CN103131351A - Binder composition - Google Patents
Binder composition Download PDFInfo
- Publication number
- CN103131351A CN103131351A CN2012104917699A CN201210491769A CN103131351A CN 103131351 A CN103131351 A CN 103131351A CN 2012104917699 A CN2012104917699 A CN 2012104917699A CN 201210491769 A CN201210491769 A CN 201210491769A CN 103131351 A CN103131351 A CN 103131351A
- Authority
- CN
- China
- Prior art keywords
- mass parts
- caking agent
- sovprene
- agent
- adhesive composite
- 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.)
- Granted
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The purpose of the invention is to provide a polychloroprene solvent binder composition which is long in adaptable period and excellent in bonding performance. In per 100 parts by weight of the polychloroprene polymer, 1-30 parts by weight of polyoxyethylene modified polyisocyanate by solid component conversion and 150-1900 parts by weight of organic solvent are mixed. According to requirements, 0.05-10 parts by weight of zinc oxide and/or 5-100 parts by weight of tackifying resin can be mixed in per 100 parts by weight of the polychloroprene polymer.
Description
Technical field
The present invention relates to the adhesive composite that the solvent take the chloroprene based polymer as principal constituent is.
Background technology
The sovprene solvent is that caking agent refers to sovprene is dissolved in organic solvent and the caking agent made.Sovprene is that polar polymer, force of cohesion are high, thereby the solvent take sovprene as principal constituent is that caking agent is used in the bonding of the various materials such as timber, rubber, plastics, metal.In addition, known to improving the thermotolerance of caking agent, the technology of weather resistance with the isocyanate compound that has two above isocyanate group in 1 molecule as solidifying agent.
For example, put down in writing the technology of the binary liquid shape caking agent that when relating to vulcanized rubber bonding, the solidifying agent that has the isocyanate compound (low molecular compound) of two above isocyanate group in host take sovprene as principal constituent and 1 molecule is combined in patent documentation 1.In addition, put down in writing in patent documentation 2 and related to the reaction product (containing the isocyanate group hydrocarbon resin) that contains hydroxyl hydrocarbon resin and polyfunctional isocyanate's compound and sovprene as the technology of the caking agent of principal constituent.
On the other hand, put down in writing the binary liquid shape caking agent that relates to the host that to contain rubber combination take sovprene as principal constituent and organic solvent, combine with the solidifying agent of isocyanate compound in patent documentation 3 as the technology of travelling belt with caking agent.In this patent documentation 3, isocyanate compound uses triphenyl methane-triisocyanate, tri o cresyl thiophosphate-(to isocyanate group-phenyl) ester, 4 ', the low molecular compound that has a plurality of isocyanate group in 1 molecules such as 4-diphenylmethanediisocyanate.
And then, put down in writing the caking agent that is formed by the polyol compound that does not have the chloroprene unit in isocyanate-terminated prepolymer, the liquid sovprene with number-average molecular weight 500 ~ 10000 of hydroxyl, molecule and inorganic filler in patent documentation 4.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 63-27534 communique
Patent documentation 2: Japanese kokai publication hei 5-239424 communique
Patent documentation 3: TOHKEMY 2001-316656 communique
Patent documentation 4: Japanese kokai publication sho 58-21470 communique
Summary of the invention
The problem that invention will solve
Yet, the reaction that in these patent documentations 1 ~ 4, the caking agent of record exists sovprene and isocyanate compound soon or the reaction of the compounding agent with hydroxyl, amino etc. in caking agent and isocyanate compound fast, the problem that working life is short.If the working life of caking agent is short, wide, coating activity duration of surface covered when long, must often just mix host and solidifying agent in several hours, thereby operating efficiency is poor.Herein, " working life " refers to host sovprene solution with after the solidifying agent isocyanate compound mixes, the time of keeping the viscosity that can be coated with.
On the other hand, in patent documentation 4, the technology of record is the caking agent that does not contain organic solvent, thereby has in the nonvolatile advantage of operation field organic solvent.Yet the liquid sovprene that the polymerization degree is low and the speed of response of isocyanate compound are slow, thereby are that caking agent is compared with solvent, and curing adhesive is spended time more.Because caking agent is aqueous, must become solid after bonding when being coated with.That is, when becoming the solid spended time, need the long period just show sufficient bonding force and can use.
Therefore, the object of the invention is to, it is adhesive composite that the sovprene solvent that working life is long, bonding force is excellent is provided.
For the scheme of dealing with problems
The inventor conducts in-depth research in order to solve aforesaid problem, found that, by the polyoxyethylene groups modified polyisocyanate to chloroprene polymer compounding specified quantitative, the sovprene solvent that can access bonding force and storage stability excellence is adhesive composite, and then has completed the present invention.
That is, sovprene solvent of the present invention is in adhesive composite, contains with respect to the chloroprene polymer of 100 mass parts polyoxyethylene groups modified polyisocyanate, 150 ~ 1900 mass parts organic solvents that are scaled 1 ~ 30 mass parts with solids component.
In addition, in this adhesive composite, as required can also be with respect to the zinc oxide of chloroprene polymer compounding 0.05 ~ 10 mass parts of 100 mass parts and/or the tackifying resin of 5 ~ 100 mass parts.
And then the isocyanate group containing ratio of aforementioned polyoxyethylene groups modified polyisocyanate can be 3 ~ 24%.
And then, in addition, with respect to the chloroprene polymer of 100 mass parts, organic solvent content can be made as 200 ~ 1000 mass parts.
And then in addition, as aforementioned tackifying resin, can use softening temperature is the tackifying resin of 80 ~ 150 ℃.
The effect of invention
According to the present invention, can realize that the sovprene solvent that working life is long, bonding force is excellent is caking agent.
Embodiment
Below, the specific embodiment of the present invention is elaborated.Need to prove, the present invention is not limited to the embodiment of following explanation.
In the adhesive composite of present embodiment, contain with solids component with respect to the chloroprene polymer of 100 mass parts and be scaled the polyoxyethylene groups modified polyisocyanate of 1 ~ 30 mass parts, the organic solvent of 150 ~ 1900 mass parts.
[chloroprene polymer]
Chloroprene polymer refer to the homopolymer of chlorbutadiene (below be designated as chloroprene) or chloroprene and can with the multipolymer of other monomer of chloroprene copolymerization.
As can with other monomer of chloroprene copolymerization, for example can list 2,3-, two chloro-1,3-butadienes, 1-chloro-1,3-butadiene, sulphur, methacrylic acid and ester class thereof, acrylicacidandesters class, also can use as required two or more.When being used in combination the monomer except chloroprene, its input amount is preferably 0.01 ~ 5 mass parts in monomer total 100 mass parts.
Chloroprene polymer is by above-mentioned monomer emulsion polymerization is obtained.Be used for the common materials such as anionic property compound that the emulsifying agent of letex polymerization and/or letex polymerization that dispersion agent can be chloroprene use, nonionic compound, cationic compound, be not particularly limited.
As the object lesson of anionic property compound, carboxylic acid type, sulfuric acid ester type etc. are arranged, be the condenses etc. of alkylsulfonate, alkyl aryl sulfate, sodium naphthalene sulfonate and the formaldehyde of 8 ~ 20 such as an alkali metal salt that can list sylvic acid, carbon number.Object lesson as the nonionic compound; can list polyvinyl alcohol or its multipolymer multipolymer of acrylamide (for example with), polyvinyl ether or its multipolymer multipolymer of toxilic acid (for example, with), Voranol EP 2001, polyoxyethylene alkylphenol, sorbitan-fatty acid ester, polyoxyethylene acyl ester etc.
As the object lesson of cationic compound, aliphatics amine salt, aliphatic quaternary ammonium salt etc. are arranged, such as listing octadecyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, dilauryl alkyl dimethyl ammonium chloride etc.
Wherein, most preferably use an alkali metal salt of sylvic acid.
With respect to total 100 mass parts of initial input monomer, the input amount of an alkali metal salt of the emulsifying agent during letex polymerization and/or rosin as disperser acid is preferably 0.5 ~ 20 mass parts.During less than 0.5 mass parts, emulsifying power is insufficient; When surpassing 20 mass parts, the foaming in polymerization becomes problem, may cause detrimentally affect to the physical property of final adhesive composite.
The condition of letex polymerization is not particularly limited, and can control molecular weight, molecular weight distribution, molecular end structure, crystallization speed by at random selective polymerization temperature, polymerization starter, chain-transfer agent, polymerization terminator, percent polymerization etc.
Polymerization temperature during letex polymerization is not particularly limited, and carries out smoothly in order to make polyreaction, preferably is made as 5 ~ 50 ℃.Initiator is organo-peroxides such as persulphate, tertbutyl peroxide such as Potassium Persulphate etc., is not particularly limited.
The kind of chain-transfer agent is not particularly limited, can use the chain-transfer agent of the letex polymerization that is generally used for chloroprene, such as using the known chain-transfer agents such as curing dialkyl group xanthate class, iodoform such as n-dodecyl mercaptan, the isometric chain alkyl thioalcohol class of uncle's lauryl mercaptan, dithiodiisopropyl xanthate, ethyl persulfide xanthate.
Polymerization terminator (stopper) is not particularly limited, and for example can use 2,6-tert-butyl-4-methyl-Phenol, thiodiphenylamine, azanol etc.
Final percent polymerization is not particularly limited, can be in 70 ~ 100% interior any adjustings.The removing of unreacted monomer (demonomerization) known method such as heated by decompression and carried out.
[polyoxyethylene groups modified polyisocyanate: be scaled 1 ~ 30 mass parts with solids component]
The polyisocyanates of the polyoxyethylene groups modification of compounding in the adhesive composite of present embodiment is following polyisocyanates: with (A) aliphatics and/or alicyclic vulcabond or the polyisocyanates (prepolymer) that is obtained by it, with (B) have an above hydroxyl and have the polyethylene glycols reaction of ethylene oxide repeating unit and the polyisocyanates that obtains.
As (A) aliphatics or alicyclic diisocyanate, can list tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, Isosorbide-5-Nitrae-vulcabond hexanaphthene etc.Especially hexamethylene diisocyanate, low due to the viscosity of the polyisocyanates that obtains, as easily to regulate caking agent viscosity, thereby most preferably.
As (B) polyethylene glycols, polyalkylene glycol monoalkyl ether, polyoxyethylene alkylidene group alkyl oxide, polyoxyethylene toluylene phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, cithrol, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene sorbitan fatty acid ester etc. are arranged.
The polyoxyethylene groups modified polyisocyanate is because the polyoxyethylene groups in compound (polyglycol chain) is brought into play function as emulsifying agent, thereby can be in water emulsion dispersion, at present, utilize as the solidifying agent with the water system caking agent of sovprene latex in raw material.Yet, be caking agent for complete moisture free solvent, do not use this solidifying agent, but low-molecular-weight isocyanate compound is used for solidifying agent.
On the other hand, use the polyisocyanates of high molecular as solidifying agent in the adhesive composite of present embodiment, thus the hydroxyl in minimizing chloroprene molecular chain and the reflecting point of isocyanate group; And then, with a part of isocyanate group of polyoxyethylene chain protection, its speed of response is controlled at lower level, thereby successfully extends working life.In addition, after bonding, therefore residual isocyanate base in bond layer can slowly be cured reaction by airborne moisture (moisture).
The isocyanate group containing ratio of polyoxyethylene groups modified polyisocyanate is 3 ~ 24% under the state (state that does not contain in fact the volatile components such as volatile vulcabond, solvent in polyisocyanates) of nonvolatile component 100%, is preferably 8 ~ 18%.As long as be that this scope just can maintain sufficient working life and the bonding force in all purposes.
" isocyanate group containing ratio " described herein can be measured by the method (with reference to following numerical expression 1) of JIS K 1603-1 defined.Need to prove, in following numerical expression 1, N
1Be isocyanate group containing ratio (%NCO), V
1Be hydrochloric acid consumption (mL), the V that needs in blank test
2The hydrochloric acid consumption (mL), the m that need in titration for sample
0Quality (g) for sample.
[numerical expression 1]
N
1=4.202×(V
1-V
2)×c/m
0
But with respect to the chloroprene polymer of 100 mass parts, the content of polyoxyethylene groups modified polyisocyanate can't obtain sufficient bonding force during with solids component conversion less than 1 mass parts; When surpassing 30 mass parts, sometimes may damage the flexible of caking agent overlay film.Therefore, with respect to the chloroprene polymer of 100 mass parts, the content of polyoxyethylene groups modified polyisocyanate is made as 1 ~ 30 mass parts that converts with solids component.
[organic solvent: 150 ~ 1900 mass parts]
In the adhesive composite of present embodiment, the organic solvent of compounding is not particularly limited, and considers that the solvability of chloroprene polymer is selected to get final product.Object lesson as organic solvent, toluene, dimethylbenzene, acetone, methylethylketone (MEK), vinyl acetic monomer, N-BUTYL ACETATE, hexanaphthene, methylene dichloride, tetrahydrofuran (THF) (THF), METHYLPYRROLIDONE (NMP) etc. can be listed, also two or more organic solvents can be mixed.
But with respect to the chloroprene polymer of 100 mass parts, when the compounding amount of organic solvent was less than 150 mass parts, solid component concentration and viscosity became too high, and screening characteristics reduces.In addition, with respect to the chloroprene polymer of 100 mass parts, when the compounding amount of organic solvent surpassed 1900 mass parts, the solid component concentration of adhesive composite became too low, and adhesiveproperties reduces.Therefore, with respect to the chloroprene polymer of 100 mass parts, the compounding amount of organic solvent is made as 150 ~ 1900 mass parts.
In addition, from the viewpoint of screening characteristics and adhesiveproperties, with respect to the chloroprene polymer of 100 mass parts, preferably the compounding amount with organic solvent is made as 200 ~ 1000 mass parts.
[zinc oxide: 0.05 ~ 10 mass parts]
In the adhesive composite of present embodiment, on the basis of aforesaid each composition, can also compounding zinc oxide.Chloroprene polymer is exposed under daylight or when at high temperature preserving for a long time, has the character of carrying out in time the desalination acid-respons.Zinc oxide plays the effect as the acid absorber of hydrochloric acid, so during compounding zinc oxide, can improve the storage stability of caking agent or suppress variable color.
With respect to the chloroprene polymer of 100 mass parts, preferably the content with zinc oxide is made as 0.05 ~ 10 mass parts.With respect to the chloroprene polymer of 100 mass parts, during compounding quantity not sufficient 0.05 mass parts of zinc oxide, the effect of the bonding force that can't be improved; In addition, when surpassing 10 mass parts and coming compounding, may hinder bonding between polymkeric substance, cause poor attachment.
The kind of zinc oxide is not particularly limited.For example, for the manufacture method of zinc oxide, the indirect method that the zinc fume oxidation that the metallic zinc gasification is formed is made is arranged; The direct method that by zinc ore reduction zinc limit, zinc fume oxidation that its gasification forms is made on the limit; The damp process of generate zinc carbonate at aqueous phase, its roasting being made etc.In addition, according to its manufacture method, the powder characteristicss such as the particle diameter of zinc oxide, surface-area, particle shape are different, can be with the zinc oxide of making by either method in the adhesive composite of present embodiment.
The particle shape of zinc oxide can be any in unsetting, porousness, particulate, spherical, laminar, needle-like, four needle-likes.In addition, be that coupling agent, aluminium are that coupling agent carries out surface treatment to zinc oxide with silane coupling agent, titanic acid ester before compounding is in the caking agent, can also seek the raising of bonding force.
[tackifying resin: 5 ~ 100 mass parts]
Can the compounding tackifying resin in the adhesive composite of present embodiment improve after coating soon binding property (viscosity), improve bonding force.It is normally used tackifying resin in the caking agent field that tackifying resin can use solvent, and its kind does not limit.
As the object lesson of tackifying resin, can list Gum Rosin, rosin ester resin, staybelite resin, polymerized rosin resin, α pinene resin, beta-pinene resin, terpene phenolic resin, C
5Cut through-stone oleo-resinous, C
9Cut through-stone oleo-resinous, C
5/ C
9Cut through-stone oleo-resinous, dicyclopentadiene (DCPD) through-stone oleo-resinous, alkyl phenolic resin, xylene resin, coumarone resin, coumarone-indene resin etc.For example, when being used for sole, parts bonding of footwear, consider heat-resistance adhesion, preferred softening temperature is the tackifying resin of 80 ~ 150 ℃.
But, with respect to the chloroprene polymer of 100 mass parts, during compounding quantity not sufficient 5 mass parts of tackifying resin, can't obtain the raising of initial bonding force and normality bonding force; In addition, when coming compounding over 100 mass parts, may damage the flexible of caking agent overlay film.Therefore, in the adhesive composite of present embodiment, with respect to the chloroprene polymer of 100 mass parts, the compounding amount of tackifying resin is made as 5 ~ 100 mass parts.
In addition, from the flexible viewpoint of bonding force and caking agent overlay film, with respect to the chloroprene polymer of 100 mass parts, preferably the compounding amount with tackifying resin is made as 20 ~ 80 mass parts.
The adhesive composite of present embodiment can be according to purposes and desired properties at random compounding thickening material, vulcanization accelerator, weighting agent (toughener), pigment, tinting material, antioxidant, UV light absorber, mould inhibitor, sanitas, antiseptic-germicide, softening agent, rust-preventive agent, polymkeric substance etc. except sovprene.
In addition, the working conditions of the adhesive composite of present embodiment is not particularly limited.As adherend, can list metal, timber, concrete, rubber, cloth, pottery etc., bonding such as the of the same race or xenogenesis of the dry goods that can be used for footwear (looped fabric of nylon, polyester, cotton etc., weave cotton cloth, non-woven fabrics), natural leather (ox-hide, kangaroo skin etc.), artificial leather (urethane, polyvinyl chloride (PVC) RESINS etc.), vulcanized rubber (SBR, CR, IR, IIR, NBR, BR), resin (foam or the non-foaies such as urethane, EVA) etc.
In addition, coating process and device specification are not particularly limited.Particularly, there are heavy curtain coating method, rod to be coated with method, rolling method, spray method etc.; And then, in rolling method, gravure rolling method, inverse type intaglio plate coating method etc. are arranged.The coating process that selection is suitable for purposes gets final product, for example, continuously, preferred rolling method in the purposes of coating equably, preferably pass through brush handwork in the purposes that surface covered is little as sole, small parts.
At this moment, compression bonding apparatus, crimping condition, press pressure are not particularly limited, the crimping operation after overlapping two adherends can be hot pressing or normal temperature press any.
The adhesive composite of present embodiment has the polyoxyethylene groups modified polyisocyanate of specified quantitative due to compounding, thereby to access the sovprene solvent that working life is long, bonding force is excellent be caking agent.
Embodiment
Below, list embodiments of the invention and comparative example, effect of the present invention is specifically described.
[embodiment 1]
In the reactor of 10 liters of internal volumes, in nitrogen atmosphere, drop into sodium salt 5 mass parts, 0.3 mass parts sodium hydroxide, sodium salt 0.6 mass parts of formaldehyde naphthalene sulfonic acid condenses, the 0.5 mass parts S-WAT of 100 mass parts water, sylvic acid, after their dissolvings, add while stirring 100 mass parts Chloroprene monomers, 0.25 mass parts n-dodecyl mercaptan.Use 0.1 mass parts Potassium Persulphate as polymerization starter, under nitrogen atmosphere, 10 ℃ of lower polymerizations, add the emulsion of thiodiphenylamine when final percent polymerization reaches 70%, stop polymerization.Under reduced pressure remove unreacted monomer, obtain the sovprene latex.This latex of lyophilize is made chloroprene polymer.
The preparation of＜caking agent 〉
Magnesium oxide (MgO) uses Kyowamag150 (Kyowa Chemical Industry Co., Ltd's manufacturing), zinc oxide uses zinc oxide JIS 2 (Zinc Oxide JIS 2, HakusuitechLtd. make), antioxidant 2,6-di-tert-butyl-4-methy phenol (BHT) uses Nocrac200 (the emerging chemical industry of imperial palace Co., Ltd. make), and tackifying resin uses the alkyl phenolic resin TAMANOL526 (Arakawa Chemical Industries, Ltd.'s manufacturing) of 115 ~ 130 ℃ of softening temperatures.
At first, 140 mass parts hexanaphthenes, 60 mass parts TAMANOL526,3 mass parts magnesium oxide were stirred 2 days with ball mill, make the cyclohexane solution of tackifying resin.Then, add 100 mass parts chloroprene polymers, 2 mass parts antioxidants (BHT), 3 mass parts magnesium oxide (MgO), 3 mass parts zinc oxide, 116.5 mass parts hexanaphthenes, 256.5 mass parts methylethylketones in the cyclohexane solution of this tackifying resin, stirred 2 days with ball mill, make the host of caking agent.
Add in above-mentioned host with respect to the chloroprene polymer of 100 mass parts is polyoxyethylene groups modified polyisocyanate (the isocyanate group containing ratio 16.6% of 10 mass parts, solids component 100%) (DURANATE WB40-100 (Asahi Chemical Corp)) as solidifying agent, forms adhesive A.
The evaluation test of＜bonding force 〉
At first, prepare two cotton ducks.The part of smearing caking agent is of a size of wide 25mm * long 50mm.These two adherends on both take glue spread as 2400wet-g/m
2The mode coating adhesive.After the placement open time of 30 minutes under 25 ℃, with both bondings, 10 pounds of rollers are come and gone 5 times carry out bonding.
Initial bonding force is that bonding is solidified the T-shaped stripping strength after 1 day afterwards.The normality bonding force is that bonding is solidified the T-shaped stripping strength after 10 days afterwards.Heat-resistance adhesion is that bonding is solidified the T-shaped stripping strength when peeling off after 10 days afterwards in 60 ℃ of atmosphere.The draw speed of normality bonding force and heat-resistance adhesion is 50mm/min.
The evaluation test of＜heat-resistant creep characteristic 〉
Be fixed on the top of stove after crimping through a bare terminal end of the test film (part of smearing caking agent is of a size of wide 25mm * long 25mm) of 5 days, keep interior 80 ℃ of stove.By the method for 180 ° of stripping tests, the counterweight of 500g is arranged on another bare terminal end, measure from counterweight is installed until the time that counterweight falls.This time is longer means that heat-resistance adhesion is higher.
The mensuration that＜viscosity changes 〉
Add solidifying agent in host, relatively after stirring 2 minutes under rotating speed 3000rpm in 23 ℃ of atmosphere after 10 minutes and the viscosity after 8 hours.
[embodiment 2]
It is polyoxyethylene groups modified polyisocyanate (the isocyanate group containing ratio 14.3% of 15 mass parts that the host identical with embodiment 1 is added with respect to the chloroprene polymer of 100 mass parts, solids component 100%) (DURANATE WT20-100 (Asahi Chemical Corp)) as solidifying agent, forms caking agent B.By the method evaluation caking agent B identical with embodiment 1.
[embodiment 3]
It is polyoxyethylene groups modified polyisocyanate (the isocyanate group containing ratio 11.3% of 22.3 mass parts that the host identical with embodiment 1 is added with respect to the chloroprene polymer of 100 mass parts, solids component 100%) (DURANATE WE50-100 (Asahi Chemical Corp)) as solidifying agent, forms caking agent C.By the method evaluation caking agent C identical with embodiment 1.
[embodiment 4]
By process similarly to Example 1,75 mass parts hexanaphthenes, 60 mass parts TAMANOL526,3 mass parts magnesium oxide were stirred 2 days with ball mill, make the cyclohexane solution of tackifying resin.Then, add 100 mass parts chloroprene polymers, 2 mass parts antioxidants (BHT), 3 mass parts magnesium oxide (MgO), 3 mass parts zinc oxide, 75 mass parts methylethylketones in the cyclohexane solution of this tackifying resin, stirred 2 days with ball mill, make the host of caking agent.
Add in above-mentioned host with respect to the chloroprene polymer of 100 mass parts is polyoxyethylene groups modified polyisocyanate (the isocyanate group containing ratio 16.6% of 10 mass parts, solids component 100%) (DURANATE WB40-100 (Asahi Chemical Corp)) as solidifying agent, forms caking agent D.By the method evaluation caking agent D identical with embodiment 1.
[embodiment 5]
By process similarly to Example 1,140 mass parts hexanaphthenes, 60 mass parts TAMANOL526,3 mass parts magnesium oxide were stirred 2 days with ball mill, make the cyclohexane solution of tackifying resin.Then, add 100 mass parts chloroprene polymers, 2 mass parts antioxidants (BHT), 3 mass parts magnesium oxide (MgO), 3 mass parts zinc oxide, 810 mass parts hexanaphthenes, 950 mass parts methylethylketones in the cyclohexane solution of this tackifying resin, stirred 2 days with ball mill, make the host of caking agent.
Add in above-mentioned host with respect to the chloroprene polymer of 100 mass parts is polyoxyethylene groups modified polyisocyanate (the isocyanate group containing ratio 16.6% of 10 mass parts, solids component 100%) (DURANATE WB40-100 (Asahi Chemical Corp)) as solidifying agent, forms caking agent E.By the method evaluation caking agent E identical with embodiment 1.
[embodiment 6]
The host of making caking agent by the formula identical with embodiment 4 and identical process.Add in this host with respect to the chloroprene polymer of 100 mass parts is polyoxyethylene groups modified polyisocyanate (the isocyanate group containing ratio 16.6% of 3 mass parts, solids component 100%) (DURANATE WB40-100 (Asahi Chemical Corp)) as solidifying agent, forms caking agent F.By the method evaluation caking agent F identical with embodiment 1.
[comparative example 1]
The host identical with embodiment 1 is added count the 27% vinyl acetic monomer solution (Desmodur RFE (Bayer company make) of three (4-isocyanate phenyl) thiophosphatephosphorothioate of 35 mass parts with respect to the chloroprene polymer of 100 mass parts with apparent mass, isocyanate group containing ratio 7.2%) as solidifying agent, form caking agent G, by process evaluation bonding force similarly to Example 1.Isocyanate group content in the caking agent of comparative example 1 is identical with embodiment 3.
[comparative example 2]
It is the prepolymer (DURANATED101 (Asahi Chemical Corp) of 12.8 mass parts that the host identical with embodiment 1 is added with respect to the chloroprene polymer of 100 mass parts, solid component concentration 100%, isocyanic ester containing ratio 19.7%) as solidifying agent, form caking agent H, by process evaluation bonding force similarly to Example 1, wherein, described prepolymer is to obtain by the condensation reaction of hexamethylene diisocyanate (HDI) with dibasic alcohol.This solidifying agent is the polyisocyanates that does not have through the polyoxyethylene groups modification.Isocyanate group content in the caking agent of comparative example 2 is identical with embodiment 3.
[comparative example 3]
It is the prepolymer (DURANATE24A-100 (Asahi Chemical Corp) of 10.7 mass parts that the host identical with embodiment 1 is added with respect to the chloroprene polymer of 100 mass parts, solid component concentration 100%, isocyanic ester containing ratio 23.5%) as solidifying agent, form caking agent I, by process evaluation bonding force similarly to Example 1, wherein, described prepolymer is the biuret type prepolymer of hexamethylene diisocyanate (HDI).This solidifying agent is the polyisocyanates that does not have through the polyoxyethylene groups modification.Isocyanate group content in comparative example 3 caking agents is identical with embodiment 3.
[comparative example 4]
With polyoxyethylene groups modified polyisocyanate (the isocyanate group containing ratio 16.6% in embodiment 1, solids component 100%) to change into the chloroprene polymer with respect to 100 mass parts be 35 mass parts to the addition of (DURANATE WB40-100 (Asahi Chemical Corp)), forms caking agent J.By the method evaluation caking agent J identical with embodiment 1.
[comparative example 5]
Polyoxyethylene groups modified polyisocyanate in not compounding embodiment 1 and form caking agent K.Estimate by the method identical with embodiment 1.
[comparative example 6]
By process similarly to Example 1,70 mass parts hexanaphthenes, 60 mass parts TAMANOL526,3 mass parts magnesium oxide were stirred 2 days with ball mill, make the cyclohexane solution of tackifying resin.Then, add 100 mass parts chloroprene polymers, 2 mass parts antioxidants (BHT), 3 mass parts magnesium oxide (MgO), 3 mass parts zinc oxide, 70 mass parts methylethylketones in the cyclohexane solution of this tackifying resin, stirred 2 days with ball mill, make the host of caking agent.
Add in above-mentioned host with respect to the chloroprene polymer of 100 mass parts is polyoxyethylene groups modified polyisocyanate (the isocyanate group containing ratio 16.6% of 10 mass parts, solids component 100%) (DURANATE WB40-100 (Asahi Chemical Corp)) as solidifying agent, forms caking agent L.By the method evaluation caking agent L identical with embodiment 1.
[comparative example 7]
By process similarly to Example 1,140 mass parts hexanaphthenes, 60 mass parts TAMANOL526,3 mass parts magnesium oxide were stirred 2 days with ball mill, make the cyclohexane solution of tackifying resin.Then, add 100 mass parts chloroprene polymers, 2 mass parts antioxidants (BHT), 3 mass parts magnesium oxide (MgO), 3 mass parts zinc oxide, 1000 mass parts hexanaphthenes, 860 mass parts methylethylketones in the cyclohexane solution of this tackifying resin, stirred 2 days with ball mill, make the host of caking agent.
Add in above-mentioned host with respect to the chloroprene polymer of 100 mass parts is polyoxyethylene groups modified polyisocyanate (the isocyanate group containing ratio 16.6% of 10 mass parts, solids component 100%) (DURANATE WB40-100 (Asahi Chemical Corp)) as solidifying agent, forms caking agent M.By the method evaluation caking agent M identical with embodiment 1.
With above following table 1 and the table 2 of the results are shown in.
[table 1]
[table 2]
By above-mentioned table 1 and table 2 as can be known, with the existing adhesive composite take the low-molecular-weight isocyanate compound as solidifying agent of comparative example 1 and comparative example 2 ~ 3 not compare as the adhesive composite of solidifying agent through the polyisocyanates of polyoxyethylene groups modification, the adhesive composite take the polyoxyethylene groups modified polyisocyanate as solidifying agent of embodiment 1 ~ 6 does not almost have viscosity to change after solidifying agent mixes, working life is long, and bonding force is excellent.In addition, the bonding force of the unsuitable adhesive composite of addition of the polyoxyethylene groups modified polyisocyanate of comparative example 4 ~ 7 and organic solvent is poor.
Claims (6)
1. a sovprene solvent is adhesive composite, it is characterized in that, with respect to the chloroprene polymer of 100 mass parts, contain with solids component and be scaled the polyoxyethylene groups modified polyisocyanate of 1 ~ 30 mass parts and the organic solvent of 150 ~ 1900 mass parts.
2. sovprene solvent according to claim 1 is adhesive composite, it is characterized in that, with respect to the chloroprene polymer of 100 mass parts, also contains the zinc oxide of 0.05 ~ 10 mass parts.
3. sovprene solvent according to claim 1 and 2 is adhesive composite, it is characterized in that, with respect to the chloroprene polymer of 100 mass parts, also contains the tackifying resin of 5 ~ 100 mass parts.
4. sovprene solvent according to claim 1 is adhesive composite, it is characterized in that, the isocyanate group containing ratio of described polyoxyethylene groups modified polyisocyanate is 3 ~ 24%.
5. sovprene solvent according to claim 1 is adhesive composite, it is characterized in that, with respect to the chloroprene polymer of 100 mass parts, organic solvent content is 200 ~ 1000 mass parts.
6. sovprene solvent according to claim 3 is adhesive composite, it is characterized in that, the softening temperature of described tackifying resin is 80 ~ 150 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011260268A JP5411915B2 (en) | 2011-11-29 | 2011-11-29 | Adhesive composition |
| JP2011-260268 | 2011-11-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103131351A true CN103131351A (en) | 2013-06-05 |
| CN103131351B CN103131351B (en) | 2017-12-08 |
Family
ID=48491820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210491769.9A Active CN103131351B (en) | 2011-11-29 | 2012-11-27 | Adhesive composite |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5411915B2 (en) |
| CN (1) | CN103131351B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245302A (en) * | 2017-08-06 | 2017-10-13 | 长沙小新新能源科技有限公司 | Guide-lighting glue of a kind of UV photocurings and preparation method thereof |
| CN111032765A (en) * | 2017-08-25 | 2020-04-17 | 日本瑞翁株式会社 | Latex composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6274062B2 (en) * | 2014-09-26 | 2018-02-07 | 日立金属株式会社 | Mixed chloroprene rubber adhesive |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1589303A (en) * | 2001-11-15 | 2005-03-02 | 电气化学工业株式会社 | Method for prolonging the pot life of two-part water-based polychloroprene adhesive |
| CN1726237A (en) * | 2002-12-19 | 2006-01-25 | 电气化学工业株式会社 | Polychloroprene latex, process for the production thereof and aqueous adhesive compositions |
| CN101151293A (en) * | 2005-03-30 | 2008-03-26 | 三井化学聚氨酯株式会社 | Two-component curable aqueous urethane-alkyd resin composition and use thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5359733A (en) * | 1976-04-30 | 1978-05-29 | Denki Kagaku Kogyo Kk | Production of chloroprene adhesive having increased heat resistance |
| JPS5821470A (en) * | 1981-07-31 | 1983-02-08 | Denki Kagaku Kogyo Kk | Adhesive composition |
| JPS62207316A (en) * | 1986-03-06 | 1987-09-11 | Denki Kagaku Kogyo Kk | Chloroprene rubber composition |
| JPH05179216A (en) * | 1991-12-27 | 1993-07-20 | Tosoh Corp | Polychloroprene adhesive composition |
| JPH05239424A (en) * | 1992-02-27 | 1993-09-17 | Nippon Oil Co Ltd | Polychloroprene adhjesive composition |
| JP2691961B2 (en) * | 1993-03-05 | 1997-12-17 | ノガワケミカル株式会社 | Modified chloroprene synthetic rubber adhesive composition |
| JP2000282001A (en) * | 1999-03-30 | 2000-10-10 | Mitsuboshi Belting Ltd | Adhesive composition for adhesion of polyolefin-based foam resin sheet and application of adhesion using the same |
| JP2001316656A (en) * | 2000-05-08 | 2001-11-16 | Bando Chem Ind Ltd | Adhesive and process for joining conveyer belts, and conveyer belt |
| JP3888965B2 (en) * | 2002-12-12 | 2007-03-07 | 電気化学工業株式会社 | Polychloroprene adhesive composition and adhesive structure |
-
2011
- 2011-11-29 JP JP2011260268A patent/JP5411915B2/en not_active Expired - Fee Related
-
2012
- 2012-11-27 CN CN201210491769.9A patent/CN103131351B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1589303A (en) * | 2001-11-15 | 2005-03-02 | 电气化学工业株式会社 | Method for prolonging the pot life of two-part water-based polychloroprene adhesive |
| CN1726237A (en) * | 2002-12-19 | 2006-01-25 | 电气化学工业株式会社 | Polychloroprene latex, process for the production thereof and aqueous adhesive compositions |
| CN101151293A (en) * | 2005-03-30 | 2008-03-26 | 三井化学聚氨酯株式会社 | Two-component curable aqueous urethane-alkyd resin composition and use thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245302A (en) * | 2017-08-06 | 2017-10-13 | 长沙小新新能源科技有限公司 | Guide-lighting glue of a kind of UV photocurings and preparation method thereof |
| CN111032765A (en) * | 2017-08-25 | 2020-04-17 | 日本瑞翁株式会社 | Latex composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5411915B2 (en) | 2014-02-12 |
| CN103131351B (en) | 2017-12-08 |
| JP2013112745A (en) | 2013-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20210198539A1 (en) | Two-component solventless adhesive compositions comprising an amine-initiated polyol | |
| US5387367A (en) | Nonaqueous polyisocyanate formulation | |
| TWI756219B (en) | Two-component solventless adhesive compositions comprising an amine-initiated polyol | |
| CN106903969B (en) | Method for forming a laminate comprising a two-part solventless adhesive composition comprising an amine-initiated polyol | |
| JP2020505493A (en) | Two-component solventless adhesive composition | |
| JP4959084B2 (en) | Carboxyimide having a carboxyl or carboxylate group | |
| CN101517025A (en) | Adhesive sheet for marking | |
| US6822048B1 (en) | Use of isocyanates in the preparation of highly viscous self-adhesive compositions | |
| CN108603084A (en) | Sticker and adhesive sheet | |
| CN114874738A (en) | Two-part solventless adhesive composition comprising an amine-initiated polyol | |
| CA2702309C (en) | Moisture curable isocyanate containing acrylic formulation | |
| TWI798376B (en) | Adhesives and synthetic leather | |
| CN103131351A (en) | Binder composition | |
| CN102994019A (en) | Aqueous dispersion pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet | |
| CA1136333A (en) | Pressure-sensitve adhesive | |
| JPH08120248A (en) | Pressure-sensitive acrylic adhesive composition | |
| JP4268557B2 (en) | Reactive hot melt adhesive | |
| JP4521026B2 (en) | Carbodiimides having thiocarbamic acid ester groups | |
| JP2012025852A (en) | Reactive hot-melt adhesive | |
| CN116194545A (en) | Adhesive composition and adhesive sheet | |
| CA2060947A1 (en) | Crosslinking agents for polymeric adhesives | |
| JPH0797560A (en) | Thermoplastic polyurethane resin adhesive | |
| CN111108166B (en) | Protective film made of a polyolefin support material, a primer and a radiation-crosslinkable hot-melt adhesive | |
| JP4673943B2 (en) | Water-dispersed pressure-sensitive adhesive composition, process for producing the same, and pressure-sensitive adhesive sheets | |
| CN112226193B (en) | Preparation method and application of water-based high-strength bi-component adhesive |
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 |
Address after: Tokyo, Japan, Japan Applicant after: DENKI KAGAKU KOGYO KK Address before: Tokyo, Japan, Japan Applicant before: Denki Kagaku Kogyo K. K. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |