CN108350233A - Vibration damping rubber composition and Shockproof rubber - Google Patents
Vibration damping rubber composition and Shockproof rubber Download PDFInfo
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- CN108350233A CN108350233A CN201680063007.5A CN201680063007A CN108350233A CN 108350233 A CN108350233 A CN 108350233A CN 201680063007 A CN201680063007 A CN 201680063007A CN 108350233 A CN108350233 A CN 108350233A
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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
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F1/00—Springs
- F16F1/36—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F15/00—Suppression of vibrations in systems; Means or arrangements for avoiding or reducing out-of-balance forces, e.g. due to motion
- F16F15/02—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems
- F16F15/04—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems using elastic means
- F16F15/08—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems using elastic means with rubber springs ; with springs made of rubber and metal
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
Abstract
The present invention provides the vibration damping rubber composition for the friction coefficient that can reduce Shockproof rubber surface and has used its Shockproof rubber.Vibration damping rubber composition, which is characterized in that contain：(I) rubber constituent：100 mass parts；(II) acid-organosilicon crylic acid graft copolymer resin is the polymer of the mixture comprising 50~99 mass parts of polysiloxane indicated by the following general formula (1) and acrylate monomer or 50~1 mass parts of methacrylate monomers：1~30 mass parts.(R1For 1 valency alkyl, R2For the alkyl or vinyl of the substitution of sulfydryl, acryloxy or methacryloxy.X is that either hydroxyl Y is X or [O Si (X) for 1 valency alkyl, alkoxy2]d2 or more in X, X and Y are hydroxyl.Z is alkyl, alkoxy or hydroxyl.It is 100~10,000, c be 1~10, d is 1~1,000 that a, which is 0~1,000, b,.)
Description
Technical field
The present invention relates to provide the abnormal sound that can inhibit to be generated in the rubber vibration isolators used in the vehicles such as automobile
Shockproof rubber vibration damping rubber composition and used its Shockproof rubber.In more detail, it is related to the stabilization suitable for automobile
The vibration damping rubber composition and Shockproof rubber of the purposes such as bushing, rear suspension bushing.
Background technology
The shockproof rubber used for automobile Shockproof rubber embedded metal parts such as stabilizer bar bushing, rear suspension bushing
For glue, when setting out, when bringing to a halt and left and right turning when etc. installation metal parts and rubber bushing surface contact portion
Abnormal sound is generated, its countermeasure is needed.
As its countermeasure, the various researchs for the friction coefficient for reducing rubber surface have been carried out.Such as it proposes in rubber
The method of contact surface stickup low teflon (registered trademark) sheet material of friction coefficient, adds the method that wax is added in rubber constituent
Add the method (patent document 1 and 2 of liquid silicone oil：International Publication No. 2011/021641, Japanese Unexamined Patent Publication 10-245451 public affairs
Report).
But the method for stickup teflon sheet material is in terms of material, cost raising in terms of process, the method for adding wax
For, the reduction degree of friction coefficient is insufficient.Although in addition, addition silicone oil method in the reduction of friction coefficient have it is excellent
Different effect, but there is following problem：With the poor compatibility of rubber constituent, mixed refining process significance difference, batch productionization difficulty.
In addition, Patent Document 2 discloses acrylic acid series silicone oil, but lasted caused by being happened at the exudation on coating surface
Variation, fails use for a long time.
Existing technical literature
Patent document
Patent document 1：International Publication No. 2011/021641
Patent document 2：Japanese Unexamined Patent Publication 10-245451 bulletins
Invention content
The subject that the invention solves
The present invention is completed in view of above-mentioned actual conditions, and it is an object of the present invention to provide giving the friction coefficient that can reduce surface
The vibration damping rubber composition of Shockproof rubber and the Shockproof rubber for having used it.
Means for solving the problems
The present inventor's sharp study to achieve the goals above, as a result knows, specific acid-organosilicon crylic acid system grafting is altogether
Poly resin and the compatibility of rubber are good, will not excessively be oozed out in rubber surface, have the self-lubricating agent ingredient as appropriateness
Function, it is found that by making the vibration damping rubber composition containing the acid-organosilicon crylic acid graft copolymer resin in rubber constituent
In the case that the Shockproof rubber that solidfied material is constituted is used in the serious positions of wear intensities such as stabilizer bar bushing, the effect of friction mitigation is maintained
Fruit completes the present invention.
Therefore, the present invention provides vibration damping rubber composition and Shockproof rubber below.
[1] vibration damping rubber composition, which is characterized in that contain：
(I) rubber constituent：100 mass parts,
(II) acid-organosilicon crylic acid graft copolymer resin, to include the poly organo indicated by the following general formula (1)
The polymer of 50~99 mass parts of alkane and acrylate monomer or the mixture of 50~1 mass parts of methacrylate monomers：1~
30 mass parts.
[changing 1]
(in formula, R1For 1 valency alkyl of identical or different unsubstituted or substituted carbon number 1~20, R2For sulfydryl, acryloyl
The alkyl or vinyl of oxygroup or the carbon number 1~6 of methacryloxy substitution.X is identical or different unsubstituted or takes
Either hydroxyl Y is X or-[O-Si (X) for 1 valency alkyl of the carbon number 1~20 in generation, the alkoxy of carbon number 1~202]dShown in-X
Identical or different group, at least two in X and Y are hydroxyl.Z be the alkyl of carbon number 1~4, carbon number 1~4 alkoxy or
Hydroxyl.The positive number that a is 0~1,000, the positive number that b is 100~10,000, the positive number that c is 1~10, d are 1~1,000 just
Number.)
[2] vibration damping rubber composition described in [1], wherein (II) acid-organosilicon crylic acid graft copolymer resin is on (i)
State 100 mass parts of polysiloxane shown in general formula (1) and (ii) acrylate monomer or methacrylate monomers 1~
The emulsion grafting polymerization object of the mixture of 100 mass parts.
[3] vibration damping rubber composition described in [2], wherein 100 mass parts of (i) ingredient and 10~100 mass of (ii) ingredient
The emulsion grafting polymerization object of the mixture of part.
[4] vibration damping rubber composition described in [1], wherein (II) acid-organosilicon crylic acid graft copolymer resin is on (i)
State 100 mass parts of polysiloxane, (ii) acrylate monomer or methacrylate monomers 1 shown in general formula (1)~
The mixture for 0.01~20 mass parts of monomer containing functional group that 100 mass parts and (iii) can be copolymerized with it, and be (i)
Total mass ratio of ingredient and (ii), (iii) ingredient are 50：50~99：The emulsion grafting polymerization of the mixture of 1 ratio
Object.
[5] vibration damping rubber composition described in [4], wherein 100 mass parts of (i) ingredient and 10~100 mass of (ii) ingredient
The mixture of part and 0.01~20 mass parts of (iii) ingredient.
[6] vibration damping rubber composition described in [4] or [5], wherein (iii) ingredient is selected from methacrylic acid, propylene
Acid, acrylamide, allyl methacrylate, vinyl methacrylate, 2-hydroxyethyl methacrylate and metering system
Sour 2- hydroxy propyl esters.
[7] any one of them vibration damping rubber composition of [2]~[6], wherein (ii) ingredient is with carbon number 1~10
Alkyl acrylate or methacrylate.
[8] any one of them vibration damping rubber composition of [1]~[7], wherein the poly organo indicated by formula (1)
Alkane is cyclic organic siloxane, α, alpha, omega-dihydroxy siloxane oligomer, α, ω-dialkoxysiloxanes oligomer or alcoxyl
The polymer of base silane and the silane coupling agent indicated by the following general formula (2).
R3 (4-e-f)R4 fSi(OR5)e (2)
(in formula, R3For the alkyl or second of the carbon number 1~6 of sulfydryl, acryloxy or methacryloxy substitution
Alkenyl, R4For the alkyl of carbon number 1~4, R5For the alkyl of carbon number 1~4, e be 2 either 3 f be 0 either 1 e+f be 2 or 3.)
[9] Shockproof rubber, it includes the cross-linking agents of any one of them vibration damping rubber composition of [1]~[8].
[10] Shockproof rubber described in [9], is used for vehicle part.
The effect of invention
The vibration damping rubber composition of the present invention is grafted altogether by being compounded specific acid-organosilicon crylic acid system in rubber constituent
Poly resin, to long in the case where the Shockproof rubber that will be made of the solidfied material of the composition is used in the positions such as stabilizer bar bushing
Time maintains friction to mitigate effect.
Specific implementation mode
The vibration damping rubber composition of the present invention contains (I) rubber constituent and (II) acid-organosilicon crylic acid system graft copolymerization tree
Fat.
It is described in detail below for each ingredient.
In the present invention, as (I) rubber constituent, it can illustrate including butadiene rubber (BR), styrene butadiene ribber
(SBR), diene series rubbers, the ethylene, propylene rubber such as nitrile rubber (NBR), isoprene rubber (IR), chloroprene rubber (CR)
The halogenated butyl rubbers such as the olefin-baseds rubber such as glue (EPR, EPDM), butyl rubber (IIR), brombutyl (Br-IIR), with
And the synthetic rubber class of polyurethane rubber, acrylic rubber, fluorubber, silicon rubber, chlorosulfonated polyethylene etc., natural rubber
Deng these can be used alone a kind or be used in mixed way two or more.
(II) acid-organosilicon crylic acid graft copolymer resin is the polysiloxane indicated by formula (1) and acrylate list
The polymer of body or methacrylate monomers, preferably make the polysiloxane that (i) is indicated by the following general formula (1) with
(ii) mixture of (methyl) acrylate monomer or these (i), (ii) contain functional group with what (iii) can be copolymerized with it
Monomer mixture carry out emulsion grafting polymerization obtained from product.
Wherein, (i) polysiloxane is indicated by the following general formula (1).
[changing 2]
(in formula, R1For 1 valency alkyl of identical or different unsubstituted or substituted carbon number 1~20, R2For sulfydryl, acryloyl
The alkyl or vinyl of oxygroup or the carbon number 1~6 of methacryloxy substitution.X is identical or different unsubstituted or takes
Either hydroxyl Y is X or by-[O-Si (X) for 1 valency alkyl of the carbon number 1~20 in generation, the alkoxy of carbon number 1~202]d- X is indicated
Identical or different group, at least two in X and Y is hydroxyl.Z be the alkyl of carbon number 1~4, carbon number 1~4 alkoxy or
Person's hydroxyl.The positive number that a is 0~1,000, the positive number that b is 100~10,000, the positive number that c is 1~10, d are 1~1,000 just
Number.)
Wherein, R1It can specifically be enumerated for 1 valency alkyl of identical or different unsubstituted or substituted carbon number 1~20
Methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, myristyl, cetyl,
The alkenyls such as the naphthenic base such as the alkyl such as octadecyl, cyclopenta, cyclohexyl, suberyl, vinyl, allyl, phenyl, tolyl,
The aralkyl such as the alkenyl aryls such as the aryl such as naphthalene, ethenylphenyl, benzyl, phenylethyl, phenyl propyl, vinyl benzyl, second
Alkenyls aralkyl such as alkenyl phenyl propyl etc., these groups hydrogen atom it is some or all by the halogens such as fluorine, bromine, chlorine original
Son, acryloxy, methacryloxy, carboxyl, alkoxy, alkenyloxy group, amino, alkyl or alkoxy or (methyl) third
Group made of the substitutions such as alkene acyloxy substituted-amino.As R1, preferably methyl.
R2For the alkyl or vinyl of the carbon number 1~6 of sulfydryl, acryloxy or methacryloxy substitution.Tool
Body, preferably mercaptopropyi, acryloxypropyl, methacryloxypropyl, vinyl etc..
X be 1 valency alkyl of identical or different unsubstituted or substituted carbon number 1~20, carbon number 1~20 alkoxy or
Hydroxyl may be exemplified and as 1 valency alkyl of unsubstituted or substituted carbon number 1~20 by R1The same group of group of illustration,
As the alkoxy of carbon number 1~20, specifically, methoxyl group, ethyoxyl, propoxyl group, butoxy, hexyloxy, oxygen in heptan can be enumerated
Base, octyloxy, decyloxy, tetradecyloxyaniline etc..As X, preferably hydroxyl, methyl, butyl, phenyl.
Y is X or by-[O-Si (X)2]dThe identical or different group that-X is indicated.
The positive number that d is 1~1,000, preferably 1~200.
In addition, in the present invention, from bridging property aspect, at least two, excellent in above-mentioned X and Y in 1 molecule
2~4 hydroxyls are selected, preferably there are them in two ends.
Z is alkoxy either the hydroxyl preferably hydroxyl or methyl of the alkyl of carbon number 1~4, carbon number 1~4.
If a becomes bigger than 1,000, then the intensity of the solidfied material obtained becomes inadequate, therefore is set as 0~1,000
Positive number, preferably 0~200 positive number, if b less than 100, lacks the flexibility of solidfied material, if than 10,000 is big, then
The tearing strength of the solidfied material arrived reduces, therefore is set as 100~10,000 positive number, preferably 1,000~5,000 positive number.c
For 1~10 positive number, if it exceeds 10, then easy to produce gelled particles in reacting.
Further more, the arrangement of above-mentioned repetitive unit can be block, can also be random.
Such (i) polysiloxane uses preferably in the form of lotion, and commercially available product can be used, can also synthesize.It carries out
In the case of synthesis, well known emulsion polymerization can be used to implement, such as making by using surfactant can be former with fluorine
The cyclic organic siloxane of the halogen atoms such as son, (methyl) acryloxy, carboxyl, alkoxy, alkenyloxy group, hydroxyl, amino etc.,
α, alpha, omega-dihydroxy siloxane oligomer, α, ω-dialkoxysiloxanes oligomer, alkoxy silane etc. with by the following general formula (2)
The silane coupling agent of expression after emulsion dispersion, is added as needed on the catalyst such as acid in water, carries out polymerisation, so as to
It is easily synthesized.
R3 (4-e-f)R4 fSi(OR5)e (2)
(in formula, R3For the alkyl or second of the carbon number 1~6 of sulfydryl, acryloxy or methacryloxy substitution
Alkenyl, R4For the alkyl of carbon number 1~4, R5For the alkyl of carbon number 1~4, e be 2 either 3 f be 0 either 1 e+f be 2 or 3.)
As above-mentioned cyclic organic siloxane, specifically, hexamethyl cyclotrisiloxane (D3), four silicon of prestox ring can be illustrated
Oxygen alkane (D4), decamethylcyclopentaandoxane (D5), ten diformazan basic rings, six siloxanes (D6), four silica of 1,1- diethyl pregnancy basic ring
Alkane, phenyl heptamethylcyclotetrasiloxane, 1,1- diphenyl hexamethyls cyclotetrasiloxane, 1,3,5,7- tetravinyl tetramethyl cyclotetrasiloxanes
Siloxanes, 1,3,5,7- tetramethyl-ring tetrasiloxanes, tetra- cyclohexyl tetramethyl-ring tetrasiloxanes of 1,3,5,7-, three (3,3,3- tri-
Fluoropropyl) trimethyl cyclotrisiloxane, 1,3,5,7- tetra- (3- methacryloxypropyls) tetramethyl-ring tetrasiloxane, 1,3,
5,7- tetra- (3- acryloxypropyls) tetramethyl-ring tetrasiloxane, 1,3,5,7- tetra- (3- carboxypropyls) tetramethyl cyclotetrasiloxane silica
Alkane, 1,3,5,7- tetra- (3- vinyloxy propyls) tetramethyl-ring tetrasiloxane, 1,3,5,7- tetra- (p- ethenylphenyl) tetramethyl
Cyclotetrasiloxane, 1,3,5,7- tetra- [3- (p- ethenylphenyl) propyl] tetramethyl-ring tetrasiloxane, (N- third of 1,3,5,7- tetra-
Enoyl--N- methyl -3- aminopropyls) tetramethyl-ring tetrasiloxane, (bis- (the lauroyl) -3- amino of N, N- of 1,3,5,7- tetra-
Propyl) tetramethyl-ring tetrasiloxane etc..It is preferable to use octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxanes.
As silane coupling agent, specifically, can enumerate vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyl tripropoxy silane, vinyl silane triisopropoxide, vinyl methyl dimethoxysilane, vinyl methyl diethyl
The vinyl silanes class such as oxysilane；γ-(methyl) acryloyloxypropyltrimethoxysilane, γ-(methyl) acryloyl-oxy
Base propyl-triethoxysilicane, γ-(methyl) acryloxypropyl tripropoxy silane, γ-(methyl) acryloxy third
Three isopropoxy silane of base, three butoxy silane of γ-(methyl) acryloxypropyl, γ-(methyl) acryloxypropyl
Methyl dimethoxysilane, γ-(methyl) acryloxypropyls diethoxy silane, γ-(methyl) acryloxy
Hydroxypropyl methyl dipropoxy silane, γ-(methyl) acryloxypropyl diisopropoxy silane, γ-(methyl) propylene
The acryl silanes classes such as methyl dibutoxy silane；γ-mercapto propyl methyl dimethoxy silane, γ-mercapto
Hydrosulphonyl silanes class such as base propyl trimethoxy silicane etc..Or oligomer made of their polycondensations can inhibit to the generation of alcohol, have
When it is more preferable.Wherein, (methyl) acryloyl-oxy basis representation acryloxy or methacryloxy.
For these silane coupling agents, relative to cyclic organic siloxane, α, alpha, omega-dihydroxy siloxane oligomer, α,
ω-dialkoxysiloxanes oligomer or 100 mass parts of alkoxy silane are, it is preferable to use 0.01~20 mass parts, more preferably
Use 0.01~5 mass parts.
By the way that silane coupling agent to be copolymerized, to the poly organo as the siloxane unit with the c in formula (1)
Alkane, the effect for being made the monomer of (ii) or (iii) ingredient be grafted.
In above-mentioned reaction, as catalyst for polymerization, well known polymerization catalyst can be used.Wherein preferred strong acid,
Hydrochloric acid, sulfuric acid, dodecyl benzene sulfonic acid, citric acid, lactic acid, ascorbic acid can be illustrated.Preferably have the 12 of emulsifying capacity
Alkyl benzene sulphonate.
As the usage amount of acid catalyst, relative to cyclic organic siloxane, α, alpha, omega-dihydroxy siloxane oligomer, α,
100 mass parts of ω-dialkoxysiloxanes oligomer or alkoxy silane, preferably 0.01~10 mass parts, more preferably
0.2~2 mass parts.
In addition, as the surfactant used in polymerization, as anionic surfactant, dodecane can be enumerated
Base sodium sulphate, laureth sodium sulphate, N- acyl aminos hydrochlorate, N- acyl taurine salts, aliphatic soap, alkylphosphonic
Deng wherein it is preferred that being easy dissolving, the anionic surfactant without polyoxyethylene chain in water.More preferably N- acyl groups
Amino-acid salt, N- acyl taurine salts, aliphatic soap and alkylphosphonic, particularly preferably lauroyl N-methyltaurine sodium,
Myristoyl N-methyltaurine sodium, lauryl sodium sulfate.
Relative to cyclic organic siloxane, α, alpha, omega-dihydroxy siloxane oligomer, α, ω-dialkoxysiloxanes are oligomeric
The usage amount of 100 mass parts of object or alkoxy silane, anionic surfactant is preferably 0.1~20 mass parts, more excellent
It is selected as 0.5~10 mass parts.
Preferably 50~75 DEG C of polymerization temperature, polymerization time preferably 10 hours or more, more preferable 15 hours or more.In turn, special
Its curing 10 hours or more is not preferably made at 5~30 DEG C after polymerisation.In addition, the pH of obtained polymeric solution be preferably 6~
8。
In above-mentioned reaction, for example, to use octamethylcyclotetrasiloxane as cyclic organic siloxane, use γ-methyl
For acryloxypropyl dimethoxysilane is as the situation of silane coupling agent, then as described below.
[changing 3]
In the present invention, (ii) acrylate monomer or methacrylate monomers (hereinafter sometimes referred to acrylic acid series at
Divide either (methyl) acrylate monomer) it is acrylate monomer or first without functional groups such as hydroxyl, acylamino-, carboxyls
Base acrylate monomer, the preferably acrylate or methacrylate of the alkyl with carbon number 1~10, more preferable acrylic acid
The glass transition temperature (hereinafter sometimes referred to Tg) of the polymer of set member is as 40 DEG C or more, preferably 60 DEG C or more of list
Body can enumerate methyl methacrylate, isopropyl methacrylate, ethyl methacrylate, metering system as the monomer
Sour cyclohexyl etc..Further more, the upper limit of Tg is preferably 200 DEG C hereinafter, more preferably 150 DEG C or less.Glass transition temperature can
It is measured based on JIS K7121.
There are 2~10 points of friendships preferably in every 1 moles of polymer for the polysiloxane of the above-mentioned formula (1) obtained in this way
Join point, be more preferably the presence of at 2~6 points, can guide and the graft polymerization of (ii) ingredient.
In the present invention, as (iii) can with above-mentioned (ii) ingredient be copolymerized the monomer containing functional group, for carboxyl,
The monomer of the functional groups such as acylamino-, hydroxyl, unsaturated bond comprising vinyl, allyl etc. specifically can enumerate methyl-prop
Olefin(e) acid, acrylic acid, acrylamide, allyl methacrylate, vinyl methacrylate, 2-hydroxyethyl methacrylate,
Methacrylic acid 2- hydroxy propyl esters can improve compatibility by being copolymerized them.
For (II) acid-organosilicon crylic acid graft copolymer resin of the present invention, first, make above-mentioned to obtain in this way
(i) polysiloxane and (ii) (methyl) acrylate monomer, preferably (ii) and (iii) can be copolymerized with it contain official
The mixture for the monomer that can be rolled into a ball carries out emulsion grafting polymerization.
In this case, the quality of the polysiloxane of formula when graft polymerization (1) and (methyl) acrylate monomer
Than being 50：50~99：1, preferably 70：30~99：1.It is fewer than 50 if silicone ingredients are indicated with mass ratio, then it does not obtain
Sufficient shock resistance is obtained, generates abnormal sound sometimes.
Further more, using above-mentioned (i), (ii) ingredient mixture in the case of, relative to 100 mass parts of (i) ingredient, preferably
Using (ii) ingredient of 1~100 mass parts, 10~100 mass parts are more preferably used, 40~100 mass are further preferably used
Part.
In addition, in the case of mixture using above-mentioned (i)~(iii) ingredients, it is excellent relative to 100 mass parts of (i) ingredient
Choosing more preferably uses 10~100 mass using (ii) ingredient of 1~100 mass parts, (iii) ingredient of 0.01~20 mass parts
Part (ii) ingredient, 0.01~20 mass parts (iii) ingredient, further preferably use 40~100 mass parts (ii) ingredient,
(iii) ingredient of 0.01~5 mass parts.In this case, it is preferable that (i)：(ii)+(iii)=50：50~99：1.
Wherein, as the radical initiator used in graft polymerization, potassium peroxydisulfate can be enumerated, ammonium persulfate waited
Sulfate, hydrogen persulfate water, t-butyl hydroperoxide, hydrogen peroxide.As needed, it can also use sodium hydrogensulfite, carving
The redox system of the reducing agents such as white powder, L-AA, tartaric acid, carbohydrate, amine.
0.1~5 mass % of the usage amount of the radical initiator preferably total amount of (ii) ingredient and (iii) ingredient, more
It is preferred that 0.5~3 mass %.
The surfactant contained in the lotion when preparing polysiloxane can be sufficiently carried out grafting
Polymerization, but in order to improve stability, as anionic surfactant, it is poly- that lauryl sodium sulfate, laruyl alcohol can be added
Ether sodium sulfate, N- acyl aminos hydrochlorate, N- acyl taurine salts, aliphatic soap, alkylphosphonic etc..In addition, can also add
The nonionic systems emulsifier such as polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether.
0.1~5 matter of the total amount of preferred (ii) ingredient of usage amount and (iii) ingredient when adding surfactant
Measure %.
In turn, in order to adjust molecular weight, the grafting rate of graft polymers, chain-transferring agent can be added.
Preferably 25~55 DEG C, more preferable 25~40 DEG C of above-mentioned graft polymerization temperature.In addition, polymerization time preferably 2~8 is small
When, more preferable 3~6 hours.
The acid-organosilicon crylic acid graft copolymer resin obtained in this way, which becomes, makes (ii) ingredient, (iii) ingredient randomly connect
Branch polymer made of (i) ingredient.
In addition, acid-organosilicon crylic acid graft copolymer resin obtained above is in terms of the solid constituent in lotion, preferably
30~50 mass %.In addition, viscosity (25 DEG C) preferably 10~5,000mPas of the lotion, more preferable 50~1,000mPa
s.Viscosity can use rotary viscosity design determining.Preferably 1 μm of the average grain diameter of the lotion hereinafter, more preferable 0.1 μm (100nm)~
0.3μm(300nm).PH preferably 6~8.It should be noted that average grain diameter can use laser diffraction/scattering formula particle size distribution measuring
Device measures.
Obtained acid-organosilicon crylic acid graft copolymer resin is de- for example, by using heating due to the form for lotion
It after the methods of water, filtering, centrifugation, decantation concentrate dispersion liquid, is washed as needed, and then passes through normal pressure or decompression
Under heat drying, dispersion liquid is sprayed into air-flow spray drying, using heat drying of flowing heat medium etc. carry out water
The removing divided, is temporarily dried, powder is made.Further more, preferably 60~105 DEG C of drying temperature.
In the case where a little cohesion has occurred in obtained powder, can take the circumstances into consideration using powder such as jet mill, ball mill, hammer-mills
Broken machine is crushed.
Also sometimes for cyclic organic siloxane remaining in the acid-organosilicon crylic acid graft copolymer resin that will be obtained, table
Face activating agent is removed and is cleaned.Solvent at this time can enumerate carbon it is preferable to use alcohol system organic solvent, hydrocarbon system organic solvent
The lower alcohol of number 1~4, the aliphatic hydrocarbon of carbon number 5~20, it is specifically, further preferred methanol, ethyl alcohol, isopropanol, hexane, different
Dodecane.
For its cleaning method, such as the powder of 100 mass parts is taken in beaker, is added 5 times of its quality or more
Above-mentioned solvent, stir a few hours after, carry out suction strainer.Then, if being washed with identical solvent or being dissolved in alcohol system etc.
The solvent of water is washed, then more effectively.In this case, it usually carries out under room temperature (25 DEG C), but can heat sometimes.
In the case of having cleaned, re-dry and powder is made, can by the powder of filtering merely use drying machine 40 DEG C with
Go up and dry a few hours at 200 DEG C of temperature below or use flowing dryer etc..
The average grain diameter of the acid-organosilicon crylic acid graft copolymer resin obtained in this way is preferably 15 μm hereinafter, particularly preferably
It is 0.1~10 μm.
In addition, the weight average molecular weight of acid-organosilicon crylic acid graft copolymer resin preferably 50,000~500,000.If less than 50,000,
It then is precipitated with possible aggravation on rubber compounding object surface, even more than 500,000, it is also insufficient to mitigate effect for friction sometimes.It should
Illustrate, weight average molecular weight is dissolved in toluene 100mL's by mixing lotion and isopropanol (IPA), after oil extract drying by its 1g
25 DEG C of kinematic viscosity measured value is converted by dimethyl silicone molecules amount and is measured.
For the compounding amount of (II) acid-organosilicon crylic acid graft copolymer resin, relative to 100 mass of (I) rubber constituent
Part, it is 1~30 mass parts, preferably 5~20 mass parts.If less than 1 mass parts, lack friction and mitigate effect, if super
30 mass parts are crossed, then are precipitated sometimes on rubber compounding object surface, suitable effect does not show.
In the vibration damping rubber composition of the present invention, other than above-mentioned neccessary composition, relative to (I) rubber constituent
100 mass parts can include the vulcanizing agent that the previous additive as rubber of 0.1~10 mass parts uses.
As vulcanizing agent, sulphur, peroxide etc. can be enumerated, as long as having vulcanization effect, then can also use other changes
Close object, resin.
It, can further respectively relative to 100 mass parts of (I) rubber constituent in the vibration damping rubber composition of the present invention
It is compounded vulcanization accelerator, reinforcing agent, vulcanization aid, softening agent, processing aid, anti-aging agent, the filler of 0.1~10 mass parts
Deng.
As reinforcing agent, filler, carbon black, acetylene black, graphite, silica, calcium carbonate, talcum, clay can be enumerated
Equal inorganic fillers.Further more, using reinforcing agent, relative to 100 mass parts of rubber constituent, 10~200 can be compounded
Mass parts.
As vulcanization accelerator, can select using tetramethylthiuram monosulfide, tetramethylthiuram disulfide, a sulphur
Change guanidines, mercaptobenzothiazoler, the dibenzothiazyl disulfides such as thiurams, Thiourea, the diphenylguanidines such as Thiuram
Sulfenamides, the dimethyl disulfide generations such as equal thiazoles, cyclohexylbenzothiazole sulfenamide, butyl benzo thiazolesulfenamide
1 kind in the higher fatty acids such as dithiocar-bamates such as carbaminate etc., stearic acid or two or more.
As vulcanization aid, can enumerate ethylene glycol dimethacrylate, trimethylol-propane trimethacrylate,
Triallyl isocyanurate etc., the flowers of zinc, magnesia, zinc oxide etc..
As anti-aging agent, aromatic amine class, bis-phenol, Polyphenols, imidazoles, Thiourea, wax etc. can be enumerated.
In above-mentioned additive, on promoting vulcanization, vulcanization accelerator and vulcanization aid are particularly preferably used.
For the vibration damping rubber composition of the present invention, it is kneaded by using common processing unit (plant) such as roller, Banbury
Machine, kneader etc. carry out mixing and extrusion molding, injection moulding etc. to these ingredients, to obtain the rubber of desired shape
Molding.
Shockproof rubber, which vulcanizes the rubber composition by using well known method, to be obtained.At this point, implementing 1~60 minute
120~250 DEG C or so of heating, rubber composition can be made to vulcanize.
Molded product depend on object shape, by coverings such as the axis of automobile, can sulfidization molding be circle
Shape desired by tubular etc., embedded object object etc. and obtain vehicle part.
Further more, obtained Shockproof rubber molded product is also excellent from the release property of mold.
It can be used as the protection component of vehicle part according to the Shockproof rubber of the present invention obtained above, Neng Gouyou
It is selected in the insert bushings such as stabilizer bar bushing and uses, metal without being adhesively fixed is contacted with rubber in addition, is being applied
The position use of rotary force, load.
Embodiment
Production Example, embodiment and comparative example described below, specifically describe the present invention, but the present invention is not by following
Embodiment limits.It should be noted that in following examples, weight average molecular weight is to mix lotion and IPA, will after being dried by oil extract
25 DEG C of the kinematic viscosity measured value that its 1g is dissolved in toluene 100mL is measured by the conversion of dimethyl silicone molecules amount.
[Production Example 1]
By octamethylcy-clotetrasiloxane 499.6g, γ-methacryloxypropyl methyl diethoxysilane 0.8g, ten
The product and dodecyl benzene sulfonic acid 5g is dissolved in the product in pure water 45g that sodium dialkyl sulfate 5g is dissolved in pure water 45g
It is fitted into the polyethylene beaker of 2L, after equably being emulsified with homomixer, is slowly added water 400g to dilute, in pressure
300kgf/cm2Down by high-pressure homogenizer 2 times, uniform white emulsion has been obtained.The lotion is transferred to stirring dress
It sets, in the glass beaker of the 2L of thermometer, reflux condenser, after 24 hours polymerisations have been carried out at 55 DEG C, at 10 DEG C
It is pH6.8 with 10 mass % aqueous sodium carbonates 12g neutralizations after curing 24 hours.After the lotion is 3 hours dry at 105 DEG C
Non-volatile content (solid constituent) be 45.4 mass %, the polysiloxane in lotion is the soft gelatinous object of illiquidity
Matter.The polysiloxane is the weight average molecular weight about 400,000 obtained by the viscosity of toluene solution measured using kinematic viscosimeter
By formula (1) indicate structure (R1=methyl, R2=γ-methacryloxypropyl, Z=ethyls, X=OH bases, methyl, a
=0, b=2,500, c=1).
Methyl methacrylate (MMA) 55.5g is instilled thereto by lasting 3~5 hours, while work is used at 30 DEG C
T-butyl hydroperoxide 1.5g for peroxide and the L-AA 1.0g as reducing agent carry out redox reaction, from
And the acid-organosilicon crylic acid graft copolymer resin lotion of 44.5 mass %, pH6.8 of non-volatile content is obtained.
The lotion is adjusted to 10~30 mass % of concentration, it is organic to obtain by being spray-dried (100 DEG C)
Silica acrylic acid graft copolymer resin powder.The average grain diameter of obtained acid-organosilicon crylic acid graft copolymer resin is 0.2 μm,
Weight average molecular weight is about 300,000.
[Production Example 2]
In Production Example 1, MMA55.5g is replaced with into butyl acrylate (BA) 118.7g and methacrylic acid 2- hydroxyl second
Ester (2-HEMA) 6.2g, used t-butyl hydroperoxide 3.4g and as the L-AA 2.2g of reducing agent other than, use
Same method has obtained acid-organosilicon crylic acid graft copolymer resin.Obtained acid-organosilicon crylic acid graft copolymer resin
Average grain diameter is 0.2 μm, and weight average molecular weight is about 300,000.
[Production Example 3]
In Production Example 1, MMA55.5g is replaced with into MMA210.5g, BA3.6g, has used t-butyl hydroperoxide 5.8g
Other than the L-AA 3.8g as reducing agent, acid-organosilicon crylic acid system graft copolymerization tree has been obtained using same method
Fat.The average grain diameter of obtained acid-organosilicon crylic acid graft copolymer resin is 0.2 μm, and weight average molecular weight is about 300,000.
[comparison manufacturing example 1]
In Production Example 1, MMA55.5g is replaced with into MMA611.4g, has used t-butyl hydroperoxide 16.5g and conduct
Other than the L-AA 11g of reducing agent, acid-organosilicon crylic acid graft copolymer resin has been obtained using same method.It obtains
Acid-organosilicon crylic acid graft copolymer resin average grain diameter be 0.2 μm, weight average molecular weight is about 300,000.
[comparison manufacturing example 2]
In Production Example 1, MMA55.5g is replaced with into MMA2.5g, has used t-butyl hydroperoxide 0.07g and as also
Other than the L-AA 0.04g of former agent, acid-organosilicon crylic acid graft copolymer resin has been obtained using same method.It obtains
Acid-organosilicon crylic acid graft copolymer resin average grain diameter be 0.2 μm, weight average molecular weight is about 300,000.
The reaction ratio of polysiloxane and (methyl) acrylate is shown in table 1.
[table 1]
[Examples 1 to 4, comparative example 1~4]
It is measured shown in table 2 and meets the acid-organosilicon crylic acid system obtained in above-mentioned Production Example 1~3, comparison manufacturing example 1,2
Additive, is in addition compounded with aftermentioned amount, is prepared for implementing by branch copolymer resins, natural rubber, butadiene rubber, carbon black compounding
The vibration damping rubber composition of example 1~4, comparative example 1~4.
Additive be 3 mass parts of aromatic series processing oil, No. 35 mass parts of zinc oxide, 1 mass parts of stearic acid, 2 mass parts of wax,
Anti-aging agent N- phenyl-N '-(1,3- dimethylbutyls)-p-phenylenediamine 6C (emerging chemical (strain) manufacture of imperial palace) 2 mass parts are prevented
2 mass parts of old agent RD (emerging chemical (strain) manufacture of imperial palace), 1.5 mass parts of sulphur, (imperial palace is emerging chemical (strain) for accelerator CZ
Manufacture) 1.5 mass parts, vulcanization accelerator tetramethylthiuram monosulfide TS (imperial palace emerging chemical (strain) manufacture) 0.5 mass parts.
The shape for being shaped to above-mentioned vibration damping rubber composition to have through hole vulcanizes 30 minutes at 150 DEG C, manufacture
Shockproof rubber.Next, metal stabiliser bar is loaded on through hole, Shockproof rubber is fastened with clamp, stabiliser bar is turned round
Turn ± 10 degree, confirmed the presence or absence of abnormal sound generation at this time in the environment of 25 DEG C.
[table 2]
○：The generation of sound without exception, ×：Generate abnormal sound.
Claims (10)
1. vibration damping rubber composition, which is characterized in that contain：(I) rubber constituent：100 mass parts, and (II) acid-organosilicon crylic acid
Graft copolymer resin, to include 50~99 mass parts of polysiloxane indicated by the following general formula (1) and acrylate
The polymer of the mixture of 50~1 mass parts of monomer or methacrylate monomers：1~30 mass parts,
In formula, R1For 1 valency alkyl of identical or different unsubstituted or substituted carbon number 1~20, R2For sulfydryl, acryloxy
Or the alkyl or vinyl of the carbon number 1~6 of methacryloxy substitution, X are identical or different unsubstituted or substituted
Either hydroxyl Y is X or by-[O-Si (X) for 1 valency alkyl of carbon number 1~20, the alkoxy of carbon number 1~202]dPhase shown in-X
With or different groups, at least two in X and Y be hydroxyl, Z is the alkoxy or hydroxyl of the alkyl of carbon number 1~4, carbon number 1~4
Base, the positive number that a is 0~1,000, the positive number that b is 100~10,000, the positive number that c is 1~10, the positive number that d is 1~1,000.
2. vibration damping rubber composition described in claim 1, wherein (II) acid-organosilicon crylic acid graft copolymer resin is (i)
100 mass parts of polysiloxane and (ii) acrylate monomer or methacrylate list indicated by above-mentioned general formula (1)
The emulsion grafting polymerization object of the mixture of 1~100 mass parts of body.
3. the vibration damping rubber composition described in claim 2, wherein for 100 mass parts of (i) ingredient and (ii) ingredient 10~100
The emulsion grafting polymerization object of the mixture of mass parts.
4. vibration damping rubber composition described in claim 1, wherein (II) acid-organosilicon crylic acid graft copolymer resin is (i)
100 mass parts of polysiloxane, (ii) acrylate monomer or the methacrylate monomers indicated by above-mentioned general formula (1)
The mixture for 0.01~20 mass parts of monomer containing functional group that 1~100 mass parts and (iii) can be copolymerized with it, and be
(i) total mass ratio of ingredient and (ii), (iii) ingredient are 50：50~99：The emulsion graft polymerization of the mixture of 1 ratio is poly-
Close object.
5. the vibration damping rubber composition described in claim 4, wherein for 100 mass parts of (i) ingredient and (ii) ingredient 10~100
The mixture of mass parts and 0.01~20 mass parts of (iii) ingredient.
6. the vibration damping rubber composition described in claim 4 or 5, wherein (iii) ingredient is selected from methacrylic acid, acrylic acid, third
Acrylamide, allyl methacrylate, vinyl methacrylate, 2-hydroxyethyl methacrylate and methacrylic acid 2- hydroxyls
Base propyl ester.
7. any one of them vibration damping rubber composition of claim 2~6, wherein (ii) ingredient is with carbon number 1~10
The acrylate or methacrylate of alkyl.
8. any one of them vibration damping rubber composition of claim 1~7, wherein the polysiloxane indicated by formula (1)
For cyclic organic siloxane, α, alpha, omega-dihydroxy siloxane oligomer, α, ω-dialkoxysiloxanes oligomer or alkoxy
The polymer of silane and the silane coupling agent indicated by the following general formula (2)：
R3 (4-e-f)R4 fSi(OR5)e (2)
In formula, R3For the alkyl or vinyl of the carbon number 1~6 of sulfydryl, acryloxy or methacryloxy substitution, R4
For the alkyl of carbon number 1~4, R5For the alkyl of carbon number 1~4, e be 2 either 3 f be 0 either 1 e+f be 2 or 3.
9. Shockproof rubber, it includes the cross-linking agents of any one of them vibration damping rubber composition of claim 1~8.
10. the Shockproof rubber described in claim 9, is used for vehicle part.
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| PCT/JP2016/077131 WO2017073194A1 (en) | 2015-10-27 | 2016-09-14 | Antivibration rubber composition and antivibration rubber |
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| JP2022131528A (en) * | 2021-02-26 | 2022-09-07 | 日信化学工業株式会社 | Vinyl acetate-silicone copolymer resin and method for producing the same |
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| WO2017073194A1 (en) | 2017-05-04 |
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