CN107207926A - Neoprene adhesive composite - Google Patents
Neoprene adhesive composite Download PDFInfo
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- CN107207926A CN107207926A CN201680010027.6A CN201680010027A CN107207926A CN 107207926 A CN107207926 A CN 107207926A CN 201680010027 A CN201680010027 A CN 201680010027A CN 107207926 A CN107207926 A CN 107207926A
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- Prior art keywords
- neoprene
- mass parts
- adhesive composite
- mass
- neoprene adhesive
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J113/00—Adhesives based on rubbers containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Abstract
Neoprene adhesive composite, said composition includes neoprene, novolak phenolics and organic solvent, the neoprene contains carboxy-modified neoprene, and the novolak phenolics are to make phenols and resin obtained by aldehydes reaction in the presence of the salt of weak acid of divalent metal.
Description
Technical field
The present invention relates to neoprene adhesive composite.
This application claims the preferential of the Japan Patent Patent 2015-029803 that application was submitted based on 2 18th, 2015
Power, quotes its content into the application.
Background technology
Heat reactivity resol type phenol resin and alkaline metal oxide are added to neoprene rubber obtained by neoprene
The cementability and heat resistance of glue sticking agent composition are excellent.Thus it is known that the adhesives composition is in industry
On be useful (referring for example to patent document 1 and 2).It is that can form the thermal response of chelate to think this excellent heat resistance
The complex compound of the methylol of the resol type phenol resin of property, dimethylene ether and phenolic hydroxyl group and alkaline metal oxide is led
Cause.Therefore, currently require that in the neoprene adhesive composite with heat resistance, used with a large amount of methylols, two
The heat reactivity resol type phenol resin of methylene ether and phenolic hydroxyl group.
But, there is the neoprene adhesive composite of excellent heat resistance then adherence (Japanese：タ ッ Network) get over
Low tendency.Therefore, in the purposes for needing initial bond power, or in the winter time etc. under cryogenic conditions, exist as described above
Adhesive composite can not give full play to the technical problem of performance.Then, all the time, using methylol, dihydroxymethyl and
(for example Showa Denko K. K (Showa Electricity works society) makes the low heat reactivity alkyl phenolic resin of the content of dimethylene ether
CKM-904, CKM-919 etc.) substitute the phenolic resin, or with coumarone indeneresin, Petropols and polyterpene
The thermoplastic adhesives such as resin assign resin combination and used, to improve adherence.However, also it is untapped go out all meet heat resistance and
The neoprene adhesive composite of adherence and initial bond.
On the other hand, due to that can occur " sick room syndrome (シ ッ Network ス Ha ウ ス syndromes) " and " chemical substance allergy
Disease ", the strict concentration of formaldehyde for limiting interior of building standard law (building Building base Quasi methods) of in July, 2003 revision.
Under this background, the exploitation of the environment reply type neoprene adhesive composite of low formolation or non-formaldehyde
Also become important problem.
On the conventional neoprene adhesive composite containing heat reactivity resol type phenol resin as described above,
The problem of in the presence of release formaldehyde slow from heat reactivity resol type phenol resin.Therefore, use at present and contain formaldehyde trapping agent
Resol type phenol resin (referring for example to patent document 3), or add formaldehyde trapping agent in neoprene adhesive composite.
But, these countermeasures can only also reduce the burst size of formaldehyde.That is, in the case where environment temperature is higher than room temperature, there is first
Aldehyde trapping agent loses the situation of trapping effect and then a large amount of release formaldehydes.In addition, though also having using novolak type phenol tree
The bonding agent (such as patent document 4) of fat and chlorobutadiene class rubber, but performance is not in terms of there is intensity and adhesion time
Sufficient technical problem.Also it is untapped go out the not release formaldehyde and neoprene with sufficient intensity glues completely as described above
Connect agent composition.
Prior art literature
Patent document
Patent document 1：Japan Patent examined patent publication 46-40877 publications
Patent document 2：Japan Patent examined patent publication 54-7820 publications
Patent document 3：Japanese Patent Laid-Open 2001-164089 publications
Patent document 4：No. 4865303 publication of Japanese Patent Laid
The content of the invention
The technical problems to be solved by the invention
The present invention is in view of the foregoing, it is therefore intended that provides and all meets heat resistance and adherence and early strength
Cementability is excellent simultaneously and neoprene adhesive composite of not release formaldehyde.
Solve the technical scheme that technical problem is used
Present inventors etc. are carefully studied to solve above-mentioned technical problem, are as a result found by carboxy-modified
Neoprene is that must mix novolak phenolics and organic solvent in the neoprene of composition, be can solve the problem that above-mentioned
Technical problem, so as to complete the present invention.Additionally, it was found that the novolak phenolics are to be deposited in specific catalyst
The resin as obtained by phenols with aldehydes reaction is advisable under.
Present inventor etc. provides neoprene adhesive composite, and the composition contains neoprene, phenolic varnish type
Phenolic resin and organic solvent, the neoprene contain carboxy-modified neoprene.
One of present invention is following neoprene adhesive composite.
(1) neoprene adhesive composite, the composition contain neoprene, novolak phenolics and
Organic solvent, the neoprene contains carboxy-modified neoprene,
The novolak phenolics be make in the presence of the salt of weak acid of divalent metal phenols and aldehydes react and
The resin obtained.
Above-mentioned neoprene adhesive composite preferably meets (2)~(9).
(2) neoprene adhesive composites of the as described in (1), wherein, the neoprene contains 1 mass %~99
The quality % carboxy-modified neoprene.
(3) neoprene adhesive composites of the as any one of (1)~(2), wherein, relative to the neoprene
The mass parts of rubber 100, containing 1 mass parts~100 mass parts the novolak phenolics.
(4) neoprene adhesive composites of the as any one of (1)~(3), wherein, the phenolic varnish type
The weight average molecular weight of phenolic resin is 300~10000.
(5) neoprene adhesive composites of the as any one of (1)~(4), wherein, relative to the neoprene
The mass parts of rubber 100, containing 0.1 mass parts~10 mass parts age resister.
(6) neoprene adhesive composites of the as any one of (1)~(5), wherein, relative to the neoprene
The mass parts of rubber 100, amount to containing 0.1 mass parts~30 mass parts selected from metal oxide, metallic salt and they
At least one of mixture.
(7) neoprene adhesive composites of the as described in (6), wherein, the metal oxide is magnesia or oxidation
Zinc.
(8) neoprene adhesive composites of the as described in (6), wherein, the metallic salt is magnesium acetate or acetic acid
Zinc.
(9) neoprene adhesive composites of the as any one of (1)~(8), wherein, solid constituent is 1 matter
Measure the mass % of %~90.
Invention effect
If using the present invention, cementability while meeting heat resistance and adherence, early strength can be provided also excellent
Good and not release formaldehyde neoprene adhesive composite.
Embodiment
The preferred exemplary to the neoprene adhesive composite of the present invention is described in detail below.In addition, of the invention
Adhesive composite be not limited to the example below., can be by implementing addition in the range of the purport without departing from the present invention
Implement the present invention with the various modes of change etc..
[neoprene adhesive composite]
The feature of the neoprene adhesive composite of the present invention is to include the neoprene rubber containing carboxy-modified neoprene
Glue, novolak phenolics and organic solvent.
By to containing carboxy-modified neoprene as specific novolaks must be mixed in the neoprene of composition
Type phenolic resin, it is possible to increase adherence and early strength, while assigning the excellent heat resistance of the composition and cementability.
(neoprene)
Time needed for the hardness of neoprene in the neoprene adhesive composite of the present invention starts rise is preferred
Below 50 hours, more preferably below 25 hours.
Hardness started time needed for rise if it exceeds 50 hours, then was difficult to obtain required adhesive property, therefore not
It is preferred that.Herein, the time needed for hardness starts rise refers to, flat board obtained by the fragment of compacting neoprene is put into 70 DEG C
Baking oven in, insulation 1 hour and except after brilliant, the warp of JIS A hardometer assay plate hardness is used in -10 DEG C of low temperature thermostat bath
During Shi Bianhua, hardness since determine when value increase more than 10% untill time.
The neoprene contained in the neoprene adhesive composite of the present invention is not particularly limited, and can arbitrarily be selected.Example
Such as, it can be used rubber obtained by 2- chloro-1,3-butadienes (chlorobutadiene) homopolymerization, or by 2- chloro-1,3-butadienes and its
Rubber obtained by his monomer copolymerization.Herein, as other monomers, as long as monomer that can be with 2- chloro-1,3-butadiene copolymerization
, it is not particularly limited.For example, chloro-1,3-butadienes of 2,3- bis- etc. can be enumerated.Though the amount of the chloro- 1,3- butadiene of 2,3- bis- etc.
It can arbitrarily select, but relative to the mass parts of 2- chloro-1,3-butadienes 100, be preferably incorporated into the mass parts of 1 mass parts~10.
By the method for the chloro- 1,3- butadiene homopolymerizations of 2- and by the method for the chloro- 1,3- butadiene of 2- and other monomers copolymerization
Can arbitrarily it select, for example, polymerization known to radical polymerization and ionic polymerization etc. can be used.
The neoprene adhesive composite of the present invention can contain without carboxy-modified neoprene.As without carboxyl
Modified neoprene, can be used for example commercially available bonding agent neoprene for being referred to as A types, the commercially available bonding for being referred to as W types
Agent neoprene etc..In addition, A types refer to the fast type of crystallization rate, W refers to the slow type of crystallization rate.For example, can
Use the fast non-sulphur modification neoprene of crystallization rate and the slow non-sulphur modification neoprene of crystallization rate etc..As referred to as
The specific example of the bonding agent neoprene of A types, can enumerate the シ ョ ウ プ レ Application (note of such as Showa Denko K. K
Volume trade mark) AD and シ ョ ウ プ レ Application (registration mark) AC.As the specific example of the bonding agent neoprene of referred to as W types,
シ ョ ウ プ レ Application (registration mark) W and シ ョ ウ プ レ Application (registration mark) of such as Showa Denko K. K can be enumerated
WHV etc..Wherein, from the point of view of heat resistance and cementability are excellent, preferably シ ョ ウ プ レ Application (registration mark) AD and シ ョ
ウ プ レ Application (registration mark) AC.
Mooney viscosity without carboxy-modified neoprene can be selected arbitrarily, preferably 30~150M, more preferably 70~
120M。
The neoprene adhesive composite of the present invention contains carboxy-modified neoprene.It is carboxy-modified in the present invention
Neoprene refer to that at least there is the rubber of carboxyl in neoprene.The amount of carboxy-modified neoprene can be any
Selection.For example, being preferably the mass % of 1 mass %~100 mass %, more preferably 20 mass %~100 in neoprene, enter
One step is preferably the mass % of 40 mass %~100, the mass % of particularly preferably 60 mass %~100, is further particularly preferably
The mass % of 80 mass %~100.Neoprene also can all carboxy-modified neoprenes.
If the content of carboxy-modified neoprene is within the above range in neoprene, it can obtain desired viscous
Connect performance.
The amount of carboxy-modified neoprene in neoprene can be changed according to required condition.Lower limit for example may be used
Select more than 1 mass %, more than 10 mass %, more than 20 mass %, more than 30 mass % or 40 mass % are with first-class.Upper limit example
Below 99 mass %, below 80 mass %, below 70 mass % or 60 mass % such as may be selected such as the following.
The polymerization of the carboxy-modified neoprene of the present invention is not particularly limited, and can arbitrarily be selected.It can enumerate for example
Chloroprene monomer and the method for carboxylic vinyl monomer polymerization, Chloroprene monomer and carboxylic vinyl monomer and root
The method polymerizeing together according to other ethylene unsaturated monomers for being capable of copolymerization needed to use.
Carboxylic vinyl monomer, as the crosslinking points for high temperature bonding power to be presented, is required composition.Carboxylic second
Alkene monomer can be selected arbitrarily.For example, acrylic acid, methacrylic acid, 2- methacryloxyethyls butanedioic acid, 2- first can be enumerated
Unrighted acids such as base acryloyl-oxyethyl hexahydrophthalic acid, fumaric acid, maleic anhydride, butenoic acid etc..These can
To be used alone, it can also be used in combination.Wherein, it is excellent from the point of view of the copolymerizable with Chloroprene monomer
Select methacrylic acid.
In the case of using methacrylic acid as carboxylic vinyl monomer, its amount can be selected arbitrarily, but relative to
The mass parts of Chloroprene monomer 100, are preferably incorporated into the mass parts methacrylic acid of 0.1 mass parts~10, more preferably mix 0.3 mass
Part~8 mass parts, the particularly preferably mass parts of 0.5 mass parts of incorporation~5.
If the incorporation of methacrylic acid is within the above range, while sufficient adhesive strength is obtained, carboxyl
Modified neoprene is chemically stable.In addition, the monomer containing carboxy vinyl beyond methacrylic acid is it is also preferred that with above-mentioned model
Enclose and used.
In addition, being capable of the ethylene unsaturated monomer of copolymerization as other, methyl acrylate, first can be also used as needed
Diene-based monomer, the benzene such as (methyl) esters of acrylic acid, butadiene, 2,3- dichloroprenes, the 1- chlorobutadienes of base acrylic acid etc.
Ethene, acrylonitrile etc. are generally used for the monomer of the copolymerization of chlorobutadiene.
These single phases are for the mass parts of Chloroprene monomer 100, with the incorporation below more than 0 mass parts 20 mass parts
Suitably used.Can also the scopes etc. of 3~10 mass parts used.
Polymerization initiator used can be selected arbitrarily in the polymerization of carboxy-modified neoprene.For example, can enumerate known
Free radical product.As polymerization initiator, persulfuric acid compound, peroxidating such as potassium peroxydisulfate, ammonium persulfate can be enumerated
The inorganic peroxides such as hydrogen, t-butyl hydroperoxide or organic peroxide etc..These polymerization initiators can only be used alone one
Kind, or also can as with reducing substances and and used with redox type initiators., can example as reducing substances
Citing such as thiosulfate, thiosulfite, organic amine.
Preferably 0 DEG C~80 DEG C of the polymerization temperature of carboxy-modified neoprene, more preferably 3 DEG C~65 DEG C, further preferred 5
DEG C~50 DEG C.By suitably changing polymerization temperature, desired crystalline carboxy-modified neoprene can be obtained.
Chain-transferring agent used can be selected arbitrarily in the polymerization of carboxy-modified neoprene, can enumerate such as alkyl hydrosulfide,
Halogenated hydrocarbons, alkyl xanthogenic acid disulphide, tetraalkyl thiuram disulphide, α-methylstyrenedimer, 1,1- diphenyl
Ethene, sulphur equimolecular quantity conditioning agent.
The polymerisation conversion of carboxy-modified neoprene is preferably 50%~100%.In the case that remaining has monomer, lead to
Monomer stripping (モ ノ マ ー ス ト リ ッ プ) etc. is crossed to remove monomer.
Short-stopper used can be selected arbitrarily in the polymerization of carboxy-modified neoprene, be conventional stopping agent i.e.
Can, it is not particularly limited.For example, phenthazine, 2,6- tert-butyl-4-methyl-Phenols, azanol etc. can be enumerated.
As the concrete example of this carboxy-modified neoprene, the commercially available bonding agent neoprene for being referred to as AF types can be used
Rubber etc..As the bonding agent neoprene of referred to as AF types, the シ ョ ウ プ レ of such as Showa Denko K. K can be enumerated
Application (registration mark) AF etc..Wherein, from the point of view of heat resistance and early strength are excellent, preferred シ ョ ウ プ レ Application (registrars
Mark) AF.
The Mooney viscosity of carboxy-modified neoprene can be selected arbitrarily, preferably 30~80M, more preferably 40~70M.Mooney
Viscosity can be determined by method as defined in JIS K6300.
(novolak phenolics)
The content of novolak phenolics in the neoprene adhesive composite of the present invention can be selected arbitrarily, phase
For the mass parts of neoprene 100, the mass parts of preferably 1 mass parts~100, the mass parts of more preferably 10 mass parts~100 are entered
One step is preferably the mass parts of 10 mass parts~90, and the mass parts of particularly preferably 40 mass parts~90, are still more preferably 60 matter
Measure the mass parts of part~90.
If the content of novolak phenolics is within the above range, desired adhesive property can be obtained.Institute
Stating the content of novolak phenolics can be selected according to required condition etc., it is also preferred that such as 60~75 mass
Part, 70~90 mass parts, 20~80 mass parts etc..
The present invention novolak phenolics preferably by for example as catalyst divalent metal weak acid
Phenols is set to react and obtain with aldehydes in the presence of salt.
As phenols, the composition used in the manufacture for being general phenolic resin can be used without particular limitation.Example
Such as, phenol, cresols, xylenol, butylphenol, octyl phenol, nonyl phenol, phenylphenol, cyclohexylphenol, naphthalene can be enumerated
Phenol, naphthalenediol, bisphenol-A, Bisphenol F, bisphenol S etc..These phenols can be used alone a kind, can also two or more be applied in combination.This
In a little compositions, from the point of view of the compatibility with neoprene, the alkylphenols such as butylphenol are preferably used.
As aldehydes, the composition used in the manufacture for being general phenolic resin can be used without particular limitation.Example
Such as, formaldehyde, paraformaldehyde, benzaldehyde, furfural etc. can be enumerated.These aldehydes can be used alone a kind, can also two or more combination
Use.
In addition, the incorporation of aldehydes is relative to 1 mole of phenols, preferably 0.1 mole~2.0 moles, more preferably 0.2~
1.5 mole.
If the incorporation of aldehydes is within the above range, the novolaks with desired weight average molecular weight can be obtained
Type phenolic resin.
Can arbitrarily it be selected as the salt of weak acid of the divalent metal of catalyst.For example, Ca, Mg, Zn, Mn, Pb etc. two can be used
The salt of the weak acid such as valency metal and acetic acid, formic acid, boric acid.As the salt of weak acid of divalent metal, such as zinc acetate, acetic acid can be enumerated
Magnesium, manganese acetate, lead acetate, zinc formate, formic acid manganese, Firebrake ZB, manganese borate etc..The salt of weak acid of these divalent metals can be used alone
1 kind, can also two or more be applied in combination.
The addition of the salt of weak acid of divalent metal is relative to the parts by weight of phenols 100, the mass of preferably 0.1 mass parts~80
Part, the mass parts of more preferably 0.5 mass parts~65, the mass parts of further preferred 1 mass parts~50.The salt of weak acid of divalent metal adds
Dosage can carry out any selection as needed, for example, be alternatively 0.5~30 mass parts, 0.5~15 mass parts, 1~10 mass parts
Deng.
If the addition of the salt of weak acid of divalent metal is within the above range, it can obtain with desired Weight-average molecular
The novolak phenolics of amount, in addition, not influenceed by remaining catalyst, can obtain desired adhesive property.
As the example of the reaction of phenols and aldehydes, known side used in the manufacture of general phenolic resin can be enumerated
Method.As this reaction, it can enumerate and for example add the salt of weak acid of phenols, aldehydes and divalent metal and in defined temperature in the lump
The method of the lower reaction of degree, or add phenols and the salt of weak acid of divalent metal, at an established temperature addition aldehydes reacted
Method etc..
Reaction temperature is preferably 50 DEG C~180 DEG C, more preferably 80 DEG C~150 DEG C.
If reaction temperature is within the above range, reaction speed will not step-down, the reaction time can be prevented long, this
Outside, it is easily controlled as defined temperature, so that it is preferred that.
Reaction time is not particularly limited, and can suitably be adjusted according to incorporation and reaction temperature of each composition etc..
It is modified that the novolak phenolics as obtained by above-mentioned reaction can further carry out oily modification and modified rubber etc..
The weight average molecular weight of the novolak phenolics obtained like this can be selected arbitrarily without particular limitation, be preferably
300~10000, more preferably 300~8000.
If the weight average molecular weight of novolak phenolics is within the above range, desired cementability can be obtained
Energy.Weight average molecular weight is according to required condition etc., preferably in the scopes such as 1000~7000,500~6000,1500~7500
It is interior.
The weight average molecular weight of novolak phenolics is measured by the method described in embodiment.
Resol type phenol resin is preferably free of in the neoprene adhesive composite of the present invention.
(organic solvent)
The organic solvent used in the neoprene adhesive composite of the present invention is general neoprene bonding agent group
The solvent used in compound, can arbitrarily be selected without particular limitation.As organic solvent, such as toluene and diformazan can be enumerated
The aromatic solvents such as benzene, MEK (MEK), methylisobutylketone (MIBK), hexane, hexamethylene, 2- Methyl-1-pentenes, acetic acid second
Ester, acetone and rubber volatile oil etc..These organic solvents can only be used alone a kind, can also two or more be applied in combination.
The amount of organic solvent in neoprene adhesive composite can be selected arbitrarily as needed.Such as preferably 5~50 mass %, more
It is preferred that 5~40 mass %, further preferred 8~35 mass %.
(other compositions)
The neoprene adhesive composite of the present invention can also contain age resister, metal oxide and gold as needed
Belong to salt etc..
Age resister can be selected arbitrarily, can enumerate such as 2, the 6- tert-butyl group -4- cresols (BHT), 2,6- di-t-butyl -4- second
The public affairs such as phenol, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols)
The phenol antioxidant known.These age resisters can only be used alone a kind, can also two or more be applied in combination.
The content of age resister in the neoprene adhesive composite of the present invention can be selected arbitrarily, relative to 100 matter
Measure the neoprene of part, the mass parts of preferably 0.1 mass parts~10, more preferably 0.5~7 mass parts.
If the content of age resister is within the above range, desired antiageing effect and cementability can be obtained
Energy.The content of age resister is according to required condition etc., or 0.1~5 mass parts, 1~4 mass parts etc..
Metal oxide can be selected arbitrarily, can be enumerated such as magnesia (MgO) and zinc oxide (ZnO).
Metallic salt can be selected arbitrarily, can enumerate such as magnesium acetate (Mg (CH3COO)2) and zinc acetate (Zn (CH3COO)2)
Deng.
These metal oxides and metallic salt can only be used alone a kind, can also two or more be applied in combination.
In the neoprene adhesive composite of the present invention, relative to the mass parts of neoprene 100, selected from metal oxidation
The content of at least one of thing, metallic salt and their mixture preferably amounts to the mass parts of 0.1 mass parts~30.
If the content selected from least one of metal oxide, metallic salt and these mixture is in above-mentioned model
In enclosing, then desired heat resistance and adhesive property can be obtained.Their content is according to required condition etc., or 1
~20 mass parts, 3~15 mass parts, 3~10 mass parts etc..
In the case of individually containing magnesia in the neoprene adhesive composite of the present invention, relative to 100 mass parts
Neoprene, preferably comprise the magnesia of the mass parts of 0.1 mass parts~20, more preferably 1~10 mass parts.
In addition, the neoprene adhesive composite of the present invention contains selected from least one of zinc oxide and metallic salt
In the case of, relative to the mass parts of neoprene 100, the content selected from least one of zinc oxide and metallic salt is preferably
The mass parts of 1 mass parts~30, the mass parts of more preferably 1 mass parts~20, the mass parts of more preferably 1 mass parts~10.
The compound method of the neoprene adhesive composite of the present invention is not particularly limited, and can arbitrarily be selected.For example, can make
With the compound method of general neoprene adhesive composite.As this compound method, it can enumerate for example in organic solvent
In directly dissolving neoprene, novolak phenolics, the age resister used as needed, metal oxide, metal
The method of salt etc., the roller machine etc. such as the age resister used by neoprene, as needed, metal oxide, metallic salt
In method of organic solvent etc. after uniform mixing, by the mixture and novolak phenolics co-dissolve.
The content of solid constituent in the neoprene adhesive composite obtained like this can be entered according to desired purposes
Row adjustment.Such as preferably 1~90 mass %, more preferably 5~70 mass %, further preferred 10~50 mass %.
If the content of solid constituent is within the above range, desired adhesive property is resulted in, in addition, can obtain
Use desired operability during neoprene adhesive composite.The content of solid constituent according to required condition etc.,
Can be 5~50 mass %, 8~40 mass %, 10~38 mass % etc..
In addition, in this specification, " operability " refers to, coating when being coated with neoprene adhesive composite to object
Easness etc..
If using the neoprene adhesive composite of the present invention, can provide and meet heat resistance and adherence, just
Cementability is also excellent while phase intensity and adhesive composite of not release formaldehyde.
Embodiment
Below by way of embodiments and comparative examples to the present invention further illustrated, but the present invention be not limited only to
Lower embodiment.
[assay method of weight average molecular weight]
The synthesis example of the novolak phenolics (Resin A~resin D) used in embodiment described below and
In the novolak phenolics (resin E~F) and resol type phenol resin G synthesis example that are used in comparative example, gained
The weight average molecular weight Mw of polymer passes through (East ソ ー societies of TOSOH Co., Ltd) system GPC8220 by following condition measure.
Eluent=tetrahydrofuran, flow velocity=1.0mL/ minutes, column temperature=40 DEG C, blob detection=differential refractometer, fill
Fill out post=TSK-gel (registration mark) G7000Hxl/TSK-gel (registration mark) GMHxl/TSK-gel (registration mark)
GMHxl/G3000Hxl/ guard columns H-L, molecular weight calculation=polystyrene conversion.
(synthesis of resin)
The synthesis example of novolak phenolics (Resin A~resin D) used in embodiment is shown.
[synthesis of Resin A]
Will by the mass parts of p-t-butyl phenol (pTBP) 50.0, the mass parts of phenol 50.0,37.0 mass % formalin
The mixture that the mass parts of the aqueous solution 50.0 and the mass parts of zinc acetate 5.0 are constituted adds four mouthfuls of burnings for possessing agitator and thermometer
In bottle, reacted 3 hours with 100 DEG C.
Afterwards, with 160 DEG C of decompression dehydrations, the novolak phenolics (resin that weight average molecular weight is 2100 is obtained
A) 112.4 mass parts.
[synthesis of resin B]
By by the mass parts of pTBP 50.0, the mass parts of phenol 50.0, the 37.0 mass % mass of formlinata aquae concentratac 70.0
The mixture that part and the mass parts of zinc acetate 5.0 are constituted is added in the four-hole boiling flask for possessing agitator and thermometer, anti-with 100 DEG C
Answer 3 hours.
Afterwards, with 160 DEG C of decompression dehydrations, the novolak phenolics (resin that weight average molecular weight is 5100 is obtained
B) 120.9 mass parts.
[resin C synthesis]
By by the mass parts of pTBP 50.0, the mass parts of phenol 50.0, the 37.0 mass % mass of formlinata aquae concentratac 70.0
The mixture that part and the mass parts of magnesium acetate 5.0 are constituted is added in the four-hole boiling flask for possessing agitator and thermometer, anti-with 100 DEG C
Answer 3 hours.
Afterwards, with 160 DEG C of decompression dehydrations, the novolak phenolics (resin that weight average molecular weight is 5000 is obtained
C) 119.8 mass parts.
[resin D synthesis]
By by the mass parts of pTBP 50.0, the mass parts of 3,5- xylenols 50.0,37.0 mass % formlinata aquae concentratac
The mixture that 50.0 mass parts and the mass parts of zinc acetate 5.0 are constituted is added in the four-hole boiling flask for possessing agitator and thermometer,
Reacted 3 hours with 100 DEG C.
Afterwards, with 160 DEG C of decompression dehydrations, the novolak phenolics (resin that weight average molecular weight is 3020 is obtained
D) 113.3 mass parts.
The novolak phenolics (resin E, F) and resol type phenol resin (resin used in comparative example are shown
G synthesis example).
[resin E synthesis]
By by the mass parts of pTBP 50.0, the mass parts of phenol 50.0, the 37.0 mass % mass of formlinata aquae concentratac 50.0
The mixture that part and the mass parts of ethanedioic acid 2.0 are constituted is added in the four-hole boiling flask for possessing agitator and thermometer, anti-with 100 DEG C
Answer 3 hours.
Afterwards, with 160 DEG C of decompression dehydrations, the novolak phenolics (resin that weight average molecular weight is 2100 is obtained
E) 118.5 mass parts.
[resin F synthesis]
By by the mass parts of pTBP 50.0, the mass parts of phenol 50.0, the 37.0 mass % mass of formlinata aquae concentratac 70.0
The mixture that part and the mass parts of ethanedioic acid 3.0 are constituted is added in the four-hole boiling flask for possessing agitator and thermometer, anti-with 100 DEG C
Answer 3 hours.
Afterwards, with 160 DEG C of decompression dehydrations, the novolak phenolics (resin that weight average molecular weight is 5100 is obtained
F) 125.9 mass parts.
[resin G synthesis]
By by the mass parts of pTBP 100.0,37.0 mass the % mass parts of formlinata aquae concentratac 170.0 and 10.0 matter
The mixture that the amount % mass parts of causticity sodium water solution 5.0 are constituted is added in the four-hole boiling flask for possessing agitator and thermometer, with
100 DEG C have been reacted 2 hours.
After reaction terminates, further the mass parts of toluene 100.0 and the mass parts of 10.0 mass % aqueous sulfuric acids 1.0 are added simultaneously
Mixing, then stands again, as described above removes the water of lower floor.
Afterwards, with 100 DEG C of decompression dehydrations, the resol type phenol resin (resin G) that weight average molecular weight is 2280 is obtained
125.9 mass parts.
(composition, manufacturing condition and the molecular weight of resin)
The proportioning composition of novolak phenolics (Resin A~F) and resol type phenol resin (resin G) is shown in table
1。
[table 1]
The formulation example of neoprene adhesive composite is then shown.
[embodiment 1]
The mass parts of Resin A 50.0 of above-mentioned gained are dissolved in the mass parts of MEK (MEK) 50.0,100.0 have been prepared
The Resin A content of mass parts is 50.0 mass % resin solution (solution 1).
Outside the solution, by the mass parts (trade name of neoprene 50.0：シ ョ ウ プ レ Application AD, Showa electrician strain formula
Commercial firm's system) and the 2,6- tert-butyl group -4- cresols (BHT, trade name：ノ Network ラ ッ Network 200, imperial palace newly with chemical industry Co., Ltd.
(imperial palace Xin Xing chemical industry society) makes) 2.0 mass parts twin-roll machines knead 20 minutes below 60 DEG C.Afterwards, by the mixture
With the carboxy-modified mass parts (trade name of neoprene 50.0：シ ョ ウ プ レ Application AF, Showa Denko K. K's system) co-dissolve
In the mixed solution being made up of the mass parts of MEK 100.0, the mass parts of ethyl acetate 150.0 and the mass parts of hexamethylene 150.0, obtain
Rubber solutions (solution 2).
The resin solution and rubber solutions are uniformly mixed with agitator, neoprene adhesive composite is obtained
602.0 mass parts.The solid constituent of the neoprene adhesive composite is 25.2 mass %.
[embodiment 2~11]
Each resin solution and rubber solutions are prepared according to the proportioning shown in table 2 below similarly to Example 1, reality is obtained
Apply the neoprene adhesive composite of example 2~12.
[comparative example 1]
The mass parts of resin E 50.0 are dissolved in MEK50.0 mass parts, the mass % of resin 50.0 resin is obtained
The mass parts of solution 100.0.
Outside the solution, by the mass parts (trade name of neoprene 50.0：シ ョ ウ プ レ Application AD, Showa electrician strain formula
Commercial firm's system), the mass parts of BHT 2.0, the mass parts (trade name of magnesia 4.0：キ ョ ー ワ マ グ 150, consonance chemical industry strain formula
Commercial firm (Association and chemical industry Co., Ltd.) system) and the mass parts twin-roll machine of zinc oxide 5.0 kneaded 20 minutes below 60 DEG C.
Afterwards, by the mixture and the carboxy-modified mass parts (trade name of neoprene 50.0：シ ョ ウ プ レ Application AF, Showa electrician strain formula
Commercial firm's system) co-dissolve constitutes in by the mass parts of MEK 100.0, the mass parts of ethyl acetate 150.0 and the mass parts of hexamethylene 150.0
Mixed solution, obtain rubber solutions.
The resin solution and the rubber solutions are uniformly mixed with agitator, the combination of neoprene bonding agent is obtained
The mass parts of thing 611.0.The solid constituent of the neoprene adhesive composite is 26.4 mass %.
[comparative example 2]
The mass parts of resin E 50.0 are dissolved in MEK50.0 mass parts, the mass % of resin 50.0 resin is obtained
The mass parts of solution 100.0.
Outside the solution, by the mass parts (trade name of neoprene 100.0：シ ョ ウ プ レ Application AD, Showa electrician strain
Formula commercial firm system), the mass parts of BHT 2.0, the mass parts (trade name of magnesia 4.0：キ ョ ー ワ マ グ 150, consonance chemical industry strain
Formula commercial firm system) and the mass parts twin-roll machine of zinc oxide 5.0 kneaded 20 minutes below 60 DEG C.Afterwards, the mixture is dissolved
In the mixed solution being made up of the mass parts of MEK 100.0, the mass parts of ethyl acetate 150.0 and the mass parts of hexamethylene 150.0, obtain
Rubber solutions.
The resin solution and the rubber solutions are uniformly mixed with agitator, the combination of neoprene bonding agent is obtained
The mass parts of thing 611.0.The solid constituent of the neoprene adhesive composite is 26.4 mass %.
[comparative example 3]
In comparative example 3, in addition to using resin F, implement and the same operation of comparative example 2, obtain neoprene and glue
Connect the mass parts of agent composition 611.0.The solid constituent of the neoprene adhesive composite is 26.4 mass %.
[comparative example 4]
In comparative example 4, in addition to using Resin A, implement and the same operation of comparative example 2, obtain neoprene and glue
Connect the mass parts of agent composition 611.0.The solid constituent of the neoprene adhesive composite is 26.4 mass %.
[comparative example 5]
The mass parts of resin G 50.0, the mass of toluene 50.0 are added in possessing the reaction unit of agitator and thermometer
Part, interior temperature is warming up to 50 DEG C, is allowed to dissolve.Afterwards, MgO (Kyowa Chemical Industry Co., Ltd's system, キ ョ ー ワ マ グ are added
150) the sequestration reaction of 3.5 mass parts and the mass parts of water 0.5, directly progress 5 hours, thereby obtains resol type phenol resin
The mass parts of chelate (resin solution 1) 104.0.
By by embodiment 1~11 and the content of each composition of the neoprene adhesive composite of the gained of comparative example 1~5 with
And the result of evaluating characteristics is shown in Table 2.
In addition, in table 2, シ ョ ウ プ レ Application AD is designated as to " シ ョ ウ プ レ Application AF is designated as " neoprene rubber by neoprene A "
Glue B ".
[evaluation]
Evaluating characteristics are implemented to the neoprene adhesive composite obtained by embodiment 1~11 and comparative example 1~5.
(1) evaluation of cementability, heat resistance and adherence
The evaluation of cementability and heat resistance is tested according to JIS K-6854-1994 T-shaped stripping adhesive strength and carried out.
(1-1) cementability
Using hairbrush on 25mm × 75mm areas of the polylith 25mm × 150mm prepared No. 11 canvas with 0.03g/
cm2Amount coating neoprene adhesive composite.Afterwards, place 1 hour at room temperature.The operation is repeated at same position
After 3 times, place 20 minutes at room temperature.Afterwards, every 2 pieces of the canvas for being coated with neoprene adhesive composite is fitted,
So that composition is located at inner side, unidirectionally crimped 5 times with 5kg hand roller.Afterwards, in thermostatic constant wet chamber (25 DEG C, humidity 60%)
Middle maintenance 1 hour, has made early strength measure test film.Further early strength measure is conserved 1 week with test film, system
Normality intensity and high-temperature capability measure test film are made.
Then, with Compression and Expansion testing machine テ Application シ ロ Application (registration mark, Baldwin company of Japan (East Yang ボ ー Le
ドウィン societies) system) under 25 DEG C of atmosphere with the velocity determination of 200mm/ minutes T-shaped stripping adhesive strength.Carry out 5 surveys
It is fixed, value is averaged as the peel strength under 25 DEG C of atmosphere.(early strength and normality are strong for peel strength under 25 DEG C of atmosphere
Degree) it is higher, then it represents that and cementability is more excellent.
(1-2) heat resistance
High-temperature capability measure placed 20 minutes with test film under 80 DEG C of air atmosphere.Then, in 80 DEG C of gas
T-shaped stripping adhesive strength was determined with the testing machine with the speed of 200mm/ minutes under atmosphere.5 measure are carried out, are averaged
Value is used as the peel strength under 80 DEG C of atmosphere.Peel strength under 80 DEG C of atmosphere is higher, then it represents that heat resistance is more excellent.
(1-3) adherence
Thickness coating neoprene bonding agent respectively with 250 μm on the surface of multiple pieces of glass plate and brown paper is combined
Thing.Place it in thermostatic constant wet chamber's (25 DEG C, humidity 60%), fitted on a glass brown paper with the interval of 10 minutes,
The time untill can not being bonded is measured to, the adhesion time is used as.The adhesion time is longer, then it represents that adherence is more excellent.
(2) Form aldehyde release speed evaluation
Form aldehyde release speed trial according to JIS A-1901-2003 " VOC (VOC) of construction material,
Formaldehyde and other carbonyls release assay method-small chamber method " is carried out.
[table 2]
Result as shown in Table 2 is understood, compared with the neoprene adhesive composite of embodiment 1~11, novolaks
Type phenolic resin is not the comparative example 1 of the resin as obtained by reacting phenols and aldehydes in the presence of the salt of weak acid of divalent metal
The poor adherence of neoprene adhesive composite.In addition we know, novolak phenolics are not in the weak of divalent metal
The neoprene adhesive composite of carboxy-modified neoprene B comparative example 2~3 is manufactured and is free of in the presence of hydrochlorate
Early strength and poor adherence.In addition, understanding that the neoprene of the comparative example 4 without carboxy-modified neoprene B glues
Connect the early strength and normality intensity difference of agent composition.Also know, without carboxy-modified neoprene B but containing resol type phenol
Urea formaldehyde, the other conditions also neoprene adhesive composite for having used resol type phenol resin of different comparative example 5
High-temperature capability and poor adherence, and release formaldehyde.Further, the neoprene rubber of embodiment 1~11 and comparative example 1~4 is confirmed
Glue sticking agent composition not release formaldehyde.
The possibility utilized in industry
The present invention is provided meets heat resistance and adherence, early strength and cementability are also excellent and do not discharge first simultaneously
The neoprene adhesive composite of aldehyde.
Claims (15)
1. neoprene adhesive composite, it is characterised in that include：
Neoprene,
Novolak phenolics and
Organic solvent,
The neoprene contains carboxy-modified neoprene,
The novolak phenolics are made in the presence of the salt of weak acid of divalent metal obtained by phenols and aldehydes reaction
Resin.
2. neoprene adhesive composite as claimed in claim 1, it is characterised in that the neoprene contains 1 matter
Measure the mass % of the %~99 carboxy-modified neoprene.
3. neoprene adhesive composite as claimed in claim 1, it is characterised in that relative to the neoprene 100
Mass parts, containing 1 mass parts~100 mass parts the novolak phenolics.
4. neoprene adhesive composite as claimed in claim 1, it is characterised in that the novolak phenolics
Weight average molecular weight be 300~10000.
5. neoprene adhesive composite as claimed in claim 1, it is characterised in that relative to the neoprene 100
Mass parts, containing 0.1 mass parts~10 mass parts age resister.
6. neoprene adhesive composite as claimed in claim 1, it is characterised in that relative to the neoprene 100
Mass parts, amount to containing 0.1 mass parts~30 mass parts in metal oxide, metallic salt and their mixture
At least one.
7. neoprene adhesive composite as claimed in claim 6, it is characterised in that the metal oxide is magnesia
Or zinc oxide.
8. neoprene adhesive composite as claimed in claim 6, it is characterised in that the metallic salt be magnesium acetate or
Zinc acetate.
9. neoprene adhesive composite as claimed in claim 1, it is characterised in that solid constituent is 1 mass %~90
Quality %.
10. neoprene adhesive composite as claimed in claim 1, it is characterised in that without resol type phenol resin.
11. neoprene adhesive composite as claimed in claim 1, it is characterised in that the carboxy-modified neoprene
It is to mix rubber obtained by the metering system acid reaction of the mass parts of 0.1 mass parts~10 relative to the mass parts of Chloroprene monomer 100
Glue.
12. neoprene adhesive composite as claimed in claim 1, it is characterised in that the organic solvent contain toluene,
Dimethylbenzene, MEK, methylisobutylketone, hexane, hexamethylene, 2- Methyl-1-pentenes, ethyl acetate, acetone and rubber are with waving
At least one of hair oil.
13. neoprene adhesive composite as claimed in claim 1, it is characterised in that the neoprene contains 40 matter
Measure the mass % of the %~100 carboxy-modified neoprene.
14. neoprene adhesive composite as claimed in claim 1, it is characterised in that relative to the neoprene 100
Mass parts, containing 40 mass parts~90 mass parts the novolak phenolics.
15. neoprene adhesive composite as claimed in claim 1, it is characterised in that the salt of weak acid of the divalent metal
It is to be selected from Ca, Mg, Zn, Mn and Pb divalent metal and selected from acetic acid, formic acid, the salt of the weak acid of boric acid, relative to the phenols
100 mass parts, the addition of the salt of weak acid of divalent metal is the mass parts of 0.1 mass parts~80.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015029803A JP6589232B2 (en) | 2015-02-18 | 2015-02-18 | Chloroprene rubber adhesive composition |
| JP2015-029803 | 2015-02-18 | ||
| PCT/JP2016/050961 WO2016132782A1 (en) | 2015-02-18 | 2016-01-14 | Chloroprene rubber adhesive composition |
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| CN107207926A true CN107207926A (en) | 2017-09-26 |
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| CN201680010027.6A Pending CN107207926A (en) | 2015-02-18 | 2016-01-14 | Neoprene adhesive composite |
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|---|---|
| JP (1) | JP6589232B2 (en) |
| CN (1) | CN107207926A (en) |
| TW (1) | TW201636410A (en) |
| WO (1) | WO2016132782A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109021863A (en) * | 2018-06-27 | 2018-12-18 | 朱宇浩 | A kind of formula of Phenolic resin-chloroprene rubber adhesive |
| CN109971393A (en) * | 2019-03-26 | 2019-07-05 | 福清市南宾树脂有限公司 | A kind of neoprene glue spraying and preparation method thereof that the high temperature resistant operating time is long |
| CN116463080A (en) * | 2023-03-02 | 2023-07-21 | 常熟市江南粘合剂有限公司 | Neoprene adhesive and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109337610A (en) * | 2018-10-19 | 2019-02-15 | 海鹰企业集团有限责任公司 | A kind of formula of metal adhesive glue and its application |
| WO2023090008A1 (en) * | 2021-11-17 | 2023-05-25 | 株式会社ブリヂストン | Adhesive composition, organic fibrous material, rubber article, organic fiber/rubber composite, and tire |
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- 2016-01-14 WO PCT/JP2016/050961 patent/WO2016132782A1/en active Application Filing
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109021863A (en) * | 2018-06-27 | 2018-12-18 | 朱宇浩 | A kind of formula of Phenolic resin-chloroprene rubber adhesive |
| CN109971393A (en) * | 2019-03-26 | 2019-07-05 | 福清市南宾树脂有限公司 | A kind of neoprene glue spraying and preparation method thereof that the high temperature resistant operating time is long |
| CN116463080A (en) * | 2023-03-02 | 2023-07-21 | 常熟市江南粘合剂有限公司 | Neoprene adhesive and preparation method thereof |
| CN116463080B (en) * | 2023-03-02 | 2024-01-30 | 常熟市江南粘合剂有限公司 | Neoprene adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016132782A1 (en) | 2016-08-25 |
| TW201636410A (en) | 2016-10-16 |
| JP2016150994A (en) | 2016-08-22 |
| JP6589232B2 (en) | 2019-10-16 |
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