CN1429259A - Tackifier and adhesive composition - Google Patents
Tackifier and adhesive composition Download PDFInfo
- Publication number
- CN1429259A CN1429259A CN01809458A CN01809458A CN1429259A CN 1429259 A CN1429259 A CN 1429259A CN 01809458 A CN01809458 A CN 01809458A CN 01809458 A CN01809458 A CN 01809458A CN 1429259 A CN1429259 A CN 1429259A
- Authority
- CN
- China
- Prior art keywords
- tackifier
- vinyl polymer
- methyl
- vinyl
- adhesive composition
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/08—Copolymers of styrene
- C09J125/10—Copolymers of styrene with conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
A pressure-sensitive adhesive composition which is less apt to color and has high tackiness and high weatherability. The composition is produced from a tacky polymer, e.g., a (meth)acrylic resin or rubber, and a tackifier. The tackifier is obtained by polymerizing a vinyl monomer at 180 to 350 DEG C. The tackifier is incorporated in an amount of 5 to 200 parts by weight per 100 parts by weight of the tacky polymer.
Description
Technical field
The present invention relates to tackifier and the binder composition that comprises tackifier, wherein tackifier are a kind of components that can improve the tackiness agent bounding force.In binder composition, The present invention be more particularly directed to contact adhesive composition and hot-melt adhesive composition.
Background technology
In binder composition such as contact adhesive composition and hot-melt adhesive composition, add the bounding force that some tackifier can improve binder composition.
In the pressure sensitive adhesion sheet and pressure-sensitive adhesive tape of routine, coating contains the contact adhesive composition of (methyl) acrylic polymers as a kind of effective composition.And, in order to improve to body material such as polyolefinic bounding force, contact adhesive composition contains tackifier, (see the patent gazette of Japanese unexamined as Gum Rosin, terpine resin, petroleum resin, low molecule acrylic polymers, flat 1-98676, clear 64-60677 and clear 63-256672).
Yet the weathering resistance of contact adhesive composition that comprises the tackifier of being made up of low molecule acrylic polymers is also unsatisfactory.And, comprise the contact adhesive composition of the tackifier of forming by Gum Rosin, terpine resin or petroleum resin, not only its weathering resistance is unsatisfactory, and has not good color or color to change.These not satisfied weathering resistancies and not good discolouration are considered to cause owing to the residue that uses a large amount of polymerization starters, chain transfer agents to produce in the production process of tackifier or degradation production.
Conventional hotmelt will be introduced below.Usually, hotmelt is compared with Solvent Adhesive, in safety, Working environment and high productivity superiority is arranged.Hotmelt is widely used in bookbinding, packing, woodworking, building, automotive interior and the health industry.As representational hotmelt, the at present known tackiness agent of mainly forming by thermoplastic resin and tackifier, tackifier such as rosin compound, terpene compound or petroleum resin (are seen the patent gazette of Japanese unexamined, 63-213586).
When rosin compound, terpene compound or petroleum resin are used as tackifier, the tackiness agent of formation may variable color or during hot melt viscosity change, perhaps bonding back tackiness agent may only demonstrate not satisfied weathering resistance.When hydrogenant petroleum resin or hydrocarbon resin were used as tackifier, the binding property that tackifier may lack with the tackiness agent of the consistency of thermoplastic resin or formation may become very poor.
Summary of the invention
In the present invention, term " tackiness agent " comprises pressure sensitive adhesive and hotmelt.
The purpose of this invention is to provide a kind of binder composition, that is to say, have the contact adhesive composition and the hot-melt adhesive composition of gratifying weathering resistance and bounding force.
In order to achieve the above object, a first aspect of the present invention provides a kind of tackifier that comprise vinyl polymer.This polymkeric substance produces by polymerization of vinyl monomer in 180 ℃ of-350 ℃ of temperature ranges.The weight-average molecular weight of vinyl polymer is preferably 500 to 50,000.Vinyl polymer has (methyl) acryl monomer unit; this polymkeric substance is to form by the monomer that polymerization contains (methyl) acryl, and the unitary content of (methyl) acryl monomer is preferably 50 to 100 quality % in all monomeric units that constitute vinyl polymer.
Second aspect of the present invention provides a pressure-sensitive binder composition, and said composition comprises pressure-sensitive polymkeric substance and tackifier.These tackifier contain vinyl polymer, and this kind polymkeric substance produces by polymerization of vinyl monomer in 180 ℃ of-350 ℃ of temperature ranges.The weight-average molecular weight of vinyl polymer is 500 to 50,000.Vinyl polymer has (methyl) acryl monomer unit; this polymkeric substance is to form by the monomer that polymerization contains (methyl) acryl, and (methyl) acryl monomer unit content is preferably 50 to 100 quality % in all monomeric units that constitute vinyl polymer.
Pressure sensitive adhesion thing polymkeric substance should contain (methyl) acrylic polymers.(methyl) acrylic polymers should be a second-order transition temperature at (methyl) acrylic ester polymer of-80 ℃-0 ℃.In 100 parts of pressure-sensitive adhesive polymers, should mix 5 to 200 mass parts vinyl polymer tackifier.
A third aspect of the present invention provides a kind of hot-melt adhesive composition.This hot-melt adhesive composition comprises binder polymer and the tackifier that contain by the vinyl polymer that obtains at 180 ℃ of-350 ℃ of polymerization of vinyl monomers.Hot-melt adhesive composition should contain in 100 mass parts pressure-sensitive adhesive polymers, 5 to 200 mass parts tackifier.Binder polymer should be ethylene copolymer or phenylethylene-dialkene multipolymer.
A fourth aspect of the present invention provides a kind of method of making binder composition.This method is included in 180 ℃ of-350 ℃ of temperature ranges and prepares vinyl polymer tackifier and mixed ethylene based polyalcohol tackifier and pressure-sensitive adhesive polymers or binder polymer with stirring tank type reactor successive polymerization vinyl monomer.
The best mode that carries out an invention (first embodiment)
Describe contact adhesive composition now in detail according to first embodiment of the invention.In this manual, term " (methyl) vinylformic acid " meaning is acrylic or methacrylic acid, and " (methyl) acryl " meaning is acryl or methacryloyl.
At first, be described below tackifier.
Tackifier comprise by at 180 ℃ of-350 ℃ of vinyl polymers that polymerization of vinyl monomers forms.Vinyl monomer is not particularly limited; but the example of vinyl monomer includes the monomer of (methyl) acryl, as (methyl) methyl acrylate; (methyl) ethyl propenoate; (methyl) vinylformic acid n-propyl; (methyl) isopropyl acrylate; (methyl) n-butyl acrylate; (methyl) isobutyl acrylate; (methyl) Ethyl acrylate; (methyl) cyclohexyl acrylate; (methyl) 2-EHA; (methyl) vinylformic acid n-octyl; (methyl) Isooctyl acrylate monomer; (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems; (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems; (methyl) decyl acrylate; (methyl) vinylformic acid; (methyl) Hydroxyethyl acrylate; (methyl) Propylene glycol monoacrylate; (methyl) vinylformic acid hydroxy butyl ester and (methyl) glycidyl acrylate.In addition, can use other monomers (vinyl monomer arbitrarily), as vinyl acetate, vinylbenzene, alpha-methyl styrene, (methyl) acrylamide, N hydroxymethyl acrylamide, N-methoxymethyl acrylamide, N-methoxyl group butyl acrylamide and (methyl) vinyl cyanide.
In all vinyl monomers, the vinyl monomer that has hydroxyl or carboxyl is preferred.By using this vinyl monomer, can obtain to have better thermotolerance and the contact adhesive composition that keeps relative high adherence.Preferred vinyl monomer is the ring compound monomer.By using the cyclic vinyl monomer, can obtain to have contact adhesive composition than high adhesion.Good especially is the alicyclic compound monomer, as (methyl) cyclohexyl acrylate.The monomeric content of cycloaliphatic vinyl is preferably 10 to 100 quality % in constituting polyvinyl all monomeric units, and good especially is 20 to 100 quality %.
Vinyl polymer should have in molecule by polymerization and have the monomer of (methyl) acryl and the monomeric unit that forms [below, be called (methyl) acryl monomer unit].The unitary content of (methyl) acryl monomer is preferably 50 to 100 quality % in constituting all monomeric units of vinyl polymer.When content was less than 50 quality %, the weathering resistance of synthetic contact adhesive composition was relatively poor relatively, and contact adhesive composition can fade.
Polymerization temperature is set at 180 ℃-350 ℃.Polymerization temperature is maintained in this scope, do not use polymerization starter to obtain relative low-molecular-weight vinyl polymer basically with chain-transfer agent.The vinyl polymer that generates plays good tackifier.When polymeric reaction temperature was lower than 180 ℃, polyreaction needed polymerization starter and chain-transfer agent.Therefore, in this case, the contact adhesive composition of unpleasant odor may be faded and produce to acquisition.And the weathering resistance of the contact adhesive composition of acquisition is relatively poor.When polymerization temperature surpasses 350 ℃, in polymerization process, decomposition reaction may occur, and the contact adhesive composition that produces can fade also.The preferable polymerization process of producing vinyl polymer is continuous bulk polymerization method and continuous solution polymerization method.Good especially method is to use the successive polymerization reaction method of stirring tank type reactor.By this polymerization of at high temperature carrying out, obtain having the vinyl polymer that small molecular weight distributes.And the contact adhesive composition that contains this vinyl polymer has the binding property that increases.Polymerization starter can be chosen use wantonly.In this case, the polymerization starter of use should be about 1 quality % of raw-material total mass or still less.
The weight-average molecular weight of vinyl polymer is preferably 500 to 50,000, is preferably 1,000 to 18,000.When weight-average molecular weight was lower than 500, vinyl polymer was soft and the hold facility of the contact adhesive composition of formation can be unsatisfactory.When weight-average molecular weight surpasses at 50,000 o'clock, vinyl polymer can become invalid tackifier.
Then, below binder polymer will be described.
Pressure-sensitive adhesive polymers (as, pressure sensitive adhesion resin or rubber is the main effective constituent of contact adhesive composition normally.The preparation of pressure-sensitive adhesive polymers is not restricted especially, and various known homopolymer or multipolymer can both use.Pressure-sensitive adhesive polymers comprises any pressure sensitive adhesive, and it comprises Solvent Adhesive, water-based (emulsion) tackiness agent, hotmelt and ultraviolet ray (UV) cure adhesive.Preferable pressure-sensitive adhesive polymers is (methyl) acrylic polymers.The content that contains the monomeric unit of (methyl) acryl in this polymkeric substance accounts for 50 to 100 quality % of all monomeric units that constitute polymkeric substance.This by using (methyl) acrylic polymers can obtain to have the contact adhesive composition of excellent weather resistance.
Pressure-sensitive adhesive polymers is by producing as emulsion polymerization.As the monomeric object lesson that is used for emulsion polymerization, that can mention has at the above-mentioned monomer that contains (methyl) acryl about mentioning in the description of tackifier.One or more are selected from these monomeric monomers and obtain (methyl) acrylic ester polymer through letex polymerization.In order to produce contact adhesive composition, should use 50 to 100 quality % to have the C of containing with excellent adhesion
1-C
4(methyl) alkyl acrylate of alkyl is as (methyl) acrylic polymers of monomeric unit.And, when use a spot of (methyl) vinylformic acid come instead of part contain (methyl) acryl select monomer the time, can obtain to contain the stable emulsion of improvement.
And, if desired, also can use the vinyl monomer arbitrarily of the vinyl acetate of mentioning when describing tackifier above comprising.In this case, the consumption of vinyl monomer should be limited in the fusible scope of not damaging (methyl) acrylic ester polymer arbitrarily.The second-order transition temperature of acrylic ester polymer should better be at-10 ℃ or lower at 0 ℃ or lower.When second-order transition temperature surpassed 0 ℃, the binding property of acrylic ester polymer, particularly viscosity can reduce and unfavorable.The lower limit of glass temperature range is not restricted especially, but is not less than-80 ℃ usually.And, for example,, can obtain to have (methyl) acrylic ester polymer of crosslinking structure when (methyl) glycidyl acrylate and N-methylol (methyl) when acrylamide is used in combination.In this case, as linking agent, suitably use polyamine, polyisocyanates, melamine resin, urea-formaldehyde resin, Resins, epoxy, polyvalent metal salt.By (methyl) acrylic ester polymer that use has crosslinking structure, the contact adhesive composition that helps obtaining to have hold facility.
For the emulsifying agent that is used for emulsion polymerization, can use any known emulsifying agent.For example, anionic emulsifier and partly-hydrolysed polyvinyl alcohol are preferable.The consumption of emulsifying agent is preferably 0.1 to 5 mass parts with respect to 100 mass parts polymkeric substance and is preferably 0.5 to 3 mass parts.
For polymerization process, except emulsion polymerization, can suitably use the radical polymerization method, as mass polymerization, solution polymerization process, suspension polymerization.As the initiator of radical polymerization method, can use various types of initiators, all be used as azo initiator, peroxide initiator.
Producing the polyreaction of pressure-sensitive adhesive polymers can carry out existing under the condition of tackifier above-mentioned.
Be used for the binder polymer of hotmelt, comprise polyethylene, polypropylene, isoprene-isobutylene rubber, synthetic polyisoprene, divinyl rubber, styrene-isoprene block polymer (SIS), styrene-butadiene block copolymer (SBS), styrene butadiene random copolymer (SBR), vinylbenzene-(ethene-butylene) segmented copolymer (SEBS), ethene-alpha-olefin copolymer, ethylene-vinyl acetate copolymer, ethene-(methyl) acrylate copolymer, (methyl) acrylate copolymer, vinylbenzene-(methyl) acrylate copolymer, vinyl acetate-(methyl) acrylate copolymer.
Then, contact adhesive composition is described below.
Contact adhesive composition contains tackifier and pressure-sensitive adhesive polymers.The preferred proportion of tackifier and pressure-sensitive adhesive polymers is that the amount of tackifier is 5 to 200 mass parts with respect to 100 mass parts pressure-sensitive adhesive polymers.When the amount of tackifier was less than 5 mass parts with respect to the amount of 100 mass parts pressure-sensitive adhesive polymers, the bounding force of the contact adhesive composition of formation was with unsatisfactory.And on the other hand, when the amount of tackifier surpassed 200 mass parts, force of cohesion that is to say, the hold facility of the contact adhesive composition of formation will reduce.When acrylic resin was used as pressure-sensitive adhesive polymers, the consumption of tackifier was preferably 5 to 50 mass parts with respect to 100 mass parts acrylic resins.When rubber was used as pressure-sensitive adhesive polymers, the consumption of tackifier was preferably 20 to 100 mass parts with respect to the rubber of 100 mass parts.
Here, contact adhesive composition comprises any pressure sensitive adhesive, and pressure sensitive adhesive comprises Solvent Adhesive, water-based (emulsion) tackiness agent, hotmelt, ultraviolet curing adhesive.
Contact adhesive composition of the present invention can be used as the pressure sensitive adhesive of general label and adhesive tape.And contact adhesive composition can be used as the pressure sensitive adhesive of film, transparent pressure-sensitive adhesive sheet, the sheet of protection transparent plastics, transparent self adhesive tape or the clear label of transparent bonding film, protection transparent plastics.In this case, contact adhesive composition is coated on predetermined body material, on transparent plastic film, sheet, adhesive tape.And contact adhesive composition also can be as the pressure sensitive adhesive of polarising sheet.
First embodiment of the present invention has following advantage.
Contact adhesive composition contains the vinyl polymer by not using chain-transfer agent and using a small amount of polymerization starter to obtain.Therefore, contact adhesive composition have higher bounding force and difficulty fade, weather resistance is good.
Contact adhesive composition contains the tackifier of weight-average molecular weight at 500 to 50,000 vinyl polymer.Therefore, contact adhesive composition all is being improved aspect bounding force, the ability that keeps bounding force and the weathering resistance.
The monomeric unit that constitutes vinyl polymer contains (methyl) acryl monomer unit of 50 to 100 quality %.Therefore, the weathering resistance of contact adhesive composition is improved, and fade (variable color) also is suppressed effectively.
First embodiment can improve as follows.
As pressure-sensitive adhesive polymers, it has to use and obtains monomer emulsion by letex polymerization through emulsification vinyl monomer and the tackifier mixture that contains vinyl polymer and obtain polymkeric substance.In this case, the contact adhesive composition that is produced has good bond properties.And tackifier help sneaking into equably contact adhesive composition.
As pressure-sensitive adhesive polymers, can use by making vinyl monomer carry out the polymkeric substance that solution polymerization obtains in the presence of the tackifier of vinyl polymer containing.
If desired, can in contact adhesive composition, add a kind of known tackifier, as Gum Rosin, terpine resin, petroleum resin, its add-on scope however the infringement weathering resistance.And, softening agent, defoamer, tensio-active agent, mould inhibitor, spices, neutralizing agent, thickening material be can add, all conditioning agent, frostproofer, pore forming material, antioxidant, UV light absorber, toughener, filler, pigment, white dyes, static inhibitor, anti, fire retardant, linking agent, organic solvent, tinting material are coated with.
Embodiment
The embodiment and the comparative example of first embodiment now will be described.In the following description, " part " and " % " all in mass.And, below several compounds adopt is abbreviated form.
HA: 2-EHA
BA: butyl acrylate
MA: methyl acrylate
MMA: methyl methacrylate
CHA: cyclohexyl acrylate
AA: vinylformic acid
HEA: vinylformic acid 2-hydroxyl ethyl ester
St: vinylbenzene
At first, be described below the synthetic of tackifier (vinyl polymer A1-A8).Synthetic embodiment 1: vinyl polymer A1 produces
The 3-ethoxyl ethyl propionate is incorporated with electric heater and capacity is the pressure stirring tank type reactor of 300ml.The inside reactor temperature maintains 230 ℃ with electric heater.And reactor pressure (gauge pressure) maintains 2.45-2.65MPa (25-27Kg/cm with pressure controller
2).
The monomer mixture that contains the vinyl monomer of 70 parts of BA and 30 parts of MA, 20 parts Virahol (IPA) are as solvent, and 0.5 part of di-t-butyl peroxide (DTBP) is ready as polymerization starter.Ready monomer mixture is kept in the head tank.Pressure in reactor is kept constant simultaneously, and monomer mixture is with constant input speed (23g/min; The residence time: 13min) add reactor from head tank continuously.During feed, reaction product is discharged from reactor outlet continuously, and output equals the inlet amount of monomer mixture.Monomer mixture charge begins back recognition reaction liquid temp decline at once.Then, elevate the temperature, but by control heater, temperature of reaction remains on about 230 ℃ by polymerization reaction heat.Temperature of reaction stable in, begin to reclaim reaction solution.The charging of monomer mixture will continue 154 minutes again, to carry out the successive polymerization reaction.In the successive polymerization reaction, use 2, the 000g monomer mixture reclaims 1, the 950g reaction solution.
When the reaction solution that reclaims was introduced into thin-film evaporator, volatile component as unreacted monomer, solvent, reduced pressure when 30mmHg, under 235 ℃ of conditions, removes from reaction solution, obtain about 1, the vinyl polymer A1 of 500g liquid form.By gas chromatographic analysis vinyl polymer A1, determine that in vinyl polymer unreacted monomer content is 0.5% or still less.By using tetrahydrofuran (THF) to make the gel permeation chromatography of solvent,, measure the weight-average molecular weight of vinyl polymer A1 with the polystyrene standard calibration.The weight-average molecular weight of vinyl polymer A1 is 2600.Synthetic embodiment 2: vinyl polymer A2 produces
Vinyl polymer A2 adopts the mode identical substantially with synthesizing embodiment 1 to produce, and except polymeric reaction temperature changes 175 ℃ into, the amount of IPA changes 10 parts into, and the amount of DTBP changes 0.1 part into.The weight-average molecular weight of vinyl polymer A2 is 15,000.Synthetic embodiment 3: vinyl polymer A3 produces
Vinyl polymer A3 adopts the mode identical substantially with synthesizing embodiment 1 to produce, except vinyl monomer changes 92 parts of CHA and 8 parts of AA into.The weight-average molecular weight of vinyl polymer A3 is 3080.Synthetic embodiment 4: vinyl polymer A4 produces
Vinyl polymer A4 adopts the mode identical substantially with synthesizing embodiment 1 to produce, and except polymeric reaction temperature changes 290 ℃ into, vinyl monomer changes 100 parts of St into, and solvent changes 30 parts dimethylbenzene into, and the amount of DTBP is changed to 1 part.The weight-average molecular weight of vinyl polymer A4 is 700.Synthetic embodiment 5: vinyl polymer A5 produces
Vinyl polymer A5 adopts the mode identical substantially with synthesizing embodiment 1 to produce, and except polymeric reaction temperature changes 220 ℃ into, vinyl monomer changes 94 parts of CHA and 6 parts of HEA into.The weight-average molecular weight of vinyl polymer A5 is 4800.Synthetic embodiment 6: the preparation of vinyl polymer A6
Agitator is being housed, is adding 80 parts of methylethylketones (hereinafter referred is MEK) in the flask of thermometer, condenser and dropping funnel, flask is being heated to 80 ℃.Preparation comprises 70 parts of MEK, 70 parts of BA, 30 parts of MA, 1 part of Diisopropyl azodicarboxylate (hereinafter referred is AIBN), the mixture solution of 8 parts of 3-thiohydracrylic acids in addition.This solution was dropped in the flask continuously by dropping funnel in 5 hours, to carry out polyreaction.After adding this solution, add 0.3 part of AIBN again in flask, 80 ℃ of reactions 3 hours, obtain vinyl polymer A6 again, its viscosity is 2400mPas, and solids content is 43.0%.Vinyl polymer A6 is a kind of multipolymer, and weight-average molecular weight is 2800.Synthetic embodiment 7: the preparation of vinyl polymer A7
Vinyl polymer A7 adopts the mode identical substantially with synthesizing embodiment 6 to produce, and just mixture solution changes into and comprises 70 parts of MEK, 70 parts of BA, and 30 parts of MA, the solution of 2 parts of AIBN, the amount that adds the AIBN that adds again behind this solution changes 0.5 part into.Vinyl polymer A7 is a kind of multipolymer, and weight-average molecular weight is 12000.Synthetic embodiment 8: the preparation of vinyl polymer A8
Vinyl polymer A8 adopts the mode identical substantially with synthesizing embodiment 1 to produce, and difference is for using 80 parts of CHA and 20 parts of BA as vinyl monomer.The weight-average molecular weight of vinyl polymer A8 is 3500.
Next, preparation and the application said composition that will set forth contact adhesive composition produced pressure sensitive adhesion sheet.
Embodiment 1
80 parts toluene are joined in the same flask of using with above-mentioned synthetic embodiment 6, and be heated to 75 ℃.Preparation comprises 50 parts of toluene, 95 parts of BA, 4 parts of AA, the mixing solutions of 1 part of HEA and 1 part of AIBN in addition.Above-mentioned solution was dropped in 4 hours in the flask continuously, carry out polyreaction.After adding mixing solutions, add 0.3 part of AIBN again in flask, 75 ℃ were reacted 3 hours, obtained copolymer solution, and its viscosity is 3500mPas, and solids content is 43.4%.
In 100 parts of (referring to solids component) above-mentioned copolymer solutions, add 10 parts of vinyl polymer A1 and 0.5 part of ColonateL (poly isocyanate, Japanese polyurethane Industrial Co., Ltd makes), obtain pressure sensitive adhesive composite.Pressure sensitive adhesive composite is coated on the thick polyester film of 50 μ m.Contact adhesive composition was descended dry 2 minutes at 100 ℃, obtain pressure sensitive adhesion sheet.The glue spread of adjusting contact adhesive composition make the glue spread of dried pressure sensitive adhesive composite be 30 grams/square metre.
The performance of pressure sensitive adhesion sheet (1)-(7) are estimated by following test method.Evaluation result sees Table 1.(1) bounding force (bounding force of polyethylene (PE))
Pressure sensitive adhesion sheet is applied on the polyethylene board, at 23 ℃, measures the stripping strength (180) of adhesive sheet under the condition of relative humidity 65% according to the standard of JIS Z-0237 " detection method of self adhesive tape and adhesive sheet ".(2) hold facility
The hold facility of pressure sensitive adhesion sheet is measured according to the method for JIS Z-0237.Prepare the stainless steel plate of a 30mm * 150mm and the pressure sensitive adhesion sheet of a 25mm * 25mm.Pressure sensitive adhesion sheet is applied on the stainless steel plate, makes that the bond area between pressure sensitive adhesion sheet and stainless steel plate is 25mm * 25mm.Stainless steel plate is vertically placed, allowed pressure sensitive adhesion sheet hang from the stainless steel plate bottom.One kilogram load is hung over the lower end of pressure sensitive adhesion sheet.Pressure sensitive adhesion sheet peels off the required time from stainless steel plate when being determined at 40 ℃ or 80 ℃.If pressure sensitive adhesion sheet still was attached on the stainless steel plate, then measure the displacement (miles of relative movement) of pressure sensitive adhesion sheet from the home position after 24 hours.(3) viscosity (spin viscosity)
Spin viscosity, is measured under the condition of relative humidity 65% at 23 ℃ according to the spin method of stipulating among the JIS Z-0237 " detection method of self adhesive tape and adhesive sheet ".(4) weathering resistance
Pressure sensitive adhesion sheet is leaving 24 hours ultraviolet radiation of ultraviolet lamp (the mercury vapor lamp H-400V type of the test that is used to fade, Toshiba produces) 30cm place acceptance.The standard visual assessment that fades below the weathering resistance basis of adhesive sheet.
Zero: do not fade Δ: faint yellow, *: deep yellow (5) transparency
The transparency of pressure sensitive adhesion sheet is according to following standard visual assessment
Zero: transparent, Δ: opaque slightly, *: opaque fully (6) color
With contact adhesive composition be coated on the glue spread that makes dried contact adhesive composition on the thick polyester film of 50 μ m be 100 grams/square metre, 100 ℃ of dryings 3 minutes, thereby obtain pressure sensitive adhesion sheet.The color of pressure sensitive adhesion sheet is according to following standard visual assessment.
Zero: do not fade Δ: faint yellow, *: yellow (7) smell
The smell of pressure sensitive adhesion sheet is estimated by the organoleptic test.
Embodiment 2
The preparation method of pressure sensitive adhesion sheet is substantially with embodiment 1, and difference is with 10 parts of vinyl polymer A1 in 10 parts of vinyl polymer A2 alternate embodiments 1.
Embodiment 3
The preparation method of pressure sensitive adhesion sheet is substantially with embodiment 1, and difference is with 10 parts of vinyl polymer A1 in 10 parts of vinyl polymer A3 alternate embodiments 1.
Embodiment 4
The preparation method of pressure sensitive adhesion sheet is substantially with embodiment 1, and difference is with 10 parts of vinyl polymer A1 in 10 parts of vinyl polymer A4 alternate embodiments 1.
Embodiment 5
Containing 87 parts of HA, 10 parts of MMA, 2 parts of AA add 33 parts of water and 4 parts of Witco 1298 Soft Acids (trade(brand)name: NEOPELEX NO.25 KAO company produces) in the monomer mixture of 1 part of HEA, obtain monomer emulsion.In addition, 65 parts water are added in the identical flask that uses with embodiment 1, flask is with nitrogen purging and be heated to 80 ℃.The Ammonium Persulfate 98.5 that in flask, adds 0.1 part, then will the above-mentioned monomer emulsion that makes with 0.5% amount adding flask of its total amount, initiated polymerization.The initiation of polyreaction is obtained confirming by the variation of reacting liquid temperature in the flask.
Keep polymeric reaction temperature at 79 ℃ in 81 ℃, with the dropping 4 hours continuously of the Ammonium Persulfate 98.5 of remaining monomer emulsion (total amount 99.5%) and 3 part 10%.After adding monomer emulsion, reaction solution remain on 80 ℃ 2 hours to finish reaction, making pH with 25% ammoniacal liquor neutralization reaction liquid then is 7, obtains copolymer emulsion, its solids content 50.2%.
Next, in 20 parts of water, add 20 parts vinyl polymer A3 and 1 part Witco 1298 Soft Acid (NEOPELEXNO.25), make it to mix.With the mixture heating up to 80 that obtains ℃, and use high-pressure homogenizer emulsification, thereby make the emulsion of vinyl polymer A3.
The emulsion of 10 parts of (referring to solids component) vinyl polymer A3 is joined in the copolymer emulsion of 100 parts of (referring to solids component) above-mentioned preparations and go.Add a kind of caustic solubility thickening material (trade(brand)name B-500 then; Toagosei company limited produces), the viscosity of the emulsion that obtains becomes 10, and 000mPas has so just obtained the contact adhesive composition of embodiment 5.Then, use with embodiment 1 in identical method make the pressure sensitive adhesion sheet of embodiment 5.
Embodiment 6
The temperaturing control pressure reactor (autoclave) that has agitator in advance with nitrogen purging.The water that in reactor, adds 100 parts, 2 parts Witco 1298 Soft Acid (NEOPELEX NO.25), 0.08 part sodium ethylene diamine tetracetate, 1.2 parts Sodium Persulfate, 0.3 the sodium hydroxide of part, 40 parts divinyl, 30 parts BA, 25 parts St, 5 parts HEA carried out polyreaction 15 hours.
Polyreaction is transferred to 7 with sodium hydroxide with the pH value of reaction solution after finishing.Monomer residual in the reaction solution is removed with the method for steam desorption, to obtain copolymer emulsion.Then, add the emulsion of the vinyl polymer A3 of 60 parts (referring to solid part) in the copolymer emulsion of 100 parts (referring to solid part) acquisition, then add thickening material B-500, the viscosity that makes the emulsion that obtains is 10,000mPas, thereby the contact adhesive composition of acquisition embodiment 6.Use the binder composition of embodiment 6 then, use the method identical to make embodiment 6 pressure sensitive adhesion sheets with embodiment 1.
Embodiment 7
With 40 parts of HA, 35 parts of MA, 25 parts of acrylic acid dimer (trade(brand)names: ARONIX M-5600; Toagosei company limited produces), and 30 parts of vinyl polymer A1 and 2 parts of benzyl methyl ketals (trade(brand)name, IRGACURE 651; CIBA special chemical article company produces) mix mutually.With the mixture of gained be coated on the glue spread that makes dried mixture on the thick polyester film of 50 μ m reach 30 grams/square metre, to make pressure-sensitive adhesive film.Pressure-sensitive adhesive film is 10cm in focal height, and line speed is to accept 10 times uviolizing under 10m/ minute the condition with the focusing high-pressure mercury vapour lamp of 80w/cm.Thereby obtained the pressure sensitive adhesion sheet of embodiment 7.The pressure sensitive adhesion sheet that obtains illustrates with uv-radiation and can finish polyreaction satisfactorily without any disagreeable monomeric smell.
Embodiment 8
The preparation method of pressure sensitive adhesion sheet is substantially with embodiment 1, and difference is with 10 parts of vinyl polymer A1 in 10 parts of vinyl polymer A5 alternate embodiments 1.
The performance of each pressure sensitive adhesion sheet among the embodiment 2-8 (1)-(7) all use with embodiment 1 in identical method estimate, the results are shown in table 1 and table 2.
Embodiment 9
With 0.04 part of lauryl mercaptan, 5 parts of vinyl polymer A1,36 parts of water, 1.5 parts of sodium alkyl sulfate (trade(brand)name SandetLNM; Sanyo chemical industry company limited produces) add and contain a HEA, 43 parts of HA, 55 parts of BA, 3 parts of MMA in the monomer mixed solution of 1 part of AA, prepare monomer emulsion.
40 parts water are added in the identical flask that uses with embodiment 1.The flask nitrogen purging, and be heated to 80 ℃.0.1 part Ammonium Persulfate 98.5 is joined in the flask, then, the monomer emulsion of above preparation is joined in the flask initiated polymerization with 0.5% amount of its total amount.
Confirm that polyreaction begins, then keep polymeric reaction temperature at 79 ℃ in 81 ℃, with the dropping 4 hours continuously of the ammonium persulphate of remaining monomer emulsion (total amount 99.5%) and 3 part 10%.After adding monomer emulsion, make reaction solution remain on 80 ℃ 2 hours to finish reaction, making pH with 25% ammoniacal liquor neutralization reaction liquid then is 7.Add caustic solubility thickening material (trade(brand)name B-500 then; The production of Toagosei company limited), make the contact adhesive composition of embodiment 9, the viscosity after it is regulated is 10,000mPas.
Use the contact adhesive composition of embodiment 9, according to embodiment 1 in essentially identical method make pressure sensitive adhesion sheet.Difference is, with the paper in the non-timber source body material as adhesive sheet, replaces polyester film.The bounding force of pressure sensitive adhesion sheet (PE bounding force) is 5.1N/25mm.
Embodiment 10
The preparation method of pressure sensitive adhesion sheet is substantially with embodiment 9, and difference is to replace vinyl polymer A1 with vinyl polymer A8.The bounding force of pressure sensitive adhesion sheet (PE bounding force) is 5.1N/25mm.
Embodiment 11
The preparation method of pressure sensitive adhesion sheet is substantially with embodiment 9, and difference is to replace 5 parts of vinyl polymer A1 with 10 parts of vinyl polymer A8.The bounding force of pressure sensitive adhesion sheet (PE bounding force) is 6.3N/25mm.Comparative example 1
The preparation method of pressure sensitive adhesion sheet does not just add vinyl polymer A1 substantially with embodiment 1.Comparative example 2
Remove with 10 parts of rosin tackifier (trade(brand)name: SUPERESTER A-115; Arakawa chemical industry company limited makes) replace beyond the vinyl polymer A1, use the method identical substantially to prepare pressure sensitive adhesion sheet with embodiment 1.Comparative example 3
Remove with 10 parts of petroleum resin tackifiers (trade(brand)name: Nisseki Neopolymer L-90; Nippon petroleum chemistry company limited makes) replace beyond the vinyl polymer A1, use the method identical substantially to make pressure sensitive adhesion sheet with embodiment 1.Comparative example 4
Except that replace vinyl polymer A1 with 10 parts of vinyl polymer A6, use the method identical substantially to make pressure sensitive adhesion sheet with embodiment 1.Prepared pressure-sensitive adhesive sheet has the intensive thiol smell.Comparative example 5
Remove with 60 parts of (pressing solids component) rosin milk tackifier (trade(brand)names: SUPERESTER E-720; Arakawa chemical industry company limited makes) replace beyond the emulsion of vinyl polymer A3, use the method identical substantially to make pressure sensitive adhesion sheet with embodiment 6.Comparative example 6
Remove with 30 parts of tackifier (trade(brand)name: SUPERESTER A-115; Arakawa chemical industry company limited makes) replace beyond the vinyl polymer A1, use the method identical substantially to make pressure sensitive adhesion sheet with embodiment 7.The pressure sensitive adhesion sheet of manufacturing is because residual monomer produces a kind of intensive offensive odour.Thinking why there is unreacted monomer, is because rosin tackifier has suppressed the polyreaction with ultraviolet radiation.Comparative example 7
Except that with 10 parts of vinyl polymer A7 as the ethylenic copolymer, use the method identical substantially to make pressure sensitive adhesion sheet with embodiment 1.
Estimate the performance of each adhesive sheet in the comparative example 1 to 7, the results are shown in table 3 and table 4.Table 1
Table 2
Table 3
Table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | ||
| Tackifier amount of preparation (part) | A1 10 | A2 10 | A3 10 | A4 10 | |
| PE bounding force (ox/25 millimeter) | 4.07 | 3.53 | 4.51 | 3.43 | |
| Hold facility | 40℃ | 0.1 millimeter of miles of relative movement | 0.3 millimeter of miles of relative movement | 0.1 millimeter of miles of relative movement | 0.3 millimeter of miles of relative movement |
| 80℃ | 140 minutes | 250 minutes | 0.5 millimeter of miles of relative movement | 280 minutes | |
| Spin finger property | 12 | 9 | 10 | 8 | |
| Weathering resistance | ○ | ○ | ○ | △ | |
| Transparency | ○ | ○ | ○ | ○ | |
| Color | ○ | ○ | ○ | ○ | |
| Smell | No | No | No | No | |
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | ||
| Tackifier amount of preparation (part) | A3 emulsion 10 | A3 emulsion 60 | A1 30 | A5 10 | |
| PE bounding force (ox/25 millimeter) | 3.68 | 4.22 | 3.97 | 4.17 | |
| Hold facility | 40℃ | 0.2 millimeter of miles of relative movement | 0.1 millimeter of miles of relative movement | 0.3 millimeter of miles of relative movement | 0.1 millimeter of miles of relative movement |
| 80℃ | 0.2 millimeter of miles of relative movement | 250 minutes | 400 minutes | 0.5 millimeter of miles of relative movement | |
| Spin viscosity | 8 | 11 | 8??? | 8?? |
| Weathering resistance | ○ | △ | ○ | △ |
| Transparency | ○ | × | ○ | ○ |
| Color | ○ | ○ | ○ | ○ |
| Smell | No | No | No | No |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | ||
| Tackifier amount of preparation (part) | No | ??SUPEREST ??ER?A-115 ??10 | ??NISSEKI ??L-90 ??10 | ??A6 ??10 | |
| PE bounding force (ox/25 millimeter) | ??1.91 | ??4.12 | ??2.65 | ??3.53 | |
| Hold facility | ??40℃ | 0.1 millimeter of miles of relative movement | 200 minutes | 300 minutes | 0.4 millimeter of miles of relative movement |
| ??80℃ | 0.3 millimeter of miles of relative movement | 10 minutes | 8 minutes | 130 minutes | |
| Spin viscosity | ??8 | ??3 | ??5 | ??10 | |
| Weathering resistance | ??○ | ??× | ??× | ??△ | |
| Transparency | ??○ | ??× | ??× | ??○ | |
| Color | ??○ | ??× | ??× | ??× | |
| Smell | No | No | No | Thiol smell | |
| Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| Tackifier amount of preparation (part) | ?E-720 ?60 | ?A-115 ?30 | ?A7 ?10 |
| PE bounding force (ox/25 millimeter) | ?4.41 | 1.37 | 3.68 | |
| Hold facility | 40℃ | 800 minutes | 10 minutes | 0.3 millimeter of miles of relative movement |
| 80℃ | 20 minutes | 0 minute | 220 minutes | |
| Spin viscosity | ?11 | 4 | 9 | |
| Weathering resistance | ?× | × | ○ | |
| Transparency | ?○ | ○ | ○ | |
| Color | ?× | × | × | |
| Smell | No | The monomer smell | No | |
Shown in table 1 and 2, the pressure sensitive adhesion sheet in embodiment 1 to 8 all has fabulous bounding force, hold facility, viscosity and weathering resistance.By contrast, as shown in table 3 and 4, the pressure sensitive adhesion sheet in the comparative example 1 that does not contain vinyl polymer A1 only has lower bounding force.In addition, at comparative example 2,3, the pressure sensitive adhesion sheet in 5 and 6 does not all have good weather.And the pressure sensitive adhesion sheet variable color in comparative example 4 is obvious, also has the intensive thiol smell simultaneously.(second embodiment)
Below will narrate hotmelt.Here " hotmelt " is meant heating and melting adherent tackiness agent then.In this manual, term " binder polymer " is meant general polymkeric substance as the hotmelt main ingredient.In addition, term " (methyl) vinylformic acid " is meant vinylformic acid or methacrylic acid, and term " (methyl) acryl " is meant acryl or methacryloyl.
The characteristics of this hot-melt adhesive composition are to contain tackifier and binder polymer, tackifier comprise above mentioned vinyl polymer, and vinyl polymer is to obtain (also being called " vinyl polymer that high temperature polymerization obtains " later on) by vinyl monomer polymerization under 180 ℃ to 350 ℃ temperature.
The tackifier that comprise the vinyl polymer that high temperature polymerization obtains increase the bounding force of hotmelt, and this tackifier are to obtain by vinyl monomer polymerization under 180 ℃ to 350 ℃ temperature.
The example of vinyl monomer comprises (methyl) acrylic monomer, aromatic vinyl monomer, vinyl acetate and other vinyl monomers.
The object lesson of (methyl) Acrylic Acid Monomer comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) vinylformic acid, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester and (methyl) butyl acrylate.
The object lesson of aromatic vinyl monomer comprises vinylbenzene and alpha-methyl styrene.The example of vinyl acetate comprises vinyl acetate and propionate.The object lesson of other vinyl monomers comprises (methyl) acrylamide, N hydroxymethyl acrylamide and (methyl) vinyl cyanide.
Because (methyl) acrylic monomer and aromatic vinyl monomer have fabulous polymerizing power, and just may have stronger bounding force by their synthetic hotmelts, therefore preferred (methyl) acrylic monomer and aromatic vinyl monomer.
The preferred tackifier that are used for hotmelt comprise vinyl polymer, and this vinyl polymer is to obtain 180 ℃ to 350 ℃ polymerizations by top mentioned vinyl monomer.Polymerization temperature is preferably 190 ℃ to 320 ℃, and is more preferably at 200 ℃ to 300 ℃.If polymerization temperature is too low, the synthetic vinyl polymer has high melt viscosity, therefore the hotmelt that mixes this vinyl polymer has relatively poor adhesive coated, thereby the effect that this vinyl polymer also just can not fine demonstration tackifier selects the bounding force of synthetic tackiness agent also just smaller.If polymerization temperature is too high, hotmelt may variable color, and weathering resistance is also poor.
About polymerization process, generally be not particularly limited, its example comprises: continuous polymerization, the batchwise polymerization method, the semi-continuous polymerzation method promptly adds starting monomer continuously or off and on and carries out the polymeric method when not reclaiming reaction solution.Have fabulous binding property and adhesive coated owing to comprise the hot-melt adhesive composition of the tackifier acquisition of the vinyl polymer that obtains by adding, so preferred continuous polymerization.Continuous polymerization can carry out (seeing the PCT communique (Kohyo) of Japanese unexamined, clear: the patent gazette of Sho 57-502171 and Japanese unexamined, clear: Sho 59-6027 and Sho 60-215007) with a kind of known method.
Above-mentioned polyreaction can be carried out with solvent or without solvent.Do not use initiators for polymerization, polyreaction also can be carried out, and polyreaction is easier carries out but the use radical polymerization initiator can make.When using initiators for polymerization, the consumption of radical polymerization initiator should be about 1 quality % or still less in vinyl monomer.If the initiators for polymerization consumption is too big, may variable color by adding hot-melt adhesive composition that the vinyl polymer that obtained by the high temperature polymerization reaction obtains, and weathering resistance is also poor.Should not use chain-transfer agent to carry out polyreaction basically, but in order to increase the vinyl polymer that obtains by high temperature polymerization reaction effect, only otherwise the weathering resistance of infringement tackiness agent also can be used chain-transfer agent as tackifier.
The vinyl polymer weight-average molecular weight that obtains by the high temperature polymerization reaction is preferably 500 to 50000, is more preferably 1000 to 18000.If the vinyl polymer weight-average molecular weight is too little, the synthetic hotmelt does not just have enough force of cohesion, and just therefore intensity also just can not show satisfied bounding force.If weight-average molecular weight is too big, the synthetic hotmelt just has bigger melt viscosity, so adhesive coated is just relatively poor, the effect that vinyl polymer also just can not fine demonstration tackifier, and the bounding force of synthetic tackiness agent is also just very little.
Obtain hot-melt adhesive composition by adding the tackifier that comprise the above-mentioned vinyl polymer that obtains through the high temperature polymerization reaction to binder polymer (being a kind of polymkeric substance) as the hotmelt main ingredient.
As binder polymer, can use common known binder polymer, its example comprises olefin homo, olefin copolymer, diene polymer, diene copolymer, the hydrogenated diene hydrocarbon polymer, hydrogenated diene hydrocarbon copolymer, vibrin and polyamide resin.As binder polymer, preferably have the binder polymer of melt temperature, particularly preferably be melt temperature at 70 ℃ or higher, better at 70 ℃ to 200 ℃ binder polymer.
The example of olefin homo comprises polyethylene, polypropylene and amorphous poly propylene.
The example of olefin copolymer comprises ethene and except the multipolymer of the alkene of ethene, propylene and except the multipolymer of the alkene of propylene, propylene and except the amorphous copolymer of the alkene of propylene, ethylene-ethyl acetate copolymer (being also referred to as " EVA ") and ethene-(methyl) acrylate copolymer etc.The object lesson of ethene-(methyl) acrylate copolymer comprises ethylene-methyl methacrylate methyl terpolymer (being also referred to as " EMMA "), ethylene-methyl acrylate copolymer (being also referred to as " EMA "), ethylene-ethyl acrylate copolymer (being also referred to as " EEA ") and ethylene-butyl acrylate copolymer (being also referred to as " EBA ").
The example of diene polymer comprises isoprene-isobutylene rubber, synthetic polyisoprene and divinyl rubber.
The example of diene copolymer comprises the phenylethylene-dialkene multipolymer, object lesson comprises styrene butadiene monomer segmented copolymer (being also referred to as " SBS "), styrene-isoprene monomer segmented copolymer (being also referred to as " SIS ") and styrene butadiene random copolymer (being also referred to as " SBR ").
The example thing of hydrogenated diene hydrocarbon copolymerization comprises vinylbenzene-(ethylene-propylene) segmented copolymer (being also referred to as " SEPS ") and vinylbenzene-(ethene-butylene) segmented copolymer (being also referred to as " SEBS "), and wherein part or all unsaturated link(age)s that comes from diolefine are hydrogenated in diene copolymer.
Two kinds or more kinds of above-mentioned binder polymer uses capable of being combined.
In above binder polymer, because the synthetic hotmelt has bigger bounding force and fabulous adhesive coated, so optimal ethylene base co-polymer, as ethylene-ethyl acetate copolymer or ethene-(methyl) acrylate copolymer, phenylethylene-dialkene multipolymer and hydrogenated styrene-diene copolymer.
When binder polymer is an ethylenic copolymer, during as ethylene-ethyl acetate copolymer or ethene-(methyl) acrylate copolymer, by what the high temperature polymerization reaction obtained (methyl) acrylic monomer units will preferably be arranged with the vinyl polymer that binder polymer is blended together, and to constitute all monomeric units of vinyl polymer, (methyl) acrylic monomer units content is preferably 10 to 100 quality %.
When binder polymer is a styrol copolymer, during as phenylethylene-dialkene multipolymer or hydrogenated styrene-diene copolymer, to the aromatic monomer unit preferably be arranged with the vinyl polymer that binder polymer is blended together by what the high temperature polymerization reaction obtained, and to constitute all monomeric units of vinyl polymer, aromatic monomer unit content is preferably 10 to 100 quality %.
The reason of doing like this is because obtain to have the hot-melt adhesive composition of even composition easily.
Hot-melt adhesive composition preferably comprises in 5 parts of 100 mass parts binder polymers to 200 mass parts, be more preferably 10 parts of tackifier to 150 mass parts, this tackifier comprise the vinyl polymer that is obtained by the high temperature polymerization reaction, the i.e. vinyl polymer that obtains by polymerization of vinyl monomers under 180 ℃ to 350 ℃ temperature.If reacted the amount of the vinyl polymer that obtains by high temperature polymerization too little or too big, hot-melt adhesive composition may have only less bounding force.Its reason may be as follows: if the amount of vinyl polymer is too little, the effect that vinyl polymer just can not fine demonstration tackifier, be chosen in adherend and tackiness agent between the interface just may peel off.If the amount of vinyl polymer is too big, the force of cohesion of tackiness agent is that intensity reduces, and polymerization destroys in may taking place in bonding coat.
In hot-melt adhesive composition of the present invention, only otherwise damage effect of the present invention, can add tackifier except other known conventional of the tackifier that comprise the vinyl polymer that obtains by the high temperature polymerization reaction.The example of known tackifier comprises rosin, from rosin derivative resin, terpine resin, coumarone-indene resin, petroleum resin [C 5 fraction, C9 cut, C5 and C9 cut and (being total to) polymkeric substance such as Dicyclopentadiene (DCPD)], hydrocarbon resin, resol, the hydrogenated products of xylene resin and these resins.Certainly from the angle of infringement characteristic of the present invention and the stability behind the hot melt and bonding after weathering resistance all good, preferred hydrogenated terpene resin and hydrogenated petroleum resin.
In hot-melt adhesive composition of the present invention, can add softening agent, paraffin, naphthenic hydrocarbon or aromatics process oil, liquid resin such as liquid polybutene, liquid polybutadiene, the hydrogenated products of liquid polyisobutene or aforesaid liquid resin, natural or synthetic wax (as Paraffin Wax Semi Refined, Witcodur 272 or low-molecular-weight polyolefin-wax).
And, if necessary, can add antioxidant, UV light absorber, photostabilizer, sorbent material, filler, pigment, dyestuff or spices.
Preparation method about hotmelt of the present invention, do not have special restriction, having of can mentioning will comprise the tackifier binder polymer of the vinyl polymer that obtains by the high temperature polymerization reaction and the method that other component hot melt makes it to mix, with organic solvent is added in the top component and hot melt, make it uniform mixing together, follow the method for redistillation solvent, from the viewpoint of industry, this melt compounding method is preferred.As for mixing equipment, can use the hot melt kneader.This kneader is not had particular restriction, can mention mixing machine, kneader, list or the twin-screw extruder and the mixing machine that for example have screw rod or helical ribbon agitator.Normally 80 to 230 ℃ of mixing temperatures, and, for anti-oxidation, preferably for example mix in the nitrogen at rare gas element.
Hotmelt of the present invention has good binding property, adhesive coated, thermostability after the fusion, with bonding back weathering resistance, therefore, can be applied on the various adherends, for example, various types of plastic shaping products, plastics film, rubber cloth, metal, timber, glass and mortar concrete.And, be specially adapted to be difficult to and the moulding product of other materials adherent polyolefin resin and material or the adherend that another kind is different from polyolefin resin as hotmelt.
As for the method for using hotmelt of the present invention in bonding, the useful heat seeling coating device that can mention carries out the spiral coating, the pearl coating, and roller coating and seam are touched coating, and still, the adherent method also is not limited to these.In addition, when composition is used for when bonding, at 100 to 230 ℃, melt viscosity is generally 1000 to 10 to melt temperature, 000mPas usually.
Embodiment
Below, with reference to the following example and more detailed explanation second embodiment of comparative example.In these embodiment and comparative example, " part " and " % " represents " mass fraction " and " quality % " respectively.In addition, the monomer implication of use is as follows:
AMS: alpha-methyl styrene
IBA: isobornyl acrylate (synthetic embodiment 9)
The pressure stirring tank type reactor that uses has the volume of one deck oil jacket and 1000ml, and the temperature of oil jacket can maintain 271 ℃.
Then, to contain 50 parts of St at the beginning, monomer mixture with 25 parts of AMS and 25 parts of IBA vinyl monomers and 0.5 part of di-t-butyl peroxide (hereinafter to be referred as DTBP) polymerization starter, from head tank, be added in the reactor continuously with fixed speed (48g/ minute, the residence time is 12 minutes).Then, in 580g, continuously discharge the product of reaction by the outlet of reactor in the content weight that keeps reactor, its output equals the monomer mixture charge amount.In present embodiment, the temperature maintenance of inside reactor is at 270 ℃, and pressure inside is 0.74MPa.In addition, the reaction product of discharging is placed in the thin-film evaporator,, and remains on 250 ℃, the volatiles that comprises unreacted monomer is removed by distillation at the state of 30kPa decompression.
After monomer mixture charge begins 36 minutes, and temperature also stable in, this time is got the recovery time opening of making reaction solution, from reclaiming time opening, sustained reaction 42 minutes.As a result, add the monomer mixture of 2000g altogether, and obtain the vinyl polymerization body A9 of 1540g.
By vapor-phase chromatography, can determine that in polymkeric substance unreacted monomeric content only is 0.5% or still less.In addition, form, can determine the 53 parts of St that consist of of vinyl polymerization body A9,20 parts of AMS and 27 parts of IBA from the unreacted monomer that distills out through thin-film evaporator.
By gel permeation chromatography (hereinafter to be referred as GPC), as solvent, with the working curve that polystyrene standard makes, the weight-average molecular weight (hereinafter to be referred as Mw) that can record this polymkeric substance is 2600 with tetrahydrofuran (THF).(synthetic embodiment 10)
The Mw of vinyl polymer A10 is 3600, and this method for producing polymer is identical with the cardinal principle of synthetic embodiment 1, except the monomer mixture that adds comprises 30 parts of CHA instead, and 70 parts of St, the mixture of 10 parts of dimethylbenzene and 0.5 part of DTBP, polymerization temperature change 245 ℃ into.(evaluation method) ● R﹠amp; B softening temperature: measure R﹠amp according to JIS-K-2207; The B softening temperature.● melt viscosity: be heated to 190 ℃ according to JAI-7-1980, with Brookfield viscometer determining melt viscosity.(unit: mPas) ● bonding shearing resistance: will form the part of wide 12.5mm with the end that hot melt applicator hot-melt adhesive composition is coated the wide glued board of 25mm, above another piece glued board is pressed in.Under 23 ℃ environment, measure tensile shear strength (unit: N/cm
2). ● bonding stripping strength:use the method identical, the rope form hot-melt adhesive composition is coated the polyethylene board of a wide 25mm, reach the glue spread of 5g/m, 23 ℃ of of environment of above another piece polyethylene board is pressed in measuring bonding shearing resistance.Under, measure stripping strength (unit:N/25mm). ● 190 ℃ of of hot-melt adhesive of thermostability:under composition heating, 24 hours, the relative variation (be taken as 0 hour value 100 o'clock relative value) of observing its outward appearance and measuring melt viscosity. ● weathering resistance:prepare and be used to test the same test piece of bonding stripping strength, be placed in the daylight type weatherometer 300 hours, then the result of visual inspection test.In embodiment and comparative example, use following starting material: ● EVA:EVAFLEX 210 (made by Du Pont-Mitsui Polychemicals company limited by ethylene-vinyl acetate copolymer; Vinyl acetate between to for plastic ester units:28wt%; MFR:400) ● EEA:EVAFLEX A704 (made by Du Pont-Mitsui Polychemicals company limited by ethylene-ethyl acrylate copolymer; Ethyl propenoate unit:25wt%; MFR:275) ● SIS:Clayton-D1107CP (styrene-isoprene block copolymer is made by Clayton Polymer Co., Ltd) ● polyvinyl A9: the polyvinyl that synthetic example 9 obtains ● polyvinyl A10: the polyvinyl that synthetic example 10 obtains ● hydrogenated wood rosin glycerol ester: ester gum 11 (being made by Arakawa Chemical Industries Co., Ltd) ● wax: microwax 155 (being made by Nippon Oil Co., Ltd) ● process oil: Dynaoil PW380 (being made by Tdemitsu Petrochemical Co., Ltd) ● antioxidant: Irganox-1010 (being made by CIBA-GEIGY) (embodiment 12)
Add 200gEVA and 2g antioxidant to the flask with agitator that is heated to 190 ℃ under nitrogen gas stream, add 200g vinyl polymer A10 subsequently again, stir about obtained hotmelt 1 in 1 hour.According to evaluation method mentioned above, this tackiness agent is estimated.That estimates the results are shown in table 5.(embodiment 13)
The preparation method of hotmelt 2 is identical with the cardinal principle that embodiment 12 introduces, and difference adds 200g vinyl polymer A9 subsequently for adding 200gEVA and 2g antioxidant, mixes 15 minutes, and then adds the 100g process oil.This tackiness agent is estimated, evaluation the results are shown in table 5.(embodiment 14)
The preparation method of hotmelt 3 is identical with the cardinal principle of embodiment 12, and difference adds 100g vinyl polymer A9 and 100g hydrogenated wood rosin glycerol ester subsequently for adding 200gEVA and 2g antioxidant, mixes 15 minutes, and then adds 100g wax.This tackiness agent is estimated, evaluation the results are shown in table 5.(embodiment 15)
The preparation method of hotmelt 4 is identical with the cardinal principle that embodiment 12 introduces, and difference adds 100g vinyl polymer A9 and 100g hydrogenated wood rosin glycerol ester subsequently for adding 200gEEA and 2g antioxidant, mixes 15 minutes, and then adds 100g wax.This tackiness agent is estimated, evaluation the results are shown in table 5.Table 5
* 1: because surperficial carbonization, so mensuration not.(embodiment 16)
| Embodiment | Comparative example | ||||||||
| ??12 | ??13 | ??14 | ??15 | ??16 | ??17 | ??8 | ??9 | ??10 | |
| The R﹠B softening temperature | ??85 | ??67 | ??84 | ??89 | ??98 | ??96 | ??75 | ??89 | ??97 |
| Melt viscosity (190 ℃) | ??9000 | ??2320 | ??1960 | ??7800 | ??83000 | ??83000 | ??2440 | ??19800 | ??7320 |
| Bonding shearing resistance | ??118.3 | ??40.6 | ??264.5 | ??252.8 | ??110.2 | ??92.9 | ??227.4 | ??250.7 | ??10.8 |
| Bonding stripping strength | ??2.7 | ??18.6 | ??7.5 | ??0.2 | ??30.2 | ??16.3 | ??12.2 | ??15.7 | ??13.6 |
| The fade relative variation of situation melt viscosity of thermostability visual inspection | Excellent 100 | Excellent 105 | Excellent 101 | Excellent 107 | Excellent 98 | Excellent 96 | Brown * 1 | Yellow 110 | Brown 85 |
| The weathering resistance visual inspection bonding situation of situation visual inspection of fading | Excellent | Excellent | Flavescence is excellent slightly | Flavescence is excellent slightly | Excellent | Excellent | Flavescence is excellent | Flavescence is excellent | Flavescence is peeled off |
Under nitrogen gas stream, add 200gSIS, 100g hydrogenated wood rosin glycerol ester and 2g antioxidant, make it melting mixing together to the kneader that is heated to 170 ℃.After confirming the whole fusions of SIS, add 100g vinyl polymer A10 again, melting mixing is about 30 minutes again, thereby obtains hotmelt 5, and this tackiness agent is estimated.That estimates the results are shown in table 5.(embodiment 17)
Be used for embodiment 16 identical methods and add 200gSIS, 100g hydrogenated wood rosin glycerol ester and 2g antioxidant, make it melting mixing together.After confirming the whole fusions of SIS, add 100g vinyl polymer A9 again, use the method identical substantially, obtain hotmelt 6, this tackiness agent is estimated with embodiment 16.That estimates the results are shown in table 5.(comparative example 8)
The preparation method of hotmelt 7 is identical with the cardinal principle of embodiment 12, and difference adds 200g hydrogenated wood rosin glycerol ester and 100g wax subsequently for adding 200gEVA and 2g antioxidant, and stir about 1 hour is estimated this tackiness agent.That estimates the results are shown in table 5.(comparative example 9)
The preparation method of hotmelt 8 is identical with the cardinal principle of embodiment 12, and difference adds 200g hydrogenated wood rosin glycerol ester and 100g wax, stir about 1 hour subsequently for adding 200gEEA and 2g antioxidant.This tackiness agent is estimated.That estimates the results are shown in table 5.(comparative example 10)
Add 200gSIS, 100g hydrogenated wood rosin glycerol ester and 2g antioxidant with the method identical, make it melting mixing together with embodiment 16.After confirming the whole fusions of SIS, add the 100g process oil, melting mixing is about 30 minutes again, obtains hotmelt 9, and this tackiness agent is estimated.The result who estimates is as shown in table 5.
Hotmelt among the embodiment 12-17, it is by the tackifier of vinyl monomer through 180 to 350 ℃ of vinyl polymerization bodies that are polymerized that use comprises, this class tackiness agent all shows big bounding force, good adhesive coated, the good weathering resistance of good hot melt stability and bonding back.
And the hotmelt among the comparative example 8-10 all uses rosin tackifier, and this class tackiness agent is all unsatisfactory aspect hot melt stability and bonding back weathering resistance.
As mentioned above, according to the embodiment second time, can obtain to have many good hot-melt adhesive composition performances, said composition not only has big bounding force, good adhesive coated, good hot melt stability, and tackiness agent also has good weathering resistance after bonding.
Industrial applicability
According to the present invention, can make a kind of again good adhesive composition of fugitive color and weatherability not of high adhesion that has.
Claims (16)
1. tackifier, it is included in the vinyl polymer that forms with polymerization of vinyl monomer under 180-350 ℃ the temperature.
2. tackifier as claimed in claim 1 is characterized in that this vinyl polymer weight-average molecular weight is 500-50,000.
3. tackifier as claimed in claim 1; it is characterized in that this vinyl polymer has (methyl) acryl monomer unit; this polymkeric substance is to form by the monomer that polymerization contains (methyl) acryl, and the unitary content of (methyl) acryl monomer is 50 to 100 quality % in all monomeric units that constitute this vinyl polymer.
4. binder composition, it comprises:
Pressure-sensitive adhesive polymers or binder polymer; With the tackifier that comprise the vinyl polymer that under 180-350 ℃ temperature, is polymerized by vinyl monomer.
5. contact adhesive composition, it comprises:
Pressure-sensitive adhesive polymers; With the tackifier that comprise the vinyl polymer that under 180-350 ℃ temperature, is polymerized by vinyl monomer.
6. in the contact adhesive composition as claimed in claim 5, it is characterized in that this vinyl polymer weight-average molecular weight is 500-50,000.
7. contact adhesive composition as claimed in claim 5; it is characterized in that this vinyl polymer has (methyl) acryl monomer unit; this polymkeric substance is to form by the monomer that polymerization contains (methyl) acryl, and the unitary content of (methyl) acryl monomer is 50 to 100 quality % in all monomeric units that constitute this vinyl polymer.
8. contact adhesive composition as claimed in claim 5 is characterized in that this pressure-sensitive adhesive polymers contains (methyl) acrylic polymers.
9. contact adhesive composition as claimed in claim 8 is characterized in that this (methyl) acrylic polymers is that second-order transition temperature (Tg) is-80-0 ℃ (methyl) acrylic ester polymer.
10. contact adhesive composition as claimed in claim 5 is characterized in that sneaking into 5-200 mass parts vinyl polymer tackifier in 100 mass parts pressure-sensitive adhesive polymers.
11. a hot-melt adhesive composition, it comprises:
Binder polymer; With the tackifier that comprise the vinyl polymer that under 180-350 ℃ temperature, is polymerized by vinyl monomer.
12. hot-melt adhesive composition as claimed in claim 11 is characterized in that this hot-melt adhesive composition contains in 100 mass parts binder polymer 5-200 mass parts tackifier.
13. hot-melt adhesive composition as claimed in claim 11 is characterized in that this tackiness agent adhesive aggregation compound is ethylene copolymer or phenylethylene-dialkene multipolymer.
14. the preparation method of a binder composition, it comprises:
Under 180-350 ℃ temperature, prepare the vinyl polymer tackifier with stirred-tank reactor with the vinyl monomer successive polymerization; With
The vinyl polymer tackifier are mixed with pressure-sensitive adhesive polymers or binder polymer.
15. the preparation method of a contact adhesive composition, it comprises:
Under 180-350 ℃ temperature, prepare the vinyl polymer tackifier with stirred-tank reactor with the vinyl monomer successive polymerization; With
The vinyl polymer tackifier are mixed with pressure-sensitive adhesive polymers.
16. the preparation method of a hot-melt adhesive composition, it comprises:
Under 180-350 ℃ temperature, prepare the vinyl polymer tackifier with stirred-tank reactor with the vinyl monomer successive polymerization; With
The vinyl polymerization tackifier are mixed with binder polymer.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP141922/00 | 2000-05-15 | ||
| JP141922/2000 | 2000-05-15 | ||
| JP2000141922 | 2000-05-15 | ||
| JP2000394718 | 2000-12-26 | ||
| JP394718/2000 | 2000-12-26 | ||
| JP394718/00 | 2000-12-26 | ||
| JP045686/01 | 2001-02-21 | ||
| JP045686/2001 | 2001-02-21 | ||
| JP2001045686 | 2001-02-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1429259A true CN1429259A (en) | 2003-07-09 |
| CN1271162C CN1271162C (en) | 2006-08-23 |
Family
ID=27343378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018094589A Expired - Lifetime CN1271162C (en) | 2000-05-15 | 2001-04-26 | Tackifier and adhesive composition |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP5217071B2 (en) |
| KR (1) | KR20040030168A (en) |
| CN (1) | CN1271162C (en) |
| AU (1) | AU2001252601A1 (en) |
| TW (1) | TWI274781B (en) |
| WO (1) | WO2001088052A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101001932B (en) * | 2004-05-21 | 2010-12-15 | 国家淀粉及化学投资控股公司 | Hot melt adhesive |
| CN102712832A (en) * | 2010-01-08 | 2012-10-03 | 阿尔卑斯电气株式会社 | TAC base for cycloolefin polymer bonding, TAC bonding member, and liquid crystal display device |
| CN103030914A (en) * | 2012-12-31 | 2013-04-10 | 宁波大榭开发区综研化学有限公司 | Acrylic ester composition, preparation method of acrylic ester composition, and adhesive tape applying composition |
| CN103249791A (en) * | 2010-12-06 | 2013-08-14 | 日本合成化学工业株式会社 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive, and adhesive sheet using same |
| WO2013182463A1 (en) * | 2012-06-04 | 2013-12-12 | Basf Se | Pressure-sensitive adhesives comprising low molecular weight acid-functional acrylic resins and methods of making and using same |
| CN106318252A (en) * | 2016-08-18 | 2017-01-11 | 宁波卓胜新材料有限公司 | Coextruded coating-type protection adhesive tape and preparation method thereof |
| CN108026224A (en) * | 2015-09-08 | 2018-05-11 | 德莎欧洲股份公司 | The adhesive substance that tacky resin is modified |
| WO2020180435A1 (en) | 2019-03-01 | 2020-09-10 | Dow Global Technologies Llc | Tackifier composition |
| CN112778954A (en) * | 2021-02-06 | 2021-05-11 | 湖北冠昌胶粘科技有限公司 | Adhesive, surface material with adhesive layer and preparation method |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5045865B2 (en) * | 2001-06-26 | 2012-10-10 | 株式会社ブリヂストン | Adhesive composition for optical functional member integrated display device and optical functional member integrated display device |
| JP4003531B2 (en) * | 2002-05-10 | 2007-11-07 | 東亞合成株式会社 | Aqueous polymer composition |
| US7238732B2 (en) * | 2004-02-18 | 2007-07-03 | Eastman Chemical Company | Radiation-curable adhesive compositions |
| JP4498057B2 (en) * | 2004-08-09 | 2010-07-07 | 日東電工株式会社 | Photopolymerizable acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet or tape using the composition |
| JP4595439B2 (en) * | 2004-08-18 | 2010-12-08 | 東亞合成株式会社 | Adhesive composition |
| KR100592421B1 (en) * | 2004-10-26 | 2006-06-26 | 주식회사 쌍 곰 | Anti-freezing Adhesives for ceramic tiles |
| KR100932371B1 (en) * | 2008-02-05 | 2009-12-16 | 김범구 | Method for producing a pressure-sensitive adhesive foam composition using the above foam composition and a method for producing a pressure-sensitive adhesive product using the foam composition prepared by the above method |
| JP6241838B2 (en) * | 2012-10-12 | 2017-12-06 | 東亞合成株式会社 | Tackifier and pressure-sensitive adhesive composition and use thereof |
| KR101470207B1 (en) | 2013-08-30 | 2014-12-08 | 현대자동차주식회사 | Environment-friendly Adhesive compositions and Tape prepared using the same |
| WO2016176821A1 (en) * | 2015-05-05 | 2016-11-10 | Dow Global Technologies Llc | Functionalized, halogenated olefin-based adhesive, articles containing and process for using thereof |
| JP6715650B2 (en) * | 2016-03-31 | 2020-07-01 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive film |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6010553B2 (en) * | 1977-06-08 | 1985-03-18 | 荒川化学工業株式会社 | pressure sensitive adhesive |
| JPS5837348B2 (en) * | 1979-06-30 | 1983-08-16 | 日東電工株式会社 | Water-dispersed pressure-sensitive adhesive composition |
| JPS603435B2 (en) * | 1981-05-06 | 1985-01-28 | 日立化成工業株式会社 | Adhesive for surface protection film |
| JPS6147772A (en) * | 1984-08-15 | 1986-03-08 | Toagosei Chem Ind Co Ltd | Resin composition for pressure-sensitive adhesive |
| US4726982A (en) * | 1987-04-10 | 1988-02-23 | Minnesota Mining And Manufacturing Company | Tackified acrylic pressure-sensitive adhesive and composite article |
| US5045569A (en) * | 1988-11-30 | 1991-09-03 | Minnesota Mining And Manufacturing Company | Hollow acrylate polymer microspheres |
| US5171793A (en) * | 1990-02-22 | 1992-12-15 | Exxon Chemical Patents Inc. | Hydrogenated resins, adhesive formulations and process for production of resins |
| JPH0431480A (en) * | 1990-05-28 | 1992-02-03 | Soken Kagaku Kk | Acrylic pressure-sensitive adhesive composition |
| US5328972A (en) * | 1992-09-28 | 1994-07-12 | Rohm And Haas Company | Process for preparing low molecular weight polymers |
| JPH10204401A (en) * | 1997-01-24 | 1998-08-04 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure sensitive adhesive composition |
| JP3533589B2 (en) * | 1997-04-09 | 2004-05-31 | 綜研化学株式会社 | Pressure-sensitive adhesive composition for polarizing plate and polarizing plate |
| US6302994B1 (en) * | 1997-06-18 | 2001-10-16 | Toagosei Co., Ltd. | Process for producing labeled article |
| JP3038549B2 (en) * | 1998-02-27 | 2000-05-08 | 三洋化成工業株式会社 | Adhesive additive and hot melt adhesive composition |
-
2001
- 2001-04-26 WO PCT/JP2001/003627 patent/WO2001088052A1/en not_active Application Discontinuation
- 2001-04-26 KR KR1020027015205A patent/KR20040030168A/en not_active Application Discontinuation
- 2001-04-26 JP JP2001585263A patent/JP5217071B2/en not_active Expired - Lifetime
- 2001-04-26 CN CNB018094589A patent/CN1271162C/en not_active Expired - Lifetime
- 2001-04-26 AU AU2001252601A patent/AU2001252601A1/en not_active Abandoned
- 2001-05-11 TW TW090111247A patent/TWI274781B/en not_active IP Right Cessation
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101001932B (en) * | 2004-05-21 | 2010-12-15 | 国家淀粉及化学投资控股公司 | Hot melt adhesive |
| CN102712832A (en) * | 2010-01-08 | 2012-10-03 | 阿尔卑斯电气株式会社 | TAC base for cycloolefin polymer bonding, TAC bonding member, and liquid crystal display device |
| CN102712832B (en) * | 2010-01-08 | 2014-07-16 | 阿尔卑斯电气株式会社 | TAC base for cycloolefin polymer bonding, TAC bonding member, and liquid crystal display device |
| CN103249791A (en) * | 2010-12-06 | 2013-08-14 | 日本合成化学工业株式会社 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive, and adhesive sheet using same |
| US9657204B2 (en) | 2012-06-04 | 2017-05-23 | Basf Se | Pressure-sensitive adhesives comprising low molecular weight acid-functional acrylic resins and methods of making and using same |
| US10093839B2 (en) | 2012-06-04 | 2018-10-09 | Basf Se | Pressure-sensitive adhesives comprising low molecular weight acid-functional acrylic resins and methods of making and using same |
| WO2013182463A1 (en) * | 2012-06-04 | 2013-12-12 | Basf Se | Pressure-sensitive adhesives comprising low molecular weight acid-functional acrylic resins and methods of making and using same |
| CN103030914B (en) * | 2012-12-31 | 2015-04-01 | 宁波大榭开发区综研化学有限公司 | Acrylic ester composition, preparation method of acrylic ester composition, and adhesive tape applying composition |
| CN103030914A (en) * | 2012-12-31 | 2013-04-10 | 宁波大榭开发区综研化学有限公司 | Acrylic ester composition, preparation method of acrylic ester composition, and adhesive tape applying composition |
| CN108026224A (en) * | 2015-09-08 | 2018-05-11 | 德莎欧洲股份公司 | The adhesive substance that tacky resin is modified |
| CN106318252A (en) * | 2016-08-18 | 2017-01-11 | 宁波卓胜新材料有限公司 | Coextruded coating-type protection adhesive tape and preparation method thereof |
| CN106318252B (en) * | 2016-08-18 | 2019-10-29 | 宁波卓胜新材料有限公司 | A kind of co-extrusion application type protective glue band and preparation method thereof |
| WO2020180435A1 (en) | 2019-03-01 | 2020-09-10 | Dow Global Technologies Llc | Tackifier composition |
| CN112778954A (en) * | 2021-02-06 | 2021-05-11 | 湖北冠昌胶粘科技有限公司 | Adhesive, surface material with adhesive layer and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2001252601A1 (en) | 2001-11-26 |
| CN1271162C (en) | 2006-08-23 |
| TWI274781B (en) | 2007-03-01 |
| WO2001088052A1 (en) | 2001-11-22 |
| JP5217071B2 (en) | 2013-06-19 |
| KR20040030168A (en) | 2004-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1271162C (en) | Tackifier and adhesive composition | |
| CN1024559C (en) | Adhesive compositions containing low molecular weight polymer additives | |
| TWI236494B (en) | Adhesive compositions containing low molecular weight polymeric additives | |
| CN1255469C (en) | Adhesive components and process for manufacture | |
| CN1221621C (en) | Adhesive compositions containing graft copolymers | |
| CN1966595A (en) | Activatable compositions | |
| CN1190421A (en) | Acrylate-containing polymer blends | |
| CN1720309A (en) | Polymer compositions | |
| JP2003049130A (en) | Method for producing acrylic adhesive tape and acrylic adhesive tape | |
| CN109642137A (en) | (methyl) acrylic oligomers | |
| CN1807076A (en) | Process for the manufacture of paperboard cartons | |
| CN110128980A (en) | A kind of plasticizer-resistant hot melt adhesive and preparation method thereof | |
| CN1753946A (en) | Elastomer composition and pressure-sensitive adhesive compositions | |
| CN1226917A (en) | Adhesive composition | |
| CN1537912A (en) | Blends of high T.g polymer emulsions and pressure sensitive adhesive polymer emulsion usefuel as pressure sensitive adhesives | |
| CN1703457A (en) | Heat sealable compositions and uses thereof | |
| JP3948279B2 (en) | Aqueous dispersion, production method and use thereof | |
| CN1043331A (en) | Use modified latex polymer laminating adhesive composition to make flexible electronic circuit | |
| JP2005521774A (en) | Rubber-acrylic adhesive formulation | |
| JP2008038057A (en) | Water dispersion containing rubber component | |
| AU2018392478B2 (en) | Post-polymerization functionalization of pendant functional groups | |
| Antosik et al. | Pressure-sensitive adhesives based on acrylics | |
| JP2004010835A (en) | Ultraviolet-curable acrylic pressure sensitive adhesive, process for producing it and pressure sensitive adhesive sheet | |
| JP2003292919A (en) | Hot-melt adhesive | |
| JP3041687B2 (en) | Adhesive modifier and hot melt adhesive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060823 |