bags.
Background technology
Curing bag is in the sulfidization molding of tire.Curing bag is configured at the inside of green tire, by filling out inside it
Hyperbaric heating medium is filled, green tire is squeezed from interior side to sulfurizing mould as a result, tyre vulcanization is made to be molded.Heat medium be steam,
Nitrogen, air etc..Curing bag is that these heat mediums are filled in inside under high pressure and 180~240 DEG C of hot conditions,
Repeat the sulfidization molding of tire.It is therefore desirable to the excellent in te pins of durability of the rubber composition of curing bag is constituted, and obtain
The fraction defective of curing bag is lower.
In recent years, it is thus proposed that the time of 1 tires is vulcanized by shortening to improve the technology of vulcanization production efficiency.Example
Such as, in patent document 1, it is proposed that by using the curing bag rubber composition containing the excellent carbon fiber of pyroconductivity,
Accelerate the heat conduction velocity to tire in vulcanization process, to shorten the technology for the time for vulcanizing 1 tires.However, being expanded into
In the curing bag of balloon-like, fiber and inorganic filler etc. are difficult to be orientated on the direction of heat transfer i.e. thickness direction.Therefore, according to
It so is difficult to obtain and shows excellent pyroconductivity, excellent in te pins of durability, and the rubber group that the fraction defective of the curing bag obtained is lower
Close object.In addition, as the plasticizer used in the butyl system rubber of curing bag, neoprene, using there is castor oil.However,
The difference of the SP values of castor oil and butyl rubber is big, can not equably be plasticized rubber composition.
[Existing technical literature]
[Patent document]
[Patent document 1]Japanese Unexamined Patent Publication 2012-224720 bulletins
Invention content
The subject that the invention solves
The object of the present invention is to provide a kind of fraction defectives for the curing bag for reducing and being generated by sulfidization molding (especially
It is bubble fraction defective), excellent in te pins of durability, and the curing bag rubber composition and curing bag that pyroconductivity is good.
The means to solve the problem
It solves to include following composition in the present invention of the above subject.
(1) a kind of curing bag rubber composition, contains rubber constituent, filler and hydrocarbon compound;The rubber
In 100 mass parts of ingredient, including butyl system rubbers more than 81 mass parts;The filler includes carbon black, and relative to the rubber
100 mass parts of glue ingredient contain the fillers more than 45 mass parts;The hydrocarbon compound includes to add up to 85mol% or more
Come from the structural unit of ethylene and come from the structural unit of propylene.
(2) the SP values of the curing bag rubber composition as described in (1), above-mentioned hydrocarbon compound are 8.5 or less.
(3) the curing bag rubber composition as described in (1) or (2), the glass transition temperature of above-mentioned hydrocarbon compound
It is -80~-50 DEG C.
(4) the curing bag rubber composition as described in any one of (1)~(3), in the rubber of 100 mass parts
In glue ingredient, the butyl system rubber contains the butyl rubber of 40 mass parts or more, and the butyl rubber contains to methylbenzene second
Alkene unit is as repetitive unit.
(5) the curing bag rubber composition as described in any one of (1)~(4) further contains and is selected from terpene
It is at least one kind of in the group that alkene system resin, rosin series resin and ethylene butene styrene copolymer resins are constituted.
(6) curing bag being made of with rubber composition the curing bag described in any one of (1)~(5).
Invention effect
According to the present invention, a kind of fraction defective for the curing bag for reducing and being generated in sulfidization molding (especially bubble is provided
Fraction defective), excellent in te pins of durability, and the curing bag rubber composition that pyroconductivity is good.In addition, vulcanizate according to the present invention
The curing bag that capsule rubber composition is constituted, it is possible to provide fraction defective (especially bubble fraction defective) low, excellent in te pins of durability, and
The good curing bag of pyroconductivity.
Specific implementation mode
< curing bags rubber composition >
The curing bag rubber composition (being also referred to as rubber composition below) of an embodiment of the invention contains rubber
Glue ingredient, filler and hydrocarbon compound.Rubber constituent contains the butyl system rubber of 81 mass % or more.Filler includes carbon black, relatively
In 100 mass parts of rubber constituent, contain fillers more than 45 mass parts.Hydrocarbon compound coming from containing 85 mass % or more in total
In ethylene structural unit and come from the structural unit of propylene.It illustrates individually below.
(rubber constituent)
Rubber constituent includes the butyl system rubber of 81 mass % or more.Butyl system rubber is not particularly limited.Lift its an example
Words, butyl system rubber is butyl rubber, halogenated butyl rubber, various modified butyl system rubbers etc..Butyl rubber (IIR) refers to making
The non-halogenated butyl rubber known by conventional butyl rubbers.IIR can use the rubber used in usual tire industry.
Halogenated butyl rubber (X-IIR) is that the intramolecular of conventional butyl rubbers has imported the butyl system rubber of halogen.Halogenation
Butyl rubber can enumerate brombutyl (Br-IIR), chlorinated scoline (Cl-IIR) etc..
Modified butyl system rubber is that the butyl system rubber of particular functional group has been imported by modifying agent.Modified butyl system rubber
Glue has other repetitive units other than isobutene units.Other repetitive units are not particularly limited.If lifting its an example, other
Repetitive unit be isoprene unit, aromatic ethenyl compound unit etc..Aromatic ethenyl compound unit is without spy
It does not limit.If lifting its an example, aromatic vinyl units are styrene units, p-methylstyrene unit, o-methyl-benzene second
Alkene unit, m-methyl styrene unit etc..Wherein, the viewpoint based on modified butyl system rubber ease of manufacturing, preferably comprises virtue
Fragrant race's vinyl compound units, further preferably at least one p-methylstyrene unit, o-methyl styrene unit,
Methylstyrene unit, further preferably p-methylstyrene unit.
The manufacturing method of modified butyl system rubber is not particularly limited.If lifting its an example, modified butyl system rubber can pass through
Make the side of the modifying agent and butyl system rubber (halobutyl system rubber) phase reaction with halogen group with nitrogen-containing functional group
Method etc. and be made.As long as halobutyl system rubber end, main chain, side chain at least one on halogen group butyl system
Rubber is not particularly limited.The manufacturing method of halobutyl system rubber is that isobutene is made to be copolymerized with the monomer with halogen group
Method makes isobutene be copolymerized, again by the method etc. of the copolymer halogenation of acquisition with other monomers.
Based on the viewpoint as curing bag with abundant durability, in 100 mass parts of rubber constituent, butyl system rubber
Content be 81 mass parts more than, more than preferably 90 mass parts, more than more preferable 92 mass parts.In addition, excellent based on obtaining
The viewpoint of different durability, in 100 mass parts of rubber constituent, the content of butyl system rubber can be 100 mass parts.In addition, being based on
Obtain the viewpoint with the cross-linking effects of other rubber constituents, in 100 mass parts of rubber constituent, the content preferably 98 of butyl system rubber
Below mass part, more preferable 96 is below mass part.In addition, butyl system rubber can be used together.At this point, the content of butyl system rubber is
The total amount of butyl system rubber of more than two kinds.
P-methylstyrene list is contained in above-mentioned modified butyl system rubber for the butyl system rubber of present embodiment
Member as repetitive unit butyl rubber (PMS butyl rubbers) preferably comprised in 100 mass parts of rubber constituent 40 mass parts with
On, more than further preferably 50 mass parts, more than further preferably 60 mass parts.Butyl system rubber is by containing 100 matter
PMS butyl rubbers more than 40 mass parts in part rubber constituent are measured, improving resistance to deterioration (can be especially aftermentioned deterioration EB).This
The PMS butyl rubbers of sample can enumerate the product that the manufactures such as Exxon Mobil Corporation are peddled.
The content of the modification base of PMS butyl rubbers is indicated with bromine content (mol%).In general, the modification base of PMS butyl rubbers
Content be 0.3~1.5mol%.Curing bag vulcanizes at a high temperature of 180~200 DEG C.Thus, for example bromine content is
The Exxpro3035 (Exxon Mobil Corporation's system) of 0.47mol% is appropriate in terms of taking into account vulcanization fraction defective.Bromine content is excessive
When, rubber composition easy tos produce bubble before generating sufficient rubber flowing.In addition, Exxpro 3035 is used as tyre surface rubber
Glue used time, rubber composition vulcanize at 160~190 DEG C.Therefore, the point based on high response, such as bromine content is
The Exxpro3745 (Exxon Mobil Corporation's system) of 1.2mol% is appropriate.
Rubber constituent can also suitably contain other rubber constituents other than above-mentioned butyl system rubber.Other such rubber
Ingredient can enumerate isoprene rubber, neoprene (CR), styreneisobutylene-styrene block copolymer (SIBS), third
Alkene nitrile butadiene rubber (NBR) etc..These other rubber constituents can be used in combination.
Among other rubber constituents, integrated based on resistance to deterioration, crosslinking reactivity, resistance to chemical reagents or curingprocess rate excellent
Viewpoint, rubber constituent preferably comprise neoprene.When containing neoprene, for the property as curing bag rubber composition
Retainable reason, in 100 mass % of rubber constituent the content preferably 2 mass % or more, more preferable 3 mass % of neoprene with
On.In addition, for the viewpoint for inhibiting deterioration, in 100 mass % of rubber constituent neoprene content preferably 10 mass % hereinafter,
More preferable 7 mass % or less.
(filler)
The rubber composition of present embodiment contains carbon black as filler.It can be filled out containing other other than carbon black in filler
Material.It is selected in the substance that other such fillers can be usual from rubber composition now.If lifting its an example, other fillers
It is aluminium hydroxide, aluminium oxide, Gui diatomaceous earths, calcium carbonate, talcum etc..
It is adequately reinforcing based on making the rubber composition of acquisition have, and the viewpoint that pyroconductivity is excellent, relative to rubber
100 mass parts of glue ingredient, the content of filler is more than 45 mass parts, more than preferably 50 mass parts.In addition, whole based on filler
The content preferably 100 of the viewpoint of the dispersibility of body, the rubber composition excellent in te pins of durability of acquisition, filler is below mass part, more excellent
It selects 90 below mass part.
Carbon black is not particularly limited.If lifting its an example, carbon black be furnace black, acetylene black, thermal black, channel black,
Graphite (blacklead) etc..These carbon blacks can be used together.
Based on the durability for improving the curing bag obtained, the viewpoint in sufficient capsule service life, the N2 adsorption of carbon black are obtained
Specific surface area (N2SA) preferred 40m2/ g or more, more preferable 60m2/ g or more.In addition, for the purpose of ensuring that good carbon black dispersion, good
The viewpoint of good pyroconductivity, N2The preferred 300m of SA2/ g is hereinafter, more preferable 140m2/ g or less.In addition, the N2 adsorption of carbon black compares table
Area can be acquired by the A methods of JIS K6217.In addition, in present embodiment, the capsule service life refers to until 1 curing bag is broken
The average tyre strip number that can be vulcanized when until damage.
Rubber composition based on acquisition has sufficient reinforcing, CrackGrowth, and the viewpoint that pyroconductivity is excellent,
Relative to 100 mass parts of rubber constituent, more than content preferably 15 mass parts of carbon black, more than more preferable 20 mass parts.In addition, base
In dispersed excellent, the viewpoint of the excellent in te pins of durability of the curing bag of acquisition that filler is whole, content preferably 90 mass of carbon black
Part is hereinafter, more preferable 80 is below mass part.
It is excellent based on pyroconductivity, and the viewpoint of the compatibility with carbon black or rubber constituent can be improved, present embodiment
Filler preferably comprises graphite.Based on by the way that graphite and carbon black to be used in combination, the viewpoint of pyroconductivity can be improved, relative to rubber constituent
100 mass parts, graphite preferably comprise 10~25 mass parts or so.
Based on opposite the content of filler can be reduced, and can improve the viewpoint of the heat conductivity of the rubber composition of acquisition,
The filler of embodiment can suitably admixed graphite or acetylene black.Particularly, pass through admixed graphite, the rubber composition of acquisition
Rubber flow, be easy to reduce obtain curing bag light fraction defective.In addition, in present embodiment, light fraction defective refers to
By visual inspection visually inspect, confirmation has bubble-free, starved, uneven thickness, extreme dent or crackle, with such defect
Curing bag is relative to the ratio shared by the curing bag for quality product.
Talcum is not particularly limited.As long as talcum is using hydrous magnesium silicate as principal component.In addition, the oil absorption of talcum without
It is particularly limited to.If citing, the oil absorption of talcum is 20~80cc/100g.
For the viewpoint of low consumption combustion property, preferably 50 μm of the average grain diameter of talcum is hereinafter, more preferable 30 μm or less.In addition, sliding
The lower limit of the average grain diameter of stone is not particularly limited.If citing, the average grain diameter of talcum is 1 μm or more.
(hydrocarbon compound)
Hydrocarbon compound is total up to containing the structural unit for coming from ethylene and the structural unit for coming from propylene
The copolymer of 85mol% or more.Display contains the structural unit for coming from ethylene and the structural unit for coming from propylene below
General formula (in formula, m, n are 1 or more integer).In present embodiment, the amount (mol%) of structural unit can be based on each structure
Unit is calculated relative to the number (m in formula or n) of general construction unit number.In addition, the hydrocarbon compound of present embodiment is aobvious
Mobility is shown.In addition, if hydrocarbon compound is only made of polyethylene, it is easy to crystallize, is easy to become solid.In addition, this reality
The compatibility of the hydrocarbon compound and butyl system rubber of applying mode is good, can reduce the viscosity of the rubber composition of acquisition, and is not easy
Volatilization.
[Change 1]
In addition, the hydrocarbon compound of present embodiment is different from the ethylene propylene diene rubber for solid under room temperature
(EPDM, with reference to general formula below.In formula, m, n, o are 1 or more integer, and X is diene ingredient).Further, present embodiment
Hydrocarbon compound structure it is simple, molecular motion is big compared with other intermixtures, have defoaming effect (surface of bubble can be reduced
Tension).
[Change 2]
Come from the structural unit of ethylene and comes from the summation (m+n) of the structural unit of propylene in 85mol% or more
, it is good based on the compatibility with butyl system rubber, the rubber composition viscosity of acquisition can be reduced and the sight of defoaming can be improved
Point, preferably 90mol% or more, more preferably 100mol%.
The composition for coming from the structural unit and the structural unit for coming from propylene of ethylene is not particularly limited.Lift one
If example, the composition of the structural unit for coming from ethylene and the structural unit for coming from propylene is 100:1~1:100.It is logical
Crossing makes composition in such range, is easy to show to the plasticity solidification of rubber composition, defoaming effect, and then be easy to
Reduce fraction defective when filler dispersion, sulfidization molding.
The hydrocarbon compound of present embodiment is not only to the plasticity of rubber composition, in the processing and forming of rubber composition
When, keep the effect (defoaming effect) that the air that in butyl system rubber or the interface of rubber constituent and filler generates overflows also excellent.
But as curing bag rubber composition, there are contain castor oil in existing plasticizer.Castor oil be less susceptible to
Butyl system rubber mixes, and exists and decomposed and volatilized by high-temperature steam, or causes hydroxyl sites to be combined by high-temperature oxydation, is oligomeric
The case where changing and then curing.In addition, castor oil be also easy to it is oxidized deterioration and oligomerization, solidification.The hydrocarbonylation of present embodiment is closed
Object suitably can partly or entirely substitute such castor oil.Accordingly, rubber composition is not easy to ooze out, no in forming
It is volatile and be not easy oligomerization, therefore can further improve the durability of the capsule of acquisition.In addition, the hydrocarbon compound of present embodiment
Bubble present in pore for fillers such as carbon blacks etc. is also easy to make it by overflowing (defoaming is good) in rubber composition.It is logical
Crossing can play that these are volatile, are not easy oligomerization and effect that defoaming is good, and rubber composition can obtain excellent in te pins of durability
Curing bag.
Hydrocarbon compound, which can also contain, to be come from the structural unit of ethylene and comes from other than the structural unit of propylene
Other structures unit.As such other structures unit, ethylene, propylene, styrene can be illustrated.Wherein, based on carbon black
The good point of compatibility, hydrocarbon compound can contain the structural unit for coming from styrene.
Based on volatile viewpoint, the number-average molecular weight (Mn) preferably 1000 or more of the hydrocarbon compound of present embodiment, more
It is preferred that 1500 or more.In addition, for the viewpoint of plasticization effect, Mn preferably 30,000 is hereinafter, more preferable 20,000 or less.In addition, this implementation
In mode, Mn and aftermentioned Mw can be converted by standard polystyren and be obtained using gel permeation chromatography (GPC).
Based on the viewpoint excellent in compatibility with butyl system rubber, the SP of the hydrocarbon compound of present embodiment (join by solubility
Number Solubility Parameter) value is preferably 8.5 hereinafter, more preferable 8.4 or less.In addition, the hydrocarbon low as SP values, fluorine tree
The SP values of the teflon (registered trademark) of fat are 6.2, and the SP values of silicone rubber are 7.3.SP values are easy in 8.4 hydrocarbon compounds below
It is mixed in butyl system rubber, when forming is not easy to ooze out, is not volatile and excellent to the plasticization effect of rubber composition.Separately
Outside, in present embodiment, SP values can be calculated by Hoy methods.More specifically, in present embodiment, for example, hydrocarbon compound SP values
When about 8.2, such hydrocarbon compound and butyl system rubber (such as SP values:7.8,Tg:- 71 DEG C) and the used time, the difference of SP values is small,
It is easy to compatible.Butyl system rubber and the compatibility of hydrocarbon compound are excellent when the difference of SP values is less than 1.0, more excellent when below 0.5
It is different.
The hydrocarbon compound of present embodiment can also be defined as low temperature plasticizer, i.e. defoaming good for transport properties of molecules
Property excellent viewpoint, the glass transition temperature (Tg) of hydrocarbon compound is preferably -80~-50 DEG C.When Tg is less than -80 DEG C, hydrocarbonylation
The molecular weight for closing object becomes smaller, and is easy to volatilize.On the other hand, when Tg is more than -50 DEG C, the defoaming effect of hydrocarbon compound is small.In addition, this
In embodiment, Tg after removing extension oil using acetone, pure SBR points can be led to according to JISK 7121 according to JIS K 6229
Differential scanning calorimetry measurement (DSC) is crossed to acquire.
The viewpoint of fraction defective based on defoaming effect and when sulfidization molding, hydrocarbon compound is relative to 100 matter of rubber constituent
More than content preferably 2 mass parts for measuring part, more than preferably 3 mass parts.In addition, for the CrackGrowth phase with rubber composition
The viewpoint of the stretch modulus M300 of pass, hydrocarbon compound is below mass part relative to the content preferably 10 of 100 mass parts of rubber constituent,
More preferable 9 is below mass part.
The hydrocarbon compound of present embodiment can use commercially available product.Such commercially available product can illustrate Exxon Mobil Corporation,
Product are peddled in the manufactures such as Mitsui Chemicals (strain).
(any ingredient)
Then, in the rubber composition of present embodiment, any ingredient that can be properly mixed illustrates.This embodiment party
The rubber composition of formula can be also randomly mixed in the manufacture of curing bag rubber composition general other than mentioned component
The other compositions used.If lifting its an example, such any ingredient be Compatibilized resin, zinc oxide, anti-aging agent, processing aid,
The resin components such as inorganic filler agent, tackifying resin other than releasing agent, stearic acid, above-mentioned filler, plasticizer, heat resistance improvers,
Fire retardant, heat conduction imparting agent, crosslinking agent etc..
Compatibilized resin
The rubber composition of present embodiment is suitable for containing Compatibilized resin.Compatibilized resin is not particularly limited.Lift its an example
Words, Compatibilized resin is terpenic series resin, rosin series resin, ethylene butene styrene copolymer resins, hydriding terpene system resin, hydrogenation
Rosin series resin etc..Compatibilized resin can be used together.Wherein, for the viewpoint for the durability for improving the rubber composition obtained, originally
The rubber composition of embodiment is preferably comprised selected from hydriding terpene system resin, hydrogenated rosin system resin and ethylene, propylene benzene second
It is at least one kind of in the group that alkene copolymer resins are constituted.
Terpenic series resin is not particularly limited.If lifting its an example, terpenic series resin is by being selected from australene, nopinene, lemon
The polyterpene resin of at least one kind of composition of the terpenes raw material such as lemon alkene, cinene with terpene compound and aromatic compound is original
The aromatic modified terpene resin of material, using terpene compound and phenol based compound as terpenic series such as the terpene phenolic resins of raw material
Resin (terpenic series resin not hydrogenated) and these terpenic series resins carry out (hydriding terpene system resin) after hydrogenation treatment
Resin.The aromatic compound of raw material as aromatic modified terpene resin can illustrate styrene, α-methylstyrene, second
Alkenyl toluene, divinyl toluene etc..The phenol based compound of raw material as terpene phenolic resin, can illustrate phenol, bis-phenol
A, cresols, dimethlbenzene etc..
Wherein, for butyl system rubber it is excellent in compatibility, become by adding hydrogen due to the double bond in chemical constitution
Singly-bound obtains the viewpoint of the superior curing bag of durability, the preferred hydriding terpene system resin of terpenic series resin.In addition, terpenes
Be resin can it is nearly 100% hydrogenation, further for the viewpoint of excellent in te pins of durability, more preferable hydrogenated polyterpene resins.In addition, right
The hydrogenation treatment of terpenic series resin can be carried out by well known method.In addition, in present embodiment, terpenic series resin can make
With commercially available hydriding terpene system resin.
For preventing the Tg of rubber composition from getting higher, the vitrifying of the viewpoint that durability deteriorates, hydriding terpene system resin turns
Preferably 60 DEG C of temperature (Tg) is hereinafter, more preferable 50 DEG C or less.In addition, the lower limit of the Tg of hydriding terpene system resin is without special limit
It is fixed.For may insure difficult volatile viewpoint, preferably 5 DEG C or more of the Tg of hydriding terpene system resin.In addition, for tensile properties
Viewpoint that is excellent, being easy to elimination gap (void), the weight average molecular weight (Mw) preferably 700 or less of hydriding terpene system resin.
The SP values of hydriding terpene system resin are preferably close to the SP values 7.7~8.1 of butyl system rubber, and preferably 8.4 or less.Separately
Outside, SP values herein are the structures based on compound, the solubility parameter (Solubility calculated by Hoy methods
Parameter).Hoy methods are for example in K.L.Hoy " solubility parameter table (Table of Solubility
) ", Parameters Union Carbide Corporation's solvent and coating material research and development portion (Solvent and Coatings
Materials Research and Development Department, Union Carbites Corp) the middle notes of (1985)
The computational methods of load.
When containing hydriding terpene system resin, for well obtain present embodiment effect viewpoint, relative to rubber at
Point 100 mass parts, more than content preferably 1 mass parts of hydriding terpene system resin, more than more preferable 2 mass parts.In addition, for can
Suitably to ensure the hardness of rubber composition, the viewpoint of shaping processability, viscosity, content preferably 8 matter of hydriding terpene system resin
Part is measured hereinafter, more preferable 6 is below mass part.
In addition, in present embodiment, terpenic series resin can use commercially available product.Such commercially available product can illustrate the former chemistry of peace
Product are peddled in the manufacture of (strain) etc..
Rosin series resin
Rosin series resin is obtained by processing rosin using rosin acid as the resin of principal component.Rosin series resin can example
Show that the resin acids such as abietic acid, neoabietic acid, palmitic acid, levopimaric acid, pimaric acid, isodextropimaric acid, dehydroabietic acid are principal component
Except the natural rosin resins such as gum rosin, wood rosin, toll oil rosin (newtrex), hydrogenated rosin resin, unsaturated carboxylic acid
The modified rosin resins such as modified rosin resin, rosin modified phenolic resin, rosin glycerides, unsaturated carboxylic acid-modified rosin ester etc.
Rosin ester, the disproportionated rosin resin etc. that rosin resin is disproportionated and is obtained.
Rosin ester resin generates by being the esterification by above-mentioned rosin and polyalcohol (glycerine, pentaerythrite etc.)
Rosin series resin.Esterification is not particularly limited.If citing, esterification be under the environment of not active gases,
Rosin and polyalcohol are heated to 200~300 DEG C, the water of generation is made to be rejected to the method outside system.
The softening point of rosin series resin is not particularly limited.The softening point of rosin series resin can be with above-mentioned terpenic series resin
Softening point it is identical.
When containing rosin series resin, for the viewpoint for obtaining tensile properties well, relative to 100 mass of rubber constituent
Part, more than content preferably 1 mass parts of rosin series resin, more than more preferable 2 mass parts.In addition, for rubber can be suitably adjusted
The content preferably 8 of the hardness of glue composition, the viewpoint of shaping processability, viscosity, rosin series resin is below mass part, and more preferable 6
It is below mass part.
In present embodiment, rosin series resin can use commercially available product.Such commercially available product can illustrate the chemical conversion of Harry agates
Product are peddled in the manufacture in (strain), waste river chemical (strain) etc..
Ethylene butene styrene copolymer resins
Ethylene butene styrene copolymer resins are copolymerized obtained by styrene monomer polymerize with vinyl monomer and propylene monomer
Resin, it includes structural units shown in following general formula (in formula, m, n, o are 1 or more integer).Rubber composition is by containing
There are ethylene butene styrene copolymer resins, compared with containing above-mentioned terpenic series resin or when rosin series resin, same journey can be maintained
The durability of degree, and when making curing bag, the viscosity of rubber surface is difficult to rise, and is not susceptible to by the mistake with capsule die
It is bad caused by degree bonding.
[Change 3]
Structural unit in ethylene butene styrene copolymer resins, to come from ethylene and the structure list for coming from propylene
Member total amount (EP contents, relative to general construction unit number above-mentioned formula m and n's and) be not particularly limited.Lift its an example
If, for the gap for eliminating butyl system rubber and filler, the viewpoint of gas permeability is improved, relative to structural unit 100mol%,
Total amount preferred 60mol% or more, more preferable 70mol% or more.In addition, for the viewpoint of tensile properties, relative to structural unit
100mol%, the preferred 98mol% of total amount are hereinafter, more preferably 95mol% or less.Ethylene and propylene with butyl system rubber phase
Hold.In addition, styrene can be compatible with carbon black.Therefore, EP contents are breathed freely by that, can balance to improve well within the above range
Property and EB.
When containing ethylene butene styrene copolymer resins, based on the viewpoint for obtaining present embodiment effect well, relatively
More than 100 mass parts of rubber constituent, content preferably 1 mass parts of ethylene butene styrene copolymer resins, more preferable 2 mass parts
More than.In addition, for can suitably ensure the hardness of rubber composition, the viewpoint of shaping processability, viscosity, ethylene, propylene benzene
The content of ethylene copolymer preferably 8 is below mass part, and more preferable 6 is below mass part.
In present embodiment, ethylene butene styrene copolymer resins can use commercially available product.Such commercially available product can illustrate
Product are peddled in the manufacture of Struktol companies, Performance additive companies, Lanxess Corporation etc..
Anti-aging agent
Based on the purpose of the thermal oxide deterioration improved under hot environment, the blended antioxidant in the mixed system rich in butyl
When, in view of volatility, exudative, fusing point (dispersibility), the preferred bis-phenol system of anti-aging agent, particularly alkyl chain are connected on phenol
Compound.In present embodiment, anti-aging agent can use commercially available product.Such commercially available product can illustrate imperial palace emerging chemical (strain) etc.
Manufacture peddle product.
When rubber composition contains anti-aging agent, the content of anti-aging agent is not particularly limited.If lifting its an example, relative to rubber
100 mass parts of ingredient, more than content preferably 0.5 mass parts of anti-aging agent, more than more preferable 0.8 mass parts.In addition, relative to rubber
The content preferably 3 of 100 mass parts of glue ingredient, anti-aging agent is below mass part, and more preferable 2 is below mass part.By making anti-aging agent
Within the above range, the oxidative degradation patience of filler is improved content, is easy to show good draftability.In addition, obtaining
Rubber composition be also easy to be kneaded.
Crosslinking agent
Crosslinking agent is not particularly limited.If lifting its an example, crosslinking agent can enumerate crosslinked resin etc..For curingprocess rate, hand over
Join density, crosslinking uniformity and then the point for obtaining the good capsule service life, the preferred crosslinked resin of crosslinking agent.Crosslinked resin can example
Show alkylphenol formaldehyde resin etc..Alkylphenol formaldehyde resin is not particularly limited.If lifting its an example, for excellent heat resistance
Point, alkylphenol formaldehyde resin is not preferably by the non-halide of halogenation.The content of methylol in alkylphenol formaldehyde resin
Usually 7~10 mass %.
The content of the crosslinking agent of 100 mass parts of rubber constituent when relative to containing crosslinking agent is not particularly limited.Crosslinking agent
Content can be suitably adjusted by the reactivity of butyl rubber, the curing temperature of capsule.If lifting its an example, crosslinking
More than the content of agent preferably 2 mass parts, more than more preferable 2.5 mass parts.In addition, the content of crosslinking agent preferably 15 mass parts with
Under, more preferable 12 is below mass part.By containing crosslinking agent within the above range, the rubber composition of acquisition can be full cross-linked,
And obtain curing bag the capsule service life and capsule performance it is excellent.
Releasing agent
Releasing agent can illustrate the releasing agent containing fatty acid metal salts, fatty acid amide, carboxylic acid amide esters etc..Fatty acid metal salts
In metal can illustrate calcium, zinc, aluminium, sodium etc..Wherein, for cheap, the reason of not becoming environmental pollution, further not shadow
Ring the viewpoint of curingprocess rate, releasing agent preferred fat acid calcium salt.
When containing releasing agent, the content of releasing agent is not particularly limited.If lifting its an example, relative to 100 matter of rubber constituent
Part is measured, more than content preferably 0.5 mass parts of releasing agent, more than more preferable 0.6 mass parts.In addition, relative to rubber constituent 100
The content preferably 10 of mass parts, releasing agent is below mass part, and more preferable 7 is below mass part.By containing demoulding in above range
Agent can assign rubber composition good release property.
In present embodiment, releasing agent can use commercially available product.Such commercially available product can illustrate Struktol companies, Rhein
Product are peddled in the manufacture of chemical company, Performance additive companies etc..
< rubber compositions and curing bag >
The curing bag of present embodiment can be manufactured with rubber composition by general method.If lifting its an example,
It, can be by using making in the ordinary rubbers industry such as Banbury mixer or kneader, opening rubber mixing machine to rubber composition
Known kneading machine, after the ingredient other than the crosslinking agent and vulcanization accelerator in each ingredient is kneaded, then thereto
Addition crosslinking agent and vulcanization accelerator are further kneaded, and method vulcanized later etc. is manufactured and obtained.
The pyroconductivity of the rubber composition of present embodiment is that the heat excellent as curing bag rubber composition passes
Conductance, based on the viewpoint of vulcanization production efficiency, preferably 0.40W/mK or more, more preferable 0.45W/mK or more.In addition, pyroconductivity
The upper limit be not particularly limited.Based on ensure obtain curing bag durability viewpoint, pyroconductivity be maintained at 1.0W/mK with
Under.In addition, in present embodiment, the pyroconductivity of the vulcanized rubber composition when pyroconductivity of rubber composition is 23 DEG C,
It can be according to Hot Wire Technique for Measuring as defined in JIS R 2616.
The curing bag of present embodiment can be made of above-mentioned rubber composition.Curing bag can be by general
Method manufactures.It, can be by the way that uncrosslinked curing bag be squeezed into rubber composition by extruder if lifting its an example
Shape is cylindric or square shape, is set to moulding press, is manufactured by heating heating molding.
[Embodiment]
Ground specific description is carried out to the present invention based on embodiment.The present invention is not limited to these Examples.
The various reagents product used in embodiment and comparative example show as follows.
(rubber constituent)
Butyl system rubber 1:Exxson268 (conventional butyl rubbers, SP values:7.8, Exxon Mobil Corporation's system)
Butyl system rubber 2:Exxpro3035 (butyl rubber, SP values comprising p-methylstyrene unit:7.8, Exxon
Mobil Corporation system)
Neoprene:ス カ イ プ レ Application B30 (neoprene, TOSOH Co., Ltd's system)
(filler)
Carbon black 1:シ ョ ー Block ラ ッ Network N330T (usual carbon, N2SA:79m2/ g, Cabot Japanese (strain) system)
Carbon black 2:シ ョ ー Block ラ ッ Network N220 (usual carbon, N2SA:115m2/ g, Cabot Japanese (strain) system)
Graphite:KS6 (artificial graphite, BET specific surface area 20m2/ g, Imerys corporations)
Acetylene black:Denka black granular (conductive carbon, primary particle size 35nm, specific surface area 68m2/ g, electrochemically industry
(strain))
(hydrocarbon compound)
Hydrocarbon compound 1:LX004 (ethylene propylene copolymer, Mn:1780,Tg:- 77 DEG C, SP values:8.23, come from ethylene
Structural unit and come from propylene structural unit total amount:85mol% or more, Mitsui Chemicals (strain) system)
Hydrocarbon compound 2:LX010 (ethylene propylene copolymer, Mn:2550,Tg:- 71 DEG C, SP values:8.23, come from ethylene
Structural unit and come from propylene structural unit total amount:85mol% or more, Mitsui Chemicals (strain) system)
Hydrocarbon compound 3:LX400 (ethylene propylene copolymer, Mn:6690,Tg:- 64 DEG C, SP values:8.26, come from ethylene
Structural unit and come from propylene structural unit total amount:85mol% or more, Mitsui Chemicals (strain) system)
Hydrocarbon compound 4:LX900Z (ethylene propylene copolymer, Mn:7420,Tg:- 62 DEG C, SP values:8.37, come from ethylene
Structural unit and come from propylene structural unit total amount:85mol% or more, Mitsui Chemicals (strain) system)
(Compatibilized resin)
Ethylene butene styrene copolymer resins 1:40MS (softening points:78 DEG C, EP contents:82 mass %, Mn:600,Tg:58
DEG C, SP values:8.9, Struktol corporations)
Ethylene butene styrene copolymer resins 2:Promix400 (softening points:78 DEG C, EP contents:92 mass %, Mn:
1000,Tg:57 DEG C, SP values:8.7, performance additive corporations)
Terpenic series resin 1:P85 (hydrogenated polyterpene resins, softening point:85℃,Mn:630,Tg:43 DEG C, SP values:8.36,
Former chemical (strain) system of peace)
Terpenic series resin 2:TO85 (hydriding terpene styrene resin, softening point:85℃,Mn:650,Tg:43 DEG C, SP values:
8.73, former chemical (strain) system of peace)
Rosin series resin:Ha リ ス タ ー TF (rosin ester resin, softening point:80℃,Tg:38 DEG C, Harry agates chemical conversion (strain)
System)
(other)
Zinc oxide:No. 2, proportion 5.6
Stearic acid:Stearic acid Chinese toon (SP values:9.1, day oily (strain) system)
Oil:Work 1 (castor oil, Mn:1490,Tg:- 55 DEG C, SP values:9.89, she makes rattan liquefaction (strain))
Retarder:ノ ッ Network セ ラ ー DM (emerging chemical (strain) system of MBTS, imperial palace)
Crosslinked resin:タ ッ キ ロ ー Le TK201 (alkyl phenol resin, field ridge chemical (strain) system)
Anti-aging agent:ノ ッ Network ラ ッ Network NS-6 (emerging chemical (strain) system of methylene bis-phenol, imperial palace)
Releasing agent:WB16 (mixture of unsaturated fatty acid amide and calcium soap, Mn:355, solid, SP values:10.0,
Struktol corporations)
(embodiment and comparative example)
According to mixing formula shown in 1~table of table 3, using 2.0L Banbury mixers with 4 minutes, discharge temperature 150
DEG C the drug other than crosslinked resin in mixing material is kneaded, obtains mixture.Then, it is added into the mixture of acquisition
Crosslinked resin is kneaded using 2.0L Banbury mixers with 3 minutes, 95 DEG C of discharge temperature, and unvulcanized rubber composition is obtained
Object.By the sheet rubber that the unvulcanized rubber composition rolling of acquisition is thickness 2mm, using experiment mold, described in table 1~2
Examples 1 to 10 and the rubber composition of comparative example 1~6 30 minutes press cures are carried out at 190 DEG C, to 3 institute of table
The rubber composition of the embodiment 11~16 and comparative example 7~10 stated carries out 12 minutes press cures at 180 DEG C, respectively
Obtain vulcanized rubber composition.Following evaluation is carried out by mixture and vulcanized rubber composition.
< pyroconductivities >
According to heat-pole method as defined in JIS R 2616, by quick conductive instrument, (capital of a country electronics industry (strain) produces
KemthermQTM-500 the pyroconductivity (W/mK) in 23 DEG C of each vulcanized rubber composition) is measured.It the results are shown in Table 1~table 3.
Pyroconductivity is higher, and expression heat-conductive characteristic is more excellent.The performance arget value of pyroconductivity in the present invention be 0.40W/mK with
On.
The light fraction defective > of <
For light fraction defective, by the visual inspection visually inspect of vulcanized rubber composition, with bubble-free, starved, uneven thickness,
The object of extreme dent is non-defective unit, carries out index assessment based on the following metewand.Light fraction defective be in 100 or more index be suitable
In commodity production.
Index 140:Light fraction defective 0.1%
Index 120:Light fraction defective 0.5%
Index 100:Light fraction defective 1%
Index 80:Light fraction defective 2%
Index 60:Light fraction defective 4%
Index 40:Light fraction defective 10%
< durabilities (new product EB) >
The rubber experiment piece that determined size is taken out from the middle layer of vulcanized rubber composition the, based on " vulcanizations of JIS K 6251
Rubber and thermoplastic elastomer-tensile properties acquire method " No. 3 dumbbell shape test films are made, under 150 DEG C of environments
Implement tension test, measures elongation at break EB (elongation at break) (%) (new product EB).The numerical value of new product EB is got over
Greatly, indicate that elongation at break is more excellent.In addition, for the point of durability, the performance arget value of the new product EB in the present invention is
500% or more.In addition, when the numerical value of new product EB is below 300%, when there is demoulding and stretching rubber, with blistering portion or with polymerize
The case where position of the poor adhesion of object is starting point cracked (major defect).
< durabilities (new product M300) >
Based on JIS K 6251:2010, each vulcanized rubber composition is made as No. 1 shape test film of dumbbell shaped, uses examination
It tests piece and implements tension test under 150 DEG C of environmental gas, stress (MPa) (new product M300) when measuring 300% stretching.New product M300
Value it is bigger, then CrackGrowth is excellent, excellent in te pins of durability.In addition, for the point of durability, new product M300's in the present invention
Performance arget value is 2.5 or more.
< durabilities (deterioration EB) >
The rubber slab for making the thick 2mm of vulcanized rubber composition, 24 are placed by the rubber slab of acquisition in 180 DEG C of baking oven
Hour, the test film after being deteriorated using the air oxidation is based on JIS K 6251 " vulcanized rubber and thermoplastic elastomer-stretching
Characteristic acquires method ", implement tension test at 150 DEG C, measures elongation at break EB (%) (deterioration EB).Deteriorate the number of EB
Value is bigger, indicates that elongation at break is more excellent.In addition, for the point of durability, the performance arget value of the deterioration EB in the present invention
It is 350% or more.
[Table 1]
[Table 2]
Table 2
[Table 3]
As shown in Table 1 to Table 3, curing bag of the invention shows excellent light fraction defective and resistance to rubber composition
Long property.In addition, as shown in table 3, curing bag rubber composition of the invention is by and with butyl system rubber 2 and quantitative
The graphite of height filling filler, can maintain with the Examples 1 to 10 using butyl rubber 1 described in table 1 with degree higher
Endurance quality and light fraction defective, and heat conductivity is largely increased.
Claims (6)
1. a kind of curing bag rubber composition, containing rubber constituent, filler and hydrocarbon compound,
In 100 mass parts of the rubber constituent, including butyl system rubbers more than 81 mass parts,
The filler includes carbon black, and relative to 100 mass parts of the rubber constituent, containing filling out described in more than 45 mass parts
Material,
The hydrocarbon compound includes to add up to coming from the structural unit of ethylene and coming from the knot of propylene for 85mol% or more
Structure unit.
2. curing bag rubber composition according to claim 1, wherein the solubility parameter SP of the hydrocarbon compound
Value is below 8.5.
3. curing bag rubber composition according to claim 1 or 2, wherein the vitrifying of the hydrocarbon compound
Transition temperature is -80~-50 DEG C.
4. according to the curing bag rubber composition described in arbitrary 1 of claims 1 to 3, in the rubber of 100 mass parts
In glue ingredient, the butyl system rubber contains the butyl rubber of 40 mass parts or more, and the butyl rubber contains to methylbenzene second
Alkene unit is as repetitive unit.
5. according to the curing bag rubber composition described in arbitrary 1 of Claims 1 to 4, further also contains and be selected from
It is at least one kind of in the group that terpenic series resin, rosin series resin and ethylene butene styrene copolymer resins are formed.
6. a kind of curing bag is made of the curing bag described in arbitrary 1 of Claims 1 to 5 with rubber composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017074485A JP2018177853A (en) | 2017-04-04 | 2017-04-04 | Rubber composition for vulcanized bladder and vulcanized bladder |
| JP2017-074485 | 2017-04-04 |
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| Publication Number | Publication Date |
|---|---|
| CN108690273A true CN108690273A (en) | 2018-10-23 |
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|---|---|---|---|
| CN201810230918.3A Pending CN108690273A (en) | 2017-04-04 | 2018-03-20 | Curing bag rubber composition and curing bag |
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| CN (1) | CN108690273A (en) |
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| CN110218460A (en) * | 2019-05-30 | 2019-09-10 | 刘光植 | A kind of preparation method of tire curing bladder |
| CN114073102A (en) * | 2019-07-08 | 2022-02-18 | 雅马哈株式会社 | Composition for acoustic member and acoustic member |
| US20230043282A1 (en) * | 2019-12-19 | 2023-02-09 | Bridgestone Corporation | Rubber composition and tire |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07164810A (en) * | 1993-12-16 | 1995-06-27 | Sumitomo Rubber Ind Ltd | Rubber composition for inner tube |
| CN102453284A (en) * | 2010-10-27 | 2012-05-16 | 住友橡胶工业株式会社 | Rubber composition for air bag and air bag |
| JP2013067676A (en) * | 2011-09-20 | 2013-04-18 | Sumitomo Rubber Ind Ltd | Heavy-duty pneumatic tire |
| CN104693623A (en) * | 2013-12-10 | 2015-06-10 | 青岛三汇橡胶机械制造有限公司 | Vulcanized inner tube rubber |
| CN105001530A (en) * | 2015-07-09 | 2015-10-28 | 安徽省华洋橡胶有限公司 | Mixing butyl rubber for anti-aging truck inner tube |
-
2017
- 2017-04-04 JP JP2017074485A patent/JP2018177853A/en active Pending
-
2018
- 2018-03-20 CN CN201810230918.3A patent/CN108690273A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07164810A (en) * | 1993-12-16 | 1995-06-27 | Sumitomo Rubber Ind Ltd | Rubber composition for inner tube |
| CN102453284A (en) * | 2010-10-27 | 2012-05-16 | 住友橡胶工业株式会社 | Rubber composition for air bag and air bag |
| JP2013067676A (en) * | 2011-09-20 | 2013-04-18 | Sumitomo Rubber Ind Ltd | Heavy-duty pneumatic tire |
| CN104693623A (en) * | 2013-12-10 | 2015-06-10 | 青岛三汇橡胶机械制造有限公司 | Vulcanized inner tube rubber |
| CN105001530A (en) * | 2015-07-09 | 2015-10-28 | 安徽省华洋橡胶有限公司 | Mixing butyl rubber for anti-aging truck inner tube |
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