CN102898568B - Polychloroprene latex and its manufacture method and water system bonding agent - Google Patents
Polychloroprene latex and its manufacture method and water system bonding agent Download PDFInfo
- Publication number
- CN102898568B CN102898568B CN201210265536.7A CN201210265536A CN102898568B CN 102898568 B CN102898568 B CN 102898568B CN 201210265536 A CN201210265536 A CN 201210265536A CN 102898568 B CN102898568 B CN 102898568B
- Authority
- CN
- China
- Prior art keywords
- bonding agent
- polychloroprene latex
- water
- polyvinyl alcohol
- water system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention provides excellent water resistance, the polyvinyl alcohol emulsifying polychloroprene latex of water system bonding agent suitable for requiring high water-fast bonding force and its manufacture method and water system bonding agent.In the presence of intramolecular has the polyvinyl alcohol of carboxyl, make chlorobutadiene individually or by chlorobutadiene and other monomers emulsion polymerization, form chloroprene latex.Then curing agent, metal oxide etc. are compounded in the chloroprene latex, water system bonding agent is formed.
Description
Technical field
Glued the present invention relates to polychloroprene latex and its manufacture method and using the water system of the polychloroprene latex
Connect agent.More specifically, it is related to the quality-improving technology of the polychloroprene latex manufactured with emulsion polymerization.
Background technology
The polychloroprene latex of polyvinyl alcohol is used in emulsifying agent（PVA emulsifying polychloroprene latex）Have as follows
Feature：With the excellent compatibility of the various compounding ingredients such as resin of tackification emulsion, thickener, the free degree for being compounded design is high, various
It is sticky excellent after being coated with adherend.PVA emulsifyings polychloroprene latex can effectively utilize these features for by glue
Used between the timber such as plywood, in the water system bonding agent that foamed thermal insulating is bonding with concrete etc..
But, these water system bonding agents are when drying, and bond layer surface has polyvinyl alcohol to ooze out sometimes, high in humidity
Place, the place being easily spontaneously wet out by water are in use, may cause poor attachment.Therefore, to having used polychloroprene latex
Water system bonding agent, the improvement of water-fast bonding force is have studied in various ways.
The improving technology of the conventional water-fast bonding force of water system bonding agent can be divided into substantially：（1）Make polychloroprene latex
In the method containing the additive beyond polyvinyl alcohol（For example, referring to patent document 1 ~ 3）；（2）Improve the knot of polychlorobutadiene
The method of structure（For example, referring to patent document 4）；（3）The method for improveing the structure of polyvinyl alcohol（For example, referring to patent document 5,
6）.
In these improving technologies, as（1）Example, as described in patent document 1, it is proposed that a kind of in the non-of specific structure
In the presence of ionization series emulsifying agent, the method for chloroprene emulsion polymerization is made under 0 ~ 20 DEG C of temperature range., can in this method
Obtain the polychloroprene latex of the excellent water system bonding agent of initial bonding force, normality bonding force, water-fast bonding force.
In addition, patent document 2 proposes one kind in the presence of polyvinyl alcohol, make the olefinic of chlorobutadiene and specified quantitative not
After saturated carboxylic acid emulsion co-polymerization, pH adjusting agent is added（Salt of weak acid）With the method for free radical scavenger.Described in the patent document 2
In manufacture method, its purpose also makes storage steady in addition to improving the water-fast bonding force of polychloroprene latex composition
It is qualitative good.And then, in the adhesive composite described in patent document 3, by being compounded thiocarbamide in polychloroprene latex
Compound, realizes the raising of water-fast bonding force.
As（2）Improving technology example, just like the manufacture of the polychloroprene latex composition described in patent document 4
Method like that, under conditions of polyvinyl alcohol and nonionic system emulsifying agent exist with specified quantitative, makes chlorobutadiene and olefinic insatiable hunger
With the method for carboxylic acid emulsion co-polymerization.In this method, the polychlorobutadiene glue that mass %, pH of gel content 10 ~ 70 is 6 ~ 9 has been obtained
Breast.
As（3）Improving technology example, just like the manufacture method of the polychlorobutadiene system latex described in patent document 5
Like that, the polyvinyl alcohol of 1 ~ 15 mole of % ethylene unit is contained as the method for emulsifying agent using intramolecular.In addition, patent document 6
It it is also proposed a kind of polychlorobutadiene glue for using the polyvinyl alcohol with 1.9 moles of more than % 1,2- diol bonds as emulsifying agent
The manufacture method of breast.In method described in these patent documents 5,6, except water-fast bonding force, contact, heat resistanceheat resistant are also achieved compacted
The raising of the adhesive properties such as denaturation.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-160804 publications
Patent document 2：Japanese Unexamined Patent Publication 2002-53703 publications（Japanese Patent Publication No. 4342706）
Patent document 3：Japanese Unexamined Patent Publication 2000-256511 publications（Japanese Patent Publication No. 4244253）
Patent document 4：Japanese Unexamined Patent Publication 2007-63370 publications
Patent document 5：Japanese Unexamined Patent Publication 2001-139611 publications
Patent document 6：Japanese Unexamined Patent Publication 2004-346183 publications
The content of the invention
Problems to be solved by the invention
However, according to foregoing improving technology, being glued using the water-fast of water system bonding agent of PVA emulsifying polychloroprene latex
Relay is improved, but abundant not enough.Specifically, in footwear the bonding of rubber components, the bipeltate and cloth of diving suit dress material
Bonding etc. require in the field of high water-fast bonding force, in addition it is also necessary to further improvement.
Therefore, it is a primary object of the present invention to the water there is provided a kind of excellent water resistance, suitable for requiring high water-fast bonding force
It is the polyvinyl alcohol emulsifying polychloroprene latex and its manufacture method and water system bonding agent of bonding agent.
The solution used to solve the problem
The present inventor has made intensive studies to solve foregoing problems, has as a result obtained opinion as follows：Recognize
The reasons why difficult for the improvement of water resistance in foregoing conventional PVA emulsifying polychloroprene latex is due to dry latex
When, drying the surface of epithelium has water miscible PVA to ooze out, and forms not water-fast PVA layers.This is used particularly in bonding agent
When planting polychloroprene latex, with foring the water-solubility PVA layer that the water capacity easily immerses on the interface of adherend, therefore it is easily caused
The reduction of water-fast bonding force.
Therefore, the present inventor is studied the point, is found by importing carboxyl in PVA strands, can
It is crosslinked with metal oxide, various curing agent, PVA's when drying latex so as to reduce oozes out.And it is it was found that logical
Cross and use the PVA as emulsifying agent, the water resistance of polychloroprene latex is improved, obtain excellent resistance to during as water system bonding agent
Water cementability, so as to complete the present invention.
That is, polychloroprene latex of the invention contains the homopolymer or chlorobutadiene of chlorobutadiene and being total to for other monomers
Polymers, carries out emulsion polymerization in the presence of intramolecular has the polyvinyl alcohol of carboxyl and obtains.
In the present invention, due to carrying out emulsion polymerization using the polyvinyl alcohol with carboxyl, by being compounded metal oxide, acyl
Hydrazine compound, compound that can be with carboxyl reaction containing amino-compound and isocyanate compound etc., so as to make poly- second
Enol is crosslinked.As a result, the water resistance of the drying epithelium of polychloroprene latex is improved.
In the polychloroprene latex, polyvinyl alcohol can for example have copolymerization units, the saponification degree of itaconic acid or maleic acid
The viscosity determined for 65 ~ 95mol% and with method specified in JIS K6726 is 3 ~ 60mPas.
In addition, the ratio of the unit based on carboxylic vinyl monomer in foregoing polyvinyl alcohol can for example be set to 0.1 ~ 2
Mole %.
And then, copolymer that also can be containing chlorobutadiene Yu carboxylic vinyl monomer.
In the manufacture method of the polychloroprene latex of the present invention, there is the presence of the polyvinyl alcohol of carboxyl in intramolecular
Under, make chlorobutadiene individually or chlorobutadiene and other monomers emulsion polymerization.
In the manufacture method, saponification degree can be used to be 65 ~ 95mol% and determined with method specified in JIS K6726
The polyvinyl alcohol of copolymerization units of the viscosity for 3 ~ 60mPas, with itaconic acid or maleic acid.
In addition, the polyvinyl alcohol for including 0.1 ~ 2 mole of units of % based on carboxylic vinyl monomer can be used.
And then, it for example can also make chlorobutadiene and carboxylic vinyl monomer emulsion polymerization.
The water system bonding agent of the present invention contains foregoing polychloroprene latex.
The bonding agent using emulsion polymerization is carried out in the presence of intramolecular has the polyvinyl alcohol of carboxyl due to being obtained
The polychloroprene latex of the excellent water resistance arrived, therefore the raising of water-fast cementability.
The effect of invention
According to the present invention, carried due to carrying out emulsion polymerization using the polyvinyl alcohol of specific structure, therefore water resistance can be obtained
It is high, as water system bonding agent when obtain the polychloroprene latex of excellent water-fast cementability.
Embodiment
The mode for implementing the present invention is described in detail below.In addition, the present invention is not implemented by following explanation
The limitation of mode.
1st embodiment
First, the polychloroprene latex to the 1st embodiment of the present invention is illustrated.The polychlorostyrene fourth of present embodiment
Diene rubber latex is by polyvinyl alcohol（Hereinafter also referred to PVA.）By the chloro- 1,3- butadiene of 2-（Hereinafter referred to as chlorobutadiene.）'s
Latex obtained from polymer emulsified（Emulsion）.
Also, the polychloroprene latex of present embodiment has the PVA of carboxyl as emulsifying agent by using intramolecular,
Make chlorobutadiene individually or chlorobutadiene carries out free-radical emulsion polymerization in water with other monomers and obtained.
Chloroprene polymer
In the chloroprene latex of present embodiment contained chloroprene polymer for chlorobutadiene homopolymer or
The copolymer of chlorobutadiene and other monomers.Herein, as can be with chlorobutadiene copolymerization other monomers, can for example include
2,3- bis- chloro-1,3-butadienes, 1- chloro-1,3-butadienes, sulphur, methacrylic acid and its esters, acrylicacidandesters class, also may be used
As needed using two or more.
It is further preferred, that chloroprene polymer contained in the polychloroprene latex of present embodiment is chlorine
The copolymer of butadiene and carboxylic vinyl monomer.If because make carboxylic vinyl monomer copolymerization,
When being compounded zinc oxide, these metal oxides of magnesia in bonding agent, divalent metal ion is crosslinked with carboxyl, can be made heat-resisting
Property, solvent resistance these adhesive properties improve.
If in addition, the PVA used in emulsifying agent carboxyl and the carboxyl of chloroprene polymer are crosslinked, making latex
Oozing out for PVA is not susceptible to when drying.Thus, polychloroprene latex water resistance improve, as water system bonding agent when obtain
Excellent water-fast cementability.
Wherein, as carboxylic vinyl monomer, most preferable acrylic acid, its addition is preferably in monomer totally 100
In mass parts, carboxylic vinyl monomer is 0.01 ~ 5 mass parts.Thus, it can make as adhesive property during bonding agent to enter one
Step is improved.
PVA
The PVA intramoleculars used during the polychloroprene latex for manufacturing present embodiment have carboxyl.Have as intramolecular
There is the PVA of carboxyl, for example, have the PVA of structure shown in following chemical formula 1 ~ 3, particularly from long-term maintenance polychloroprene latex
From the viewpoint of storage-stable, the PVA of the copolymerization units desirably with itaconic acid or maleic acid.Wherein, following chemistry
In formula 1 ~ 3, R is hydrogen or saturated hydrocarbyl, and X is hydrogen, sodium or potassium.
Chemical formula 1
Chemical formula 2
Chemical formula 3
This PVA has anti-to metal oxide, hydrazide compound, containing amino-compound and isocyanate compound etc.
Ying Xing, but do not reacted with chlorobutadiene.Therefore, the PVA with carboxyl does not react in polymerization with chlorobutadiene, only in compounding energy
Reacted when reaching the compound with carboxyl reaction.Therefore, when the PVA with carboxyl is used in emulsifying agent, it is possible to decrease make to gather
PVA when chloroprene latex is dried oozes out, and can improve the water resistance of epithelium.
Intramolecular has the PVA of carboxyl by making after vinyl acetate monomer and carboxylic vinyl monomer copolymerization, and saponification is simultaneously
Further cleaned as needed, dried and obtained.
As the vinyl acetate monomer now used, have no particular limits, vinyl formate, vinyl acetate can be included
Ester, propionate, vinyl valerate, caprate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, spy
Vinyl valerate and tertiary ethylene carbonate etc..In addition, in these, especially vinyl acetate due to the stability in polymerization it is excellent
Different and low boiling point, therefore be easily removed polymerization and terminate rear unreacted monomer.Therefore, it is desirable that vinyl acetate monomer uses second
Vinyl acetate.
By making carboxylic vinyl monomer and foregoing vinyl acetate monomer copolymerization, reactivity can be imported in PVA main chains
Carboxyl.The carboxylic vinyl monomer of copolymerization has no particular limits, for example, can include acrylic acid, methacrylic acid, bar
The unsaturation acids or its esters etc. such as beans acid, maleic acid, itaconic acid, fumaric acid, citraconic acid.
In addition, the ratio of the unit based on carboxylic vinyl monomer in PVA（Copolymerization amount）Do not limit specifically, base
More in the unit of carboxylic vinyl monomer, the amount of the water soluble group of gained PVA intramoleculars more increases, and water solubility is carried
It is high.But, when the unit based on carboxylic vinyl monomer is excessive, most carboxyl can not be anti-with zinc oxide, curing agent
Answer and remain, there is the worry of the water resistance reduction of bond layer.It is therefore preferable that carboxylic using being based on comprising 0.1 ~ 2 mole of %
The PVA of the unit of vinyl monomer.
On the other hand, during PVA manufacture, as needed, foregoing each monomer and other monomers copolymerization can also be made.Now, make
To be capable of the other monomers of copolymerization, olefines, acrylamide, carbon such as can include ethene, propylene, 1- butylene, isobutene
N- alkyl acrylamides, the N of atomicity 1 ~ 18, N- dialkylacrylamides, diacetone acrylamide, 2- acrylamide propane sulfonic acids
And its salt, acrylamide propyl dimethylamine and its acrylic amide such as salt or its quaternary salt, Methacrylamide, carbon number 1 ~ 18
N- alkyl methacrylamides, N, N- dialkyl methacrylamides, two acetone Methacrylamides, 2- Methacrylamides
Propane sulfonic acid and its salt, Methacrylamide diemethylamine and its methacryl such as salt or its quaternary salt amine, with carbon atom
The vinyl ethers such as alkyl vinyl ether, hydroxyalkyl vinylether, the alkoxyalkyl vinyl ethers of the alkyl chain length of number 1 ~ 18,
The N- vinylamides such as NVP, N- vinyl formamides, N- vinyl acetamides class, acrylonitrile, methyl-prop
Ethylene halide class, three such as the acrylonitrile such as alkene nitrile class, vinyl chloride, vinylidene chloride, PVF, vinylidene, bromine ethene, inclined bromine ethene
The allyls such as the vinyl silanes such as methoxy-ethylene base silane class, allyl acetate, allyl chloride, allyl alcohol, dimethallyl alcohol
The vinyl silane compounds and methylvinyl acetate etc. such as based compound, vinyl trimethoxy monosilane, but do not limit
Due to them.
In addition, the usage amount of these other monomers for being capable of copolymerization has no particular limits, preferably with respect to monomer total amount
For 1.0 × 10-3More than mol%, and less than 20mol%.
The polymerization of these monomers has no particular limits, can be using known free radical polymerisation process.Typically,
It can be manufactured by the polymerisation in solution using alcohol such as methanol, ethanol and isopropanols as solvent, polymerisation in bulk, emulsion can also be used and gathers
Conjunction, suspension polymerisation etc. are manufactured.In addition, when carrying out polymerisation in bulk or polymerisation in solution, continuous polymerization can be carried out, can also be gathered in batches
Close.And then, monomer can be added together, can be also separately added into, or also can continuously or intermittently be added.
The polymerization initiator used in radical polymerization has no particular limits, and can be used azodiisobutyronitrile, azo double
（2,4- methyl pentane nitriles）, azo it is double（4- methoxyl group -2,4- methyl pentane nitriles）Deng azo-compound, acetyl peroxide, peroxide
Change benzoyl, lauroyl peroxide, acetyl group peroxidating cyclohexylsulfonyl, 2,4,4- tri-methyl-amyl -2- benzoyl peroxide epoxides
The peroxide such as acetic acid esters, the di-isopropyl peroxydicarbonate, -2- ethylhexyls of dicetyl peroxydicarbonate two, dicetyl peroxydicarbonate
The peroxocarbonate such as diethoxy ethyl ester compound, new peroxide tert-butyl caprate (tert-butyl
Peroxyneodecanoate), peroxidating neodecanoic acid α-withered ester (α-cumyl peroxyneodecanoate), the peroxidating new last of the ten Heavenly stems
The peresters such as tert-butyl acrylate（perester）Known to compound, azobis dimethyl valeronitrile, azo bi-methoxy valeronitrile etc. certainly
By base polymerization initiator.
Polymeric reaction temperature has no particular limits, and can generally be set in 30 ~ 90 DEG C or so of scope.
On the other hand, Saponification Conditions when manufacturing PVA also have no particular limits, and will use polymer made from preceding method
With known method saponification.Typically, can be by the presence of base catalyst or acid catalyst, making the ester in molecule
Partial hydrolysis is carried out.Now, had no particular limits as the concentration of the copolymer in the alcohol of polymer solvent, it is generally desirable to
10 ~ 80 mass %.
As the base catalyst now used, for example can be used sodium hydroxide, potassium hydroxide, sodium methoxide, caustic alcohol and
Hydroxide, alkoxide of the alkali metal such as potassium methoxide etc..In addition, as acid catalyst, it is inorganic such as usable hydrochloric acid and sulfuric acid
The organic acids such as aqueous acid, p-methyl benzenesulfonic acid, but particularly desirably use sodium hydroxide.
And then, the temperature of saponification also has no particular limits, it is generally desirable to be preferably 10 ~ 70 DEG C, more preferably 30 ~
40 DEG C of scope.Reaction time has no particular limits, it is generally desirable to carried out in the range of 30 minutes ~ 3 hours.
PVA saponification degree is preferably 65 ~ 95mol%.When saponification degree is less than 65mol%, PVA is slack-off to the dissolution velocity of water,
Productivity ratio is reduced.When other saponification degree is more than 95mol%, because PVA emulsifiability is reduced, there is the emulsion that can not be stablized
The worry of polymerization.Wherein, defined saponification degree is the value determined with method specified in JIS K6726 herein.
The solution viscosity that PVA is determined with method specified in JIS K6726（The mass % of concentration 4 aqueous solution is at 20 DEG C
Viscosity）It is preferred for 3 ~ 60mPas.When the solution viscosity is less than 3mPas, the aqueous solution becomes easily to disperse.Separately
Outside, when solution viscosity is more than 60mPas, PVA is slack-off to the dissolution velocity of water or adhesion amount of inwall in dissolution vessel
Increase.
In addition, in the case that intramolecular has the PVA of modified group, method specified in JIS K6726 to be used determines poly-
When right, sometimes by the fully saponified pretreatment stage of unsaponified vinyl acetate unit crosslink it is insoluble and
The correct degree of polymerization can not be obtained.Therefore in the polychloroprene latex of present embodiment, JIS is provided instead of the degree of polymerization
The suitable scope of solution viscosity specified in K6726.Specifically, it is suitable poly- when not occurring insoluble in pre-treatment
Right scope is 200 ~ 2500.
When manufacturing the polychloroprene latex of present embodiment, it is generally desirable to which PVA addition is relative to being initially added list
The mass parts of total amount 100 of body, are set to 0.5 ~ 10 mass parts.Because when PVA addition is less than 0.5 mass parts, sometimes
Less than sufficient emulsifying ability, in addition, during more than 10 mass parts, the reduction of bonding agent water resistance is made sometimes.
Other emulsifying agents
It should be noted that in the polychloroprene latex of present embodiment, to improve storage-stable, prevent winter
For the purpose of freezing, also it can be combined using the emulsifying agent beyond PVA.Now the species of the emulsifying agent to being applied in combination is not special
Limitation, may be selected anionic property, nonionic, cationic it is any.
For example, as anionic emulsifier, there is carboxylic acid type, sulfuric acid ester type etc., for example, it can include the alkali gold of rosin acid
It is condensation product of the alkylsulfonate of 8 ~ 20, alkyl aryl sulfate, sodium naphthalene sulfonate and formaldehyde etc. to belong to salt, carbon number.
As the concrete example of non-ionic emulsifier, polyvinyl alcohol or its copolymer can be included（For example with acrylamide
Copolymer）, polyvinylether or its copolymer（For example with the copolymer of maleic acid）, polyoxyethylene alkyl ether, polyoxyethylene alkane
Base phenol, sorbitan alcohol fatty acid ester, polyoxyethylene acyl ester etc..
As the concrete example of cationic emulsifier, there are aliphatic amine salt, aliphatic quaternary ammonium salt etc., for example, can include ten
Eight alkyl trimethyl ammonium chlorides, DTAC, dilauryl ammonium chloride etc..
When wherein, using the emulsifying agent beyond PVA, preferably with respect to the mass parts of total amount 100 of monomer, its addition is set to
0.1 ~ 2.0 mass parts.Because when the addition of the emulsifying agent beyond PVA is less than 0.1 mass parts, cannot its addition effect
Really, in addition, during more than 2.0 mass parts, the water resistance reduction of the drying epithelium of polychloroprene latex can be made.
The polymerizing condition of chlorobutadiene
When manufacturing the polychloroprene latex of present embodiment, in the presence of intramolecular has the PVA of carboxyl, make neoprene
Diene is individually or chlorobutadiene carries out free-radical emulsion polymerization with other monomers in water.Now, any selective polymerization temperature is passed through
Degree, polymerization initiator, chain-transferring agent, polymerization terminator, aggregate rate etc., can control molecular weight, molecular weight distribution, gel to contain
Amount, molecular end structure, crystallization rate.
These polymerizing conditions have no particular limits, and such as polymerization temperature comes from the viewpoint for successfully carrying out polymerisation
See, be preferably set to 5 ~ 50 DEG C.In addition, the persulfate such as potassium peroxydisulfate, TBHP etc. can be used in initiator
Organic peroxide etc..
The material for the emulsion polymerization for being generally used for chlorobutadiene can be used in chain-transferring agent, such as usable n- dodecyl mereaptan,
Two sulphur such as the isometric chain alkyl thioalcohol class of tert-dodecyl mercaptan, dithiodiisopropyl xanthate, ethyl persulfide xanthate
Change chain-transferring agent known to dialkyl xanthogen esters, iodoform etc..In addition, being used as polymerization terminator（Polymerization inhibitor）, for example, can make
With 2,6- tert-butyl-4-methyl-Phenols, phenthazine and azanol etc..
Final aggregate rate also has no particular limits, and can arbitrarily be adjusted between 70 ~ 100%.In addition, unreacted monomer
Remove（Demonomerization）Carried out by method known to heating under reduced pressure etc..
Contained chlorobutadiene in the polychloroprene latex of present embodiment（Altogether）The preferred toluene insoluble composition of polymer
For 20 ~ 99%.If the bonding agent of the balancing good of initial bonding force and normality bonding force within the range, can be made.
As described in detail above, the polychloroprene latex of present embodiment due to had using intramolecular the PVA of carboxyl as
Emulsifying agent, by be compounded metal oxide, hydrazide compound, can be with carboxylic containing amino-compound and isocyanate compound etc.
The compound of base reaction, can be crosslinked PVA.Thus, the water resistance of the drying epithelium of polychloroprene latex is improved, and is used as water system
Excellent water-fast cementability is obtained during bonding agent.
2nd embodiment
Then, the water system bonding agent of the 2nd embodiment of the present invention is illustrated.The water system bonding agent of present embodiment
Contain the polychloroprene latex of foregoing 1st embodiment as principal component.
In the water system bonding agent of present embodiment, according to purposes and performance is required, in addition to polychloroprene latex, also
Metal oxide, resin of tackification, thickener, vulcanization accelerator, filler can be compounded（Reinforcing agent）, it is pigment, colouring agent, anti-oxidant
Agent, ultra-violet absorber, mould inhibitor, preservative, antiseptic, plasticizer, pH adjusting agent, defoamer, antirust agent, polychlorobutadiene
Polymer emulsion in addition etc..In addition, curing agent, which also can be combined, is made 2 liquid type bonding agents.
As the concrete example of metal oxide, zinc oxide can be included（The flowers of zinc）, magnesia etc..The metal oxide is in glue
When the viscosity of breast is high, can directly be added with pulverulence, but preferably with emulsifying agent make its in water emulsification/dispersion into after emulsion
It is compounded again.
As the concrete example of resin of tackification, rosin resin, rosin ester resin, hydrogenated rosin resin, polymerization pine can be included
Botany bar gum, α pinene resin, nopinene resin, terpene phenol resin, C5Cut through-stone oleoresin, C9Cut through-stone oleoresin, C5/
C9Cut through-stone oleoresin, DCPD through-stones oleoresin, alkyl phenol resin, xylene resin, coumarone resin, coumarone-indenes tree
Fat etc..
In addition, the adding method of resin of tackification has no particular limits, in order that it is equably compounded in bonding agent, it is excellent
Form slection into adding after emulsion again.As the manufacture method of the resin of tackification emulsion, have such as having and make in toluene using emulsifying agent
The resin dissolved in machine solvent heat decompression in water after emulsification/dispersion, by organic solvent while the method that removes and
It is ground into particulate and makes method of its emulsification/dispersion etc..Wherein, the former method of the smaller emulsion of particulate can preferably be made.
As the concrete example of thickener, polyacrylic, Polyacrylamide, HEUR systems can be included（By polycyclic oxygen second
Two ends of alkane are with the polymer obtained by hydrophobic grouping is blocked）Deng organic system thickener, such as hectorite（hectorite）, cover
De- soil（montmorillonite）Deng inorganic system's thickener as silicate compound.Among these, HEUR systems are due to a small amount of
The viscosity stability that addition can obtain after big thickening effect and compounding is excellent, therefore is suitable.
As vulcanization accelerator, thiocarbamide system, dithiocar-bamate, xanthates etc. can be included.It is used as thiocarbamide system
The concrete example of compound, can include ethylene thiourea, dibutyl thiourea, dilauryl thiocarbamide, N, N '-rhenocure CA, three
Methylthiourea（TMU）, N, N '-diethyl thiourea（EUR）Deng.
As the example of dithiocar-bamate, PZ, the sulphur of diethyl two can be included
For carbaminate, zinc dibutyl dithiocarbamate, N- zinc pentamethylene dithiocarbamates, dibenzyl dithio ammonia
Base zinc formate, cupric dimethyldithio carbamate（II）, ferric dimethyl dithiocarbamate（III）, DMDS generation
Carbamic acid tellurium（IV）Deng.As the example of xanthates, zinc butyl xanthate, zinc isopropyl xanthate, ethyl can be included
Xanthic acid gallium（III）Deng.
When on the other hand, for using 2 liquid type bonding agent of curing agent, it is generally desirable to use water dispersed isocyanate chemical combination
Thing is used as curing agent.Water dispersed isocyanate compound due to the moisture in its NCO and latex, PVA hydroxyl and
Carboxyl etc. is reacted, therefore the water resistance of bonding agent can be made further to improve.Low molecular isocyanate compound is in addition
Reacted at once with the water in latex when in polychloroprene latex, thus with the carboxyl of PVA intramoleculars reactivity not
Foot.On the other hand, water dispersed isocyanate compound is protected by hydrophilic radical due to NCO, thus with latex
The reaction of water is difficult to, and the carboxyl of PVA intramoleculars can be made reliably to be crosslinked, so that suitably as curing agent.
Herein, water dispersed isocyanate compound refer to it is being obtained by aliphatic and/or alicyclic diisocyanate,
Intramolecular has biuret, isocyanuric acid ester, carbamate, uretdione（uretdione）, allophanate
（allophanate）The compound of hydrophilic radical is imported with isostructural polyisocyanic acid ester polymer.That is, it is to add in water
And the self-emulsifying isocyanate compound that can be dispersed in water when stirring as particulate.
Here, as aliphatic and/or alicyclic isocyanate, for example, tetramethylene diisocyanate, five can be included
Methylene diisocyanate, hexamethylene diisocyanate（HDI）, trimethyl hexamethylene diisocyanate, lysine two it is different
Cyanate（LDI）, IPDI（IPDI）, hydrogenated xylene diisocyanate（Hydrogenate XDI）, toluene diisocyanate
Acid esters（TDI）, 4,4 '-methyl diphenylene diisocyanate（MDI）, polymeric MDI, XDI（XDI）, naphthalene two it is different
Cyanate（NDI）, PPDI（PPDI）, tetramethylxylene diisocyanate（TMXDI）, dicyclohexyl methyl hydride two
Isocyanates（HMDI）, isopropylidene it is double（4- cyclohexyl isocyanates）（IPC）, cyclohexyl diisocyanate（CHPI）, connection first
Phenylene diisocyanate（TODI）Deng.Wherein, HDI, MDI, IPDI, hydrogenation XDI industrially easily start with, and are good.
In addition, hydrophilic radical by make the emulsifying agent of the repeat unit with oxirane with it is foregoing by aliphatic and/or
A part for the strand for the polymer that alicyclic diisocyanate is obtained reacts and imported.As with oxirane
The emulsifying agent of repeat unit, if considering the dispersiveness to water, particularly preferred MPEG-550.
It is more by as defined in JIS K-7301 compared with being influenceed by starting compound as the effect of curing agent
The NCO containing ratio influence that method is calculated.In order to obtain good bonding force, the isocyanate compound used it is different
Cyanic acid ester group containing ratio is that 17 ~ 25 mass % are preferred.
And then, using water dispersed isocyanate compound as curing agent and when 2 liquid type bonding agent is made, with relative
Water dispersed isocyanate in the polychloroprene latex that 100 mass parts are calculated as with solid constituent in host, curing agent
It is preferred that compound is mixed in the way of solid constituent is calculated as 0.5 ~ 15 mass parts.Water dispersed isocyanate compound is not enough
During 0.5 mass parts, there is the worry of bonding force not enough, in addition, when addition is more than 15 mass parts, having after mixing host and curing agent
Working life（The time that can be used）The worry shortened.
As described in detail above, in the water system bonding agent of present embodiment, due to use the PVA that there is carboxyl using intramolecular as
The polychloroprene latex of emulsifying agent manufacture, therefore water-fast bonding force is excellent.
Embodiment
Hereinafter, examples and comparative examples of the present invention are enumerated, the effect to the present invention is specifically described.The present embodiment
In, having manufactured intramolecular has the PVA- of carboxyl（A）~（E）And the general PVA- without carboxyl（F）~（I）.Then, make
With each PVA of these embodiments and comparative example as emulsifying agent, the emulsion polymerization of polychlorobutadiene is carried out, in the PVA breasts of gained
Resin of tackification etc. is compounded in change type polychloroprene latex to make bonding agent, evaluates its bonding force.
PVA-（A）Manufacture
175g vinyl acetates, 780g methanol, 1.0g acetic acid and 0.83g are added in the reactor equipped with reflux condensing tube
Azodiisobutyronitrile, by reactor with being warming up to boiling point after nitrogen displacement.Afterwards, in reactor, continuously added through 14 hours
Plus 2100g vinyl acetates, 445g methanol, the mixed liquor of 7g itaconic acids and it polymerize it, aggregate rate stops poly- when reaching 95%
Close.
Then, methanol vapor is blown into while heating response device, removes unreacted vinyl acetate.Then, in institute
The methanol solution of sodium hydroxide is mixed in the methanol solution of polymer, carry out saponification at 35 DEG C of reaction temperature.Then,
After the saponification liquid of solidification in methyl alcohol case of wet attrition, filter slurry, in 90 DEG C of gill formula testing machine（Geer oven）
Middle drying 90 minutes, makes PVA-（A）.
PVA-（B）Manufacture
Added in the reactor equipped with reflux condensing tube 2900g vinyl acetates, 620g methanol, 22g itaconic acids and
2.5g azodiisobutyronitriles, by, with boiling point is warming up to after nitrogen displacement, aggregate rate stops polymerization when reaching 75% in reactor.
Then, methanol vapor is blown into while heating response device, removes unreacted vinyl acetate.Then, in institute
The methanol solution of sodium hydroxide is mixed in the methanol solution of polymer, carry out saponification at 35 DEG C of reaction temperature.Then,
After the saponification liquid of solidification in methyl alcohol case of wet attrition, filter slurry dries 2 small in 90 DEG C of gill formula testing machine
When, make PVA-（B）.
PVA-（C）Manufacture
Added in the reactor equipped with reflux condensing tube 2900g vinyl acetates, 620g methanol, 39.5g maleic acids and
2.5g azodiisobutyronitriles, by, with boiling point is warming up to after nitrogen displacement, aggregate rate stops polymerization when reaching 75% in reactor.
Then, methanol vapor is blown into while heating response device, removes unreacted vinyl acetate.Then, in institute
The methanol solution of sodium hydroxide is mixed in the methanol solution of polymer, carry out saponification at 35 DEG C of reaction temperature.Then,
After the saponification liquid of solidification in methyl alcohol case of wet attrition, filter slurry dries 2 small in 90 DEG C of gill formula testing machine
When, make PVA-（C）.
PVA-（D）Manufacture
Added in the reactor equipped with reflux condensing tube 1640g vinyl acetates, 500g methanol, 7.6g maleic acids and
2.0g azodiisobutyronitriles, by reactor with being warming up to boiling point after nitrogen displacement.When starting backflow, from reactor top 8
The mixed liquor of 510g vinyl acetates, 230g methanol and 30.6g maleic acids is little by little continuously added dropwise in hour, and aggregate rate reaches
Stop polymerization when 60%.
Then, methanol vapor is blown into while heating response device, removes unreacted vinyl acetate.In gained polymerization
The methanol solution of sodium hydroxide is mixed in the methanol solution of thing, saponification is carried out at 35 DEG C of reaction temperature.Then, it will solidify
Saponification liquid in methyl alcohol after case of wet attrition, filter slurry is dried 1 hour in 90 DEG C of gill formula testing machine, is made
PVA-（D）.
PVA-（E）Manufacture
Added in the reactor equipped with reflux condensing tube 1670g vinyl acetates, 1300g methanol, 30g fumaric acid and
2.0g azodiisobutyronitriles, by reactor with being warming up to boiling point after nitrogen displacement.When starting backflow, pass through from reactor top
The mixed liquor for 520g vinyl acetates, 270g methanol and 24.1g fumaric acid being little by little continuously added dropwise in 5 hours, aggregate rate reaches
Stop polymerization when 65%.
Then, methanol vapor is blown into while heating response device, removes unreacted vinyl acetate.Then, in institute
The methanol solution of sodium hydroxide is mixed in the methanol solution of polymer, carry out saponification at 35 DEG C of reaction temperature.Then,
After the saponification liquid of solidification in methyl alcohol case of wet attrition, filter slurry dries 90 points in 90 DEG C of gill formula testing machine
Clock, makes PVA-（E）.
PVA-（F）~（I）Manufacture
120g vinyl acetates, 560g methanol, 1 mass % first of 1.6g azodiisobutyronitriles are added in polymerisation tank
Alcoholic solution, by tank with being heated to boiling point after nitrogen displacement.Then, through 14 hours continuous addition 1720g methyl acetates,
1 mass % methanol solutions of 607g methanol, 406g azodiisobutyronitriles.Then, after continuous addition terminates 1 hour, acetic acid second is confirmed
The aggregate rate of alkene ester reaches 99%, stops polymerisation.
Then, unreacted vinyl acetate is removed by conventional method, resulting polymers is passed through using sodium hydroxide
After conventional method saponification, dried 90 minutes in gill formula testing machine at 90 DEG C.Now, regulation amount of sodium hydroxide, saponification are anti-
The temperature and time answered, makes the different PVA- of saponification degree（F）~（I）.These PVA-（F）~（I）Do not have carboxyl for intramolecular
Conventional PVA.
PVA specificity analysis
The modified polyvinylalcohol manufactured to preceding method（PVA-（A）~（I））With method as shown below, determine（a）Saponification
Degree,（b）Acetic acid sodium content,（c）The degree of polymerization,（d）Solution viscosity.
（a）Saponification degree：Determined according to JIS K6726.
（b）Acetic acid sodium content：Determined according to JIS K6726.
（c）The degree of polymerization：Determined according to JIS K6726.
（d）Solution viscosity：Determined according to JIS K6726.
The manufacture of polychloroprene latex
Then, using foregoing PVA-（A）~（I）, manufacture embodiment 1 ~ 5 and the polychloroprene latex of comparative example 1 ~ 4.Tool
For body, using 3 liters of reactor of internal volume, in stream of nitrogen gas, under 60 DEG C of temperature conditionss, dissolve 3.2 mass parts PVA
In 86 mass parts water.The polyvinyl alcohol water solution is cooled to after room temperature, add wherein 97 mass parts Chloroprene monomers,
3 mass parts methacrylic acids, 0.3 mass parts octyl mercaptan.40 DEG C are held it in, and uses potassium peroxydisulfate as initiator
It is polymerize.
Polymerization terminate after reaction solution in add the 20 mass % diethanol amine aqueous solution, by the pH of solution be adjusted to 7 it
Afterwards, unreacted monomer being removed under reduced pressure, and then being concentrated moisture evaporation under reduced pressure, obtaining solid component concentration is
50 mass % polychloroprene latex.Then, the species of PVA in the present embodiment is changed（PVA-（A）~（I））, and adjust pungent
The addition of base mercaptan, makes the different embodiment 1 ~ 5 of gel content and the polychloroprene latex of comparative example 1 ~ 4.
Then, the embodiment and each polychloroprene latex of comparative example made to preceding method, with side as shown below
Method determines solid component concentration and gel content.
Solid component concentration
By α of the quality of aluminium dish in itself, the quality of aluminium dish that is put into after 2ml polychloroprene latex samples is β, makes to be put into
Quality after the aluminium dish of latex sample is dried 1 hour at 125 DEG C is γ, is calculated according to following formula 1.
Formula 1
Solid component concentration (quality %)={ (γ-α)/(β-α) } × 100
Gel content（Toluene insoluble composition）
The gel content of embodiment and each polychloroprene latex of comparative example（Quality %）Obtained according to following formula 2.This
M in place, following formula 2allTo weigh the quality obtained afterwards by polychloroprene latex sample is freeze-dried.In addition, MgelTo incite somebody to action
Sample after this is freeze-dried is dissolved at 23 DEG C with toluene（It is adjusted to 0.6 mass %）After 20 hours, using centrifugal separator,
And then 200 mesh woven wire separating gel composition, by the gel component air-dry after in 110 DEG C of atmosphere dry 1 hour, weigh
Gained material and the quality obtained.
Formula 2
Gel content (quality %)=(Mgel/Mall)×100
Then, using embodiment and each polychlorobutadiene of comparative example, adhesive test is carried out.Specifically, relative to
Solid constituent, which converts, is calculated as the polychloroprene latex of 100 mass parts, is compounded the oxidation that 5 mass parts are calculated as with solid constituent conversion
Zinc emulsion（Great Qi Industrial Co., Ltd system, AZ-SW）, being converted with solid constituent is calculated as the terpene phenol resin emulsions of 40 mass parts
（Arakawa Chemical Industries, Ltd.'s system, TamanolE-100）, converted with solid constituent be calculated as 2 mass parts aqueous dispersions are made
Zinc isopropyl xanthate（Ouchi Shinko Chemical Ind Co., Ltd.'s system, Nocceler ZIX）, the μ of 5 mass parts average grain diameter 10
M, specific surface area 191m2/ g wet silicon dioxide（Tokuyama Corporation. systems, TokusilU）, with solid constituent
Conversion is calculated as the HEUR systems thickener of 0.1 mass parts（Rohm and Haas Japan Corporation. systems, RM-8W）, system
Make the host of bonding agent.Relative to the 100 mass parts host（wet）, mix 3 mass parts water dispersed isocyanates（Asahi
Kasei Chemicals Corporation. systems, WB40-100）, 2 liquid type bonding agents are made.
Then, respectively in two sheet of canvas（Bonding agent smears the size of part：Width 25mm × length 70mm）On, use brush
It is coated with 150g（wet）/m2Bonding agent, make its in 23 DEG C of atmosphere dry 3 hours after, 300g is coated with thereon with brush
（wet）/m2Bonding agent.After making it dry 5 minutes in 70 DEG C of atmosphere, fitted and crimped with hand roller.
Initial bonding force
Crimp after 1 day, with cupping machine with the draw speed of 200mm/ minutes, determined 180 ° of peel strengths.
Normality bonding force
Crimp after 7 days, with cupping machine with the draw speed of 200mm/ minutes, determined 180 ° of peel strengths.
Water resistance bonding force
Crimp after 1 day, soaked 7, then surveyed with cupping machine with the draw speed of 200mm/ minutes in pure water
Fixed 180 ° of peel strengths.
Evaluation result above is shown in table 1 below in the lump.
Table 1
As shown in Table 1 above, it can confirm：There is the PVA- of carboxyl using intramolecular（A）~（I）The embodiment 1 being polymerize
~ 5 polychloroprene latex and the PVA- for not having carboxyl using intramolecular（F）~（I）Comparative example 1 ~ 4 polychlorobutadiene
Latex is compared, and bonding force when being made bonding agent is high, and particularly water-fast bonding force is excellent.
Claims (8)
1. a kind of water system bonding agent, it contains polychloroprene latex and water dispersed isocyanate compound, or containing poly-
Chloroprene latex, metal oxide and water dispersed isocyanate compound,
The polychloroprene latex contains the homopolymer or chlorobutadiene of chlorobutadiene and the copolymer of other monomers,
The polychloroprene latex is to carry out emulsion polymerization in the presence of the polyvinyl alcohol that intramolecular has carboxyl and obtain
's.
2. water system bonding agent according to claim 1, it is characterised in that the polyvinyl alcohol has itaconic acid or maleic acid
Copolymerization units, saponification degree be 65~95mol%, and with specified in JIS K 6726 method determine viscosity be 3~
60mPa·s。
3. water system bonding agent according to claim 1, it is characterised in that the polyvinyl alcohol in intramolecular with carboxyl
Vinyl acetate monomer is set to be obtained with carboxylic vinyl monomer copolymerization, in the polyvinyl alcohol, based on carboxylic ethene
The ratio of the unit of base monomer is 0.1~2 mole of %.
4. water system bonding agent according to claim 1, it is characterised in that contain chlorobutadiene and carboxylic vinyl list
The copolymer of body.
5. a kind of manufacture method of water system bonding agent, it is characterised in that by polychloroprene latex and water dispersed isocyanate
Compound is compounded, or polychloroprene latex, metal oxide and water dispersed isocyanate compound are compounded,
The polychloroprene latex is to make chlorobutadiene individually in the presence of intramolecular has the polyvinyl alcohol of carboxyl or chlorine
Butadiene is obtained with other monomers emulsion polymerization.
6. the manufacture method of water system bonding agent according to claim 5, it is characterised in that the polyvinyl alcohol has clothing health
Acid or maleic acid copolymerization units, saponification degree be 65~95mol%, and with specified in JIS K 6726 method measure viscosity
For 3~60mPas.
7. the manufacture method of water system bonding agent according to claim 5, it is characterised in that described that there is carboxyl in intramolecular
Polyvinyl alcohol vinyl acetate monomer is obtained with carboxylic vinyl monomer copolymerization, in the polyvinyl alcohol, based on containing
The ratio of the unit of the vinyl monomer of carboxyl is 0.1~2 mole of %.
8. the manufacture method of the water system bonding agent according to any one of claim 5~7, it is characterised in that make neoprene
Diene and carboxylic vinyl monomer emulsion polymerization.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011167613A JP2013028773A (en) | 2011-07-29 | 2011-07-29 | Polychloroprene latex, method for producing the same, and water-based adhesive |
| JP2011-167613 | 2011-07-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102898568A CN102898568A (en) | 2013-01-30 |
| CN102898568B true CN102898568B (en) | 2017-07-21 |
Family
ID=47571081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210265536.7A Active CN102898568B (en) | 2011-07-29 | 2012-07-27 | Polychloroprene latex and its manufacture method and water system bonding agent |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2013028773A (en) |
| CN (1) | CN102898568B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6490670B2 (en) * | 2014-04-18 | 2019-03-27 | デンカ株式会社 | Rubber latex, rubber latex composition and molded article |
| KR20200026915A (en) * | 2017-07-04 | 2020-03-11 | 덴카 주식회사 | Polymer Latex Compositions and Their Uses |
| CN107674150B (en) * | 2017-10-12 | 2019-07-26 | 山纳合成橡胶有限责任公司 | A kind of preparation method of high-stability carboxylic polychloroprene latex |
| CN110669160B (en) * | 2019-10-31 | 2022-05-20 | 重庆化医长寿化工集团有限公司 | Preparation method of neoprene latex for engineering water prevention |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3071253B2 (en) * | 1991-09-03 | 2000-07-31 | 株式会社クラレ | Dispersion stabilizer for emulsion polymerization |
| JPH06287360A (en) * | 1993-03-30 | 1994-10-11 | Denki Kagaku Kogyo Kk | Polychloroprene latex and its composition |
| JP3483957B2 (en) * | 1993-10-19 | 2004-01-06 | 電気化学工業株式会社 | Method for producing polychloroprene latex |
| JP3790525B2 (en) * | 1993-10-19 | 2006-06-28 | 電気化学工業株式会社 | Method for producing polychloroprene latex |
| JP2001139611A (en) * | 1999-11-17 | 2001-05-22 | Kuraray Co Ltd | Chloroprene latex and its preparation process |
| JP4342706B2 (en) * | 2000-08-08 | 2009-10-14 | 電気化学工業株式会社 | Polychloroprene latex composition and method for producing the same, and adhesive composition using the same |
| DE602004032133D1 (en) * | 2003-05-21 | 2011-05-19 | Denki Kagaku Kogyo Kk | PROCESS FOR PREPARING POLYCHLOROPRENATE LATEX AND COMPOSITION |
| JP2004346183A (en) * | 2003-05-22 | 2004-12-09 | Kuraray Co Ltd | Polychloroprene latex and its manufacturing method |
-
2011
- 2011-07-29 JP JP2011167613A patent/JP2013028773A/en active Pending
-
2012
- 2012-07-27 CN CN201210265536.7A patent/CN102898568B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102898568A (en) | 2013-01-30 |
| JP2013028773A (en) | 2013-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102898568B (en) | Polychloroprene latex and its manufacture method and water system bonding agent | |
| KR101612461B1 (en) | Vulcanisable compositions based on epoxy group-containing nitrile rubbers | |
| JP5905486B2 (en) | Vulcanizable composition based on nitrile rubber containing epoxy groups | |
| CN109952327A (en) | Acrylic copolymer and its cross-linking agent | |
| RU2614384C2 (en) | Vulcanisable compositions based on nitrile rubbers containing epoxy groups | |
| JP2004285143A (en) | Polyvinyl alcohol-based resin having 1,2-glycol bonds in side chains and method for producing the same | |
| JP4975939B2 (en) | Rubber mixtures comprising uncrosslinked and crosslinked rubbers and polyfunctional isocyanates based on polyurethane | |
| EP2386600B1 (en) | Cross-linking agent for nitrile rubbers containing isocyanate groups | |
| WO2006018870A1 (en) | Polyvinyl alcohol having 1,2-glycol bond in side chain and process for producing the same | |
| KR101551044B1 (en) | Compositions that can be vulcanized and that are based on nitrile rubbers containing epoxy groups | |
| JP6000124B2 (en) | Rubber adhesive composition containing vinylpyridine latex polymer containing nitrogen-containing monomer | |
| JP7192381B2 (en) | Rubber composition and its manufacturing method | |
| JP2012188489A (en) | Polychloroprene latex and production method therefor, and water-based adhesive | |
| CN110914352B (en) | Curable composition containing hydrogenated nitrile-diene-carboxylate copolymer and silica | |
| JP7470894B2 (en) | Rubber foam, its manufacturing method and uses | |
| JP6040751B2 (en) | Adhesive aid, RFL adhesive treatment liquid and rubber composition-fiber composite | |
| CN105121580A (en) | Adhesive agent composition | |
| WO2011125224A1 (en) | Copolymer latex for adhesive | |
| US20070010605A1 (en) | Process for preventing gel formation in lattices of hydrogenated, low molecular weight, functionalized elastomers | |
| JP2012176999A (en) | Aqueous adhesive | |
| JPH1143516A (en) | Chloroprene rubber for chloroprene rubber composition having excellent dynamic fatigue resistance, chloroprene rubber composition and boots made thereof | |
| JP2022067609A (en) | Rubber composition and vulcanized rubber | |
| JP2014173002A (en) | Vinyl chloride polymer latex composition and method for manufacturing the same as well as adhesion adjuvant, adhesive treatment liquid for a rubber composition-fiber composite, and rubber composition-fiber composite | |
| JP2006291043A (en) | Adhesive composition and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: Tokyo, Japan, Japan Applicant after: DENKI KAGAKU KOGYO KK Address before: Tokyo, Japan, Japan Applicant before: Denki Kagaku Kogyo K. K. |
|
| GR01 | Patent grant |