CN1910209A - Modified petroleum resin emulsion and acrylic pressure -sensitive adhesive compositions containing the same - Google Patents
Modified petroleum resin emulsion and acrylic pressure -sensitive adhesive compositions containing the same Download PDFInfo
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- CN1910209A CN1910209A CNA2005800025262A CN200580002526A CN1910209A CN 1910209 A CN1910209 A CN 1910209A CN A2005800025262 A CNA2005800025262 A CN A2005800025262A CN 200580002526 A CN200580002526 A CN 200580002526A CN 1910209 A CN1910209 A CN 1910209A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
Abstract
The invention relates to a modified petroleum resin emulsion containing a modified petroleum resin which comprises 10 to 100 % by mass of C4-6 olefinic unsaturated hydrocarbon monomer units and 0 to 90 % by mass of C7-11 olefininc unsaturated hydrocarbon monomer units and has a softening point of 30 1/2 C or above and an acid value of 0.1 to 100 KOHmg/g, and provides acrylic pressure-sensitive adhesive compositions which are excellent both in the peel adhesion to polyolefin resin adherends and in the balance between initial tack and holding power and a modified petroleum resin emulsion useful as the tackifier for the compositions.
Description
Technical field
The present invention relates to the acrylic pressure-sensitive adhesive compositions of modified petroleum resin emulsion and this emulsion of use, say in further detail, The present invention be more particularly directed to the polyolefin resin adherend peeled off the bonding strength excellence, and at initial bond strenght with keep acrylic pressure-sensitive adhesive compositions also excellent aspect the equilibrium of forces and be preferably used as the modified petroleum resin emulsion of these binder composition tackifier.
Background technology
With acrylic polymers emulsion is the aqueous adhesive composition of main component, water white transparency and ageing-resistant performance excellence, and be widely used because of the volatilization of organic solvent is not easy to produce environmental problem.In described acrylic pressure-sensitive adhesive compositions, be purpose to improve adhesion characteristics such as peel adhesion strength, initial adhesion strength and confining force, be mixed with tackifying resins such as rosin based tackifying resin, terpenes tackifying resin and tree oil lipid tackifying resin usually.
For example, disclose in the patent documentation 1 and in acrylic polymers emulsion, mixed the water-borne acrylic type binder composition that contains petroleum resin emulsion, wherein petroleum resin contain aromatic vinyl monomer unit such as the vinylbenzene of 10-60% quality or alpha-methyl styrene, and softening temperature is 10-20 ℃.Disclose in the patent documentation 2 and mixed the water-borne acrylic type binder composition that contains tackifying resin emulsion in acrylic polymers emulsion, wherein tackifying resin is with the aromatic ring partial hydrogenation of C9 cut polymerization gained aromatic resins such as Vinyl toluene, indenes and make.Yet above-mentioned binder composition is poor to the peel adhesion strength of the so nonpolar adherend of polyethylene.
Further, the water-borne acrylic type binder composition is disclosed in the patent documentation 3, said composition is by being the solids component of-60 ℃ to-30 ℃ acrylic polymers emulsion with respect to 100 mass parts second-order transition temperatures, mixes 3-45 mass parts liquid tackifying resin and linking agent and makes.Yet this binder composition confining force is poor.
Patent documentation 1: Japanese kokai publication sho 61-275363 communique
Patent documentation 2: Japanese kokai publication hei 9-188864 communique
Patent documentation 3: TOHKEMY 2000-319618 communique
Summary of the invention
In view of the foregoing, the object of the invention is to provide the peel adhesion strength excellence to the polyolefin resin adherend, and in initial adhesion strength with keep acrylic pressure-sensitive adhesive compositions also excellent aspect the equilibrium of forces and be preferably used as the modified petroleum resin emulsion of these binder composition tackifier.
The inventor etc. further investigate in order to achieve the above object, found that: use and contain the modified petroleum resin emulsion that modified petroleum resin is made, can obtain peel adhesion strength excellence to the polyolefin resin adherend, and in initial adhesion strength with keep also excellent acrylic acid or the like binding compositions aspect the equilibrium of forces, wherein modified petroleum resin contains the ethylenically unsaturated hydrocarbons monomeric unit of the carbonatoms 7-11 of the ethylenically unsaturated hydrocarbons monomeric unit of carbonatoms 4-6 of 10-100% quality and 0-90% quality, have specific softening temperature and acid number, realized the present invention finally based on above discovery.
Therefore, the invention provides and contain the modified petroleum resin emulsion that modified petroleum resin is made, wherein modified petroleum resin contains the ethylenically unsaturated hydrocarbons monomeric unit of the carbonatoms 7-11 of the ethylenically unsaturated hydrocarbons monomeric unit of carbonatoms 4-6 of 10-100% quality and 0-90% quality, softening temperature is more than 30 ℃, and acid number is 0.1-100KOHmg/g.
The present invention also provides the acrylic pressure-sensitive adhesive compositions that contains acrylic polymers emulsion and above-mentioned modified petroleum resin emulsion.
The adhesive tape that the present invention further provides coating aforesaid propylene acids binder composition on carrier and make.
The best mode that carries out an invention
Below describe the present invention in detail.
(modified petroleum resin emulsion)
Modified petroleum resin emulsion of the present invention contains modified petroleum resin and is prepared from, wherein modified petroleum resin contains the hydro carbons unsaturated hydrocarbon monomer unit of the carbonatoms 7-11 of the ethylenically unsaturated hydrocarbons monomeric unit of carbonatoms 4-6 of 10-100% quality and 0-90% quality, softening temperature is more than 30 ℃, and acid number is 0.1-100KOHmg/g.
Above-mentioned modified petroleum resin contains the 10-100% quality, is preferably the 40-95% quality, more preferably the carbonatoms 4-6 of 50-85% quality ethylenically unsaturated hydrocarbons monomeric unit and 0-90% quality, be preferably 5-60% quality, the ethylenically unsaturated hydrocarbons monomeric unit of the carbonatoms 7-11 of 15-50% quality more preferably.If the content of the ethylenically unsaturated hydrocarbons monomeric unit of carbonatoms 4-6 is few, then poor to the peel adhesion strength of polyolefin resin adherend, initial adhesion strength is also low.From further raising the peel adhesion strength of polyolefin resin adherend and the angle of confining force are considered, be preferably the modified petroleum resin of the ethylenically unsaturated hydrocarbons monomeric unit that contains carbonatoms 7-11.
Being used as the ethylenically unsaturated hydrocarbons monomer of the carbonatoms 4-6 of raw material, for example can be that the monoene of carbonatoms 4-6 belongs to unsaturated hydrocarbons and diolefinic unsaturated hydrocarbons.
The monoene of carbonatoms 4-6 belongs to unsaturated hydrocarbons, for example can be chain monoene such as iso-butylene, 1-butylene, 2-butylene, 1-amylene, 2-amylene, methyl butene, methylpentene, hexene; Ring-type monoene such as cyclopentenes, methyl cyclopentene, tetrahydrobenzene etc.
The diolefinic unsaturated hydrocarbon monomer of carbonatoms 4-6 for example can be 1,3-butadiene, isoprene, 1,3-pentadiene, 1, chain conjugated diolefines such as 3-hexadiene; Cyclic conjugated diene such as cyclopentadiene, methyl cyclopentadiene; 1,1, non-conjugated dienes such as 4-pentadiene etc.
During the preparation modified petroleum resin, the monomeric consumption of the ethylenically unsaturated hydrocarbons of carbonatoms 4-6 with respect to the monomer total amount, is preferably more than 10% weight, and more preferably the 45-95% quality is preferably the 55-85% quality especially.If its consumption is very few, then poor to the peel adhesion strength of polyolefin resin adherend, initial adhesion strength is also low.
The monoene of carbonatoms 4-6 belongs to the ratio of the diolefinic unsaturated hydrocarbon monomer of unsaturated hydrocarbon monomer and carbonatoms 4-6, by quality ratio, is preferably 20/80-80/20, and 30/70-70/30 more preferably is preferably the scope of 35/65-65/35 especially.
Among the present invention, the preferred use contained above, the more preferably diolefinic unsaturated hydrocarbons of the carbonatoms 4-6 of the above isoprene of 90% quality and/or 1,3-pentadiene of 70% quality.
Being used as the ethylenically unsaturated hydrocarbons monomer of the carbonatoms 7-11 of raw material as required, for example can be aromatic vinyl monomers such as vinylbenzene, alpha-methyl styrene, p-methylstyrene, ethyl styrene, t-butyl styrene; 2,4,4-trimethylammonium-1-amylene, 2,4, the chain monoene of carbonatoms 7-11 such as 4-trimethylammonium-2-amylene, heptene, octene; The ring-type alkene of carbonatoms 7-11 such as tetrahydrotoluene, dicyclopentadiene, indenes, coumarone etc.Wherein, preferably use aromatic vinyl monomer, more preferably use vinylbenzene.
During the preparation modified petroleum resin, the monomeric consumption of the ethylenically unsaturated hydrocarbons of carbonatoms 7-11 with respect to the monomer total amount, is preferably below 90% quality, and more preferably the 5-55% quality is preferably the 15-45% quality especially.If use with above-mentioned scope, then can obtain peel adhesion strength and the more excellent acrylic pressure-sensitive adhesive compositions of confining force to the polyolefin resin adherend.
The softening temperature of modified petroleum resin is more than 30 ℃, preferred 50-130 ℃, and more preferably 80-120 ℃.If 30 ℃ of softening temperature less thaies, the binder composition of the power that then is maintained difference.
The acid number of modified petroleum resin is 0.1-100KOHmg/g, is preferably 0.3-50KOHmg/g, more preferably 1-20KOHmg/g.If acid number is low or high, then poor to the peel adhesion strength of polyolefin resin adherend.
The weight-average molecular weight of modified petroleum resin is preferably 1,000-4,000, more preferably 1,500-3,500 scope.If weight-average molecular weight is above-mentioned scope, then can obtain peel adhesion strength and the more excellent acrylic pressure-sensitive adhesive compositions of confining force to the polyolefin resin adherend.
Above-mentioned modified petroleum resin can be by at first making petroleum resin, then ethylenic unsaturated carboxylic acid and gained petroleum resin are carried out addition reaction and obtain, described petroleum resin can be by usually in polymer solvent, use the carboxylic acid halides metal catalyst, make above-mentioned monomer carry out cationoid polymerisation and obtain.
Polymer solvent is not so long as hinder the solvent of polyreaction to get final product, and there is no particular limitation as to it.For example can be aliphatic hydrocarbons such as pentane, hexane, heptane, pentamethylene, hexanaphthene, iso-pentane, methylpentane; Aromatic hydrocarbons such as benzene,toluene,xylene etc.Above-mentioned polymer solvent can use separately or multiple being used in combination.
The consumption of polymer solvent with respect to 100 mass parts monomer total amounts, is generally the 40-200 mass parts, is preferably the 60-100 mass parts.
As the carboxylic acid halides metal catalyst of polymerizing catalyst, so long as Friedel-Craft type catalyzer gets final product, there is no particular limitation as to it.Its representation example has: fluorochemical, muriate, bromide and the iodide of metals such as aluminium, boron, iron.Wherein preferably use aluminum halides such as aluminum chloride, aluminum bromide, more preferably use aluminum chloride.
The consumption of carboxylic acid halides metal catalyst, the monomer total amount is generally the 0.1-10% quality relatively, is preferably the 0.5-5% quality.
The carboxylic acid halides metal catalyst is contacted in advance with the ring-type monoene.This ring-type monoene preferably uses the ring-type monoene of carbonatoms 5-6, more preferably uses cyclopentenes.Preferably be at least 5 times of amounts of carboxylic acid halides metal catalytic dosage in the amount of this used ring-type monoene.
Converging operation can adopt the method for conventional known.
Polymerization temperature is generally-20 ℃-100 ℃, is preferably 0 ℃-80 ℃ scope.
After polyreaction begins,, add polymerization terminator, polyreaction is stopped in the moment that reaches the regulation polymerisation conversion.Polymerisation conversion when stopping polyreaction is generally the 50-95% quality, is preferably the 60-90% quality.
After stopping polyreaction, heat up in a steamer unreacted monomer and polymer solvent, further as required,, remove low-molecular-weight oligopolymer composition, can obtain petroleum resin by at high temperature carrying out wet distillation.
Next, make ethylenic unsaturated carboxylic acid and gained petroleum resin carry out addition reaction, make petroleum resin modified.
The ethylenic unsaturated carboxylic acid for example can be ethene unsaturated monocarboxylics such as vinylformic acid, methacrylic acid; The unsaturated polycarboxylic acids of ethylenic such as toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid; The unsaturated polybasic acid anhydride of ethylenic such as maleic anhydride, itaconic anhydride; The part ester of the unsaturated polycarboxylic acid of ethylenic such as monomethyl maleate, monomethyl fumarate etc.Wherein preferably use unsaturated polycarboxylic acid of ethylenic and the unsaturated polybasic acid anhydride of ethylenic, more preferably use the unsaturated polybasic acid anhydride of ethylenic, especially preferably use maleic anhydride.
The consumption of ethylenic unsaturated carboxylic acid with respect to the above-mentioned petroleum resin that make of 100 mass parts, is preferably the 0.01-20 mass parts, and 0.05-10 mass parts more preferably is preferably the scope of 0.5-5 mass parts especially.
The condition that makes the ethylenic unsaturated carboxylic acid carry out addition reaction, under 50-300 ℃, preferably under 200-270 ℃, preferred reaction 5 minutes to 20 hours was more preferably reacted 10 minutes to 3 hours usually.When addition reaction, also can add thinner, anti-gelifying agent, reaction promotor etc. under the necessary situation.
Modified petroleum resin emulsion of the present invention is to make the above-mentioned gained modified petroleum resin emulsion that emulsification makes in water medium.
Water medium can make water usually, also can use the aqueous solution of water-miscible organic solvents such as ethanol, ethylene glycol, glycerine.
The consumption of water medium with respect to 100 mass parts modified petroleum resins, is generally the 50-200 mass parts, is preferably the 60-150 mass parts.Emulsification method is not particularly limited, for example can is: in (1) water medium, under the temperature of the not enough softening temperature of modified petroleum resin, make modified petroleum resin wet method dispersive method; (2) in the water medium, make modified petroleum resin heat to the state of temperature of fluidised form degree the method for emulsification modified petroleum resin; (3) in the water medium, make the organic solvent solution emulsive method of modified petroleum resin; (4) heating to the modified petroleum resin of the temperature of fluidised form degree the Phase inversion emulsification method of adding water medium while stirring; (5) in the organic solvent solution of modified petroleum resin, add the Phase inversion emulsification method of water medium etc. while stirring.Wherein, the modified petroleum resin particulate volume average particle size from easy adjusting modified petroleum resin emulsion to the angle of preferable range is considered, the preferred method that adopts (3) or (5).Under the situation with an organic solvent, preferably heat up in a steamer organic solvent the emulsion after emulsification.
Make modified petroleum resin emulsive mode of the present invention, can be (a) impacting with high pressure formula (go-リ Application homogenizer: go-リ Application company is made), (b) rotor-stator mode (エ バ ラ マ ィ Le ダ-: weak original manufacturer manufacturing), (c) internal shear (liquid-liquid is sheared) mode (for example Network レ ア ミ Star Network ス, エ system テ Network ニ Star Network company makes), (d) stationary tube mode (static mixer), (e) anchor type alr mode, (f) ラ ィ Application ミ Le mode, (g) oscillatory type, (h) film emulsifying-type, (i) centrifugal thin-film contact etc.Wherein, the modified petroleum resin particulate volume average particle size from easy adjusting modified petroleum resin emulsion to the angle of preferable range is considered, preferably adopts (a) and (b) or mode (c), especially preferably adopts the mode of (a).
Make modified petroleum resin dissolved organic solvent, can there is no particular limitation as to it so long as dissolve the organic solvent of this resin.For example can be: aromatic hydrocarbons such as benzene, toluene; Aliphatic hydrocarbons such as pentane, hexane, heptane; Alicyclic hydrocarbon such as pentamethylene, hexanaphthene etc.If consider the easiness that security in the emulsifying process or organic solvent heat up in a steamer, then preferably use boiling point to be 30-120 ℃ organic solvent.
Strength of solution is generally the 10-90% quality, is preferably the 50-80% quality.
During emulsification, the modified petroleum resin particulate volume average particle size from easy adjusting modified petroleum resin emulsion to the angle of the package stability excellence of preferable range, gained modified petroleum resin emulsion is considered, preferably uses emulsifying agent.
Emulsifying agent is not particularly limited, for example can is: anionic emulsifiers such as the half ester salt of the sulfo-succinic acid of alpha-alefinically sulfonated bodies, alkyl-sulphate, alkyl sulfate-base, polyoxyethylene alkylphenyl ether sulfate salt, polyoxyethylene alkyl phenyl ether, rosined soap; Nonionic emulsifier such as Voranol EP 2001, polyoxyethylene alkyl phenyl ether.The consumption of emulsifying agent with respect to 100 mass parts modified petroleum resins, is generally about the 1-10 mass parts, and excellent is the 1-5 weight part.
Modified petroleum resin particulate volume average particle size in the modified petroleum resin emulsion is preferably 0.1-1 μ m, more preferably 0.2-0.6 μ m.If make volume average particle size become above-mentioned scope, then can obtain more excellent acrylic pressure-sensitive adhesive compositions aspect bonding physical properties balance.
In the modified petroleum resin emulsion of this patent invention, preferable particle size is the above few emulsions of modified petroleum resin particle of 30 μ m.Above granule number is too much if particle diameter is 30 μ m, when then coating the gained binder composition on the carrier, there is binder composition air spots degraded appearance, simultaneously because of producing the film that flake can not get homogeneous, form time goods, peel adhesion strength is hanged down inferior problem.Particle diameter is the above modified petroleum resin particulate granule numbers of 30 μ m, can use accurate particle size distribution device, is limited in the specific particle size range and measures.Particle diameter is that the above modified petroleum resin particulate granule number of 30 μ m carries out relative evaluation with following method, promptly measuring whole particle diameters is the granule number of the modified petroleum resin of 4-64 μ m, and getting wherein, particle diameter is the modified petroleum resin particulate number ratio of 30-64 μ m.
At particle diameter is in the modified petroleum resin particle of 4-64 μ m, particle diameter is that the above modified petroleum resin particulate number ratio of 30 μ m is preferably below 1%, more preferably below 0.1%, more preferably below 0.05%, especially preferably not having particle diameter is the above particles of 30 μ m.
To making particle diameter is that the method that the modified petroleum resin particulate granule number of 4-64 μ m is scattered in above-mentioned scope is not particularly limited, and for example can be the method for the condition when suitably regulating the emulsification modified petroleum resin, be modified petroleum resin particulate method more than the 30 μ m etc. removing particle diameter behind the emulsification modified petroleum resin.Adjustable condition such as temperature, pressure and stirring intensity etc. are regulated above-mentioned condition as required during the emulsification modified petroleum resin.Removing particle diameter behind the emulsification modified petroleum resin is modified petroleum resin particulate method more than the 30 μ m, for example can be to use the gravity of filter screen or pressure filtration method, use the method for the pressure filtration that the membrane filter filtration unit is housed etc., consider from removing device and aspect easy and simple to handle, preferably use filter screen to carry out pressure filtration.In order to make particle diameter is that the modified petroleum resin particulate granule number of 4-64 μ m is scattered in above-mentioned scope, can repeat above-mentioned filter operation.
The solid component concentration of modified petroleum resin emulsion is preferably more than 30% quality, more preferably the 40-70% quality.
In modified petroleum resin emulsion, can further add Synergist S-421 95s such as defoamer, tackifier, weighting agent, antioxidant, sanitas, antiseptic-germicide as required.
(acrylic pressure-sensitive adhesive compositions)
Acrylic pressure-sensitive adhesive compositions of the present invention is the composition that contains acrylic polymers emulsion and above-mentioned modified petroleum resin emulsion.
The acrylic polymers that constitutes acrylic polymers emulsion is the polymkeric substance of main component for containing with (methyl) alkyl acrylate monomer units.
(methyl) alkyl acrylate monomer for example can be: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA etc.These monomers can be used alone or in combination.
Acrylic polymers, can be (methyl) alkyl acrylate monomer and can with other monomeric multipolymer of its copolymerization.
Can with other monomer of (methyl) alkyl acrylate monomer copolymerization, for example can be: (methyl) vinylformic acid, (methyl) glycidyl acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, N-methylol (methyl) acrylamide, (methyl) vinyl cyanide, vinyl acetate, vinylbenzene etc.
Second-order transition temperature to acrylic polymers is not particularly limited, and is generally-80 ℃ to 0 ℃, is preferably-60 ℃ to-10 ℃.If second-order transition temperature is too high, then there is the low tendency of initial adhesion strength, on the contrary, if cross the low low tendency of confining force that then exists.
Acrylic polymers emulsion is prepared from by the above-mentioned monomer of emulsion polymerization usually.Method to emulsion polymerization is not particularly limited, and can adopt the method for conventional known.
Acrylic polymers particulate volume average particle size in the acrylic polymers emulsion is not particularly limited, is generally 0.05-1 μ m, be preferably 0.1-0.6 μ m.
The solid component concentration of acrylic polymers emulsion is generally the 40-70% quality.
Acrylic pressure-sensitive adhesive compositions of the present invention, with respect to the solids component of 100 mass parts acrylic polymers emulsions, preferably contain with solids component count the 0.1-50 mass parts, more preferably the 2-40 mass parts, be preferably 5-30 mass parts modified petroleum resin emulsion especially.If make the consumption of modified petroleum resin emulsion become above-mentioned scope, then can obtain peel adhesion strength excellence, the binder composition that initial adhesion strength and confining force are more excellent to the polyolefin resin adherend.
In acrylic pressure-sensitive adhesive compositions, can further add Synergist S-421 95s such as softening agent, paraffin, UV light absorber, defoamer, tackifier, weighting agent, antioxidant, sanitas, antiseptic-germicide, anti-hydrated agent, membrane producing promoter as required.Substantially do not hinder under the prerequisite of effect of the present invention, also can add the emulsion that contains tackifying resin of conventional known.
(adhesive tape)
The adhesive tape that adhesive tape of the present invention is made for coating aforesaid propylene acids binder composition on carrier.
Carrier is not particularly limited, for example can is: stationeries such as kraft paper, Japan paper, good quality paper, synthetic paper; Dry goods such as continuous cloth, Artificial Fibers cloth, mylar; Resin films such as cellulose film, polyester film, polyamide layer, polyvinyl chloride film, polypropylene film, polyethylene film; Tinsel such as aluminium foil, Copper Foil; The non-woven fabrics of polyester non-woven fabrics, artificial silk system non-woven fabrics etc. etc.These carriers can be in advance Corona discharge Treatment to be carried out on its surface, also can be the carriers that was coated with priming paint in advance.
Carrier thickness is generally about 10 μ m-2mm.
Apparatus for coating can use the device of conventional known, for example can use ダ ィ コ--, コ Application マ コ--, roll-type spreadometer etc.
The glue spread of acrylic pressure-sensitive adhesive compositions with dried thickness gauge, is generally 1-200 μ m, is preferably 5-100 μ m.
Behind coating acrylic pressure-sensitive adhesive compositions on the carrier, make the water medium volatilization in the said composition, can obtain adhesive tape.
Adhesive tape of the present invention is owing to especially to the peel adhesion strength excellence of nonpolar polyolefin hydrocarbon resin adherend, therefore be preferably used as the adhesive tape that nonpolar polyolefin hydrocarbon resin goods are used.Certainly, also can preferably use with the adhesive tape of nonpolar polyolefin hydrocarbon resin goods as carrier.
Here, so-called polyolefin resin mainly is meant the homopolymer or the multipolymer of olefinic monomers such as ethene, propylene, butylene, iso-butylene.Also can contain material in the polyolefin resin with minute quantity polar group.
Embodiment
Below enumerate embodiment the present invention is described, but the present invention is not limited to these embodiment." % " and " part " among the embodiment are quality standard except that special qualification.
Estimate according to following.
(1) the vinylbenzene unit vol (%) in the resin: use
1H-NMR analyzes and tries to achieve.
(2) weight-average molecular weight: use gel permeation chromatography, try to achieve as standard polyolefine scaled value.
(3) softening temperature (℃): according to JIS K 2531, measure with ring and ball method.
(4) acid number (KOHmg/g): measure according to JIS K 0070.
(5) volume average particle size of emulsion: measure with scattering of light particle size determination device (LS-230: ベ Star Network マ Application コ-Le -company makes).
The modified petroleum resin particulate number ratio that (6) 30 μ m are above: (ィ ソ ト Application-(solid component concentration: 50%), stirring is made to measure and is used sample II) to be added into 0.1g modified petroleum resin emulsion with 200ml electrolytic solution.With accurate particle size distribution device (マ Le チ サ ィ ザ-3: ベ Star Network マ Application コ-Le -company makes), be the scope of 4-64 μ m at particle diameter, measuring particle diameter with 2 μ m scales is the above modified petroleum resin particulate numbers of 30 μ m.Using the aperture in the mensuration is ア パ チ ャ-pipe of 140 μ m.
Above-mentioned particle diameter is the above modified petroleum resin particulate number ratios of 30 μ m, is used in the modified petroleum resin that particle diameter is 4-64 μ m, and particle diameter is that the modified petroleum resin particulate number ratio of 30-64 μ m is represented.
(7) peel adhesion strength (N/m): under 23 ℃, use polyethylene, measure based on PSTC-1 (180 ° of release adhesives according to the adhesive tape council (U.S.) are tested) as adherend.High more good more with value.
(8) confining force (minute): use stainless steel as adherend, based on PSTC-6 (according to the confining force test method(s) of the adhesive tape council (U.S.)), use the wide adhesive tape of 25mm, bond site is 25 * 25mm, load is 3.92 * 104Pa, under 50 ℃ of temperature, measure time till peeling off (minute).The longer the better with the time.
(9) initial adhesion strength (mm): ロ-リ Application グ ボ-Le Star Network is based on PSTC-6 (according to the initial adhesion strength test of the adhesive tape council (U.S.)) mensuration under 23 ℃.The smaller the better to be worth.
(synthesis example 1)
86 parts of pentamethylene, 14 parts of cyclopentenes and 1 part of aluminum chloride are added in the reactor, are warming up to 50 ℃ then.Subsequently, to contain 14 parts of cyclopentenes, 44 part 1, the surplus monomer mixture of the chain monoene (containing 1-amylene, 2-butylene, methyl butene etc.) of 3-pentadiene, 18 parts of vinylbenzene and 10 parts of carbonatoms 4-6 was added in the reactor continuously with 60 minutes, carried out polymerization simultaneously.Further, continue reaction 10 minutes down at 50 ℃, the mixture with methyl alcohol and ammoniacal liquor is added in the reactor then, stops polyreaction.The polymerisation conversion in this moment is 85%.
The throw out that will stop generating because of polymerization after removing by filter, is packed resulting polymers solution in the still pot into, heats under nitrogen atmosphere, removes polymer solvent and unreacted monomer.Next, with temperature more than 240 ℃, be blown into saturated steam and remove low-molecular-weight oligopolymer composition simultaneously.
Next, with respect to the resin of 100 parts of molten states, add 2.97 parts of maleic anhydrides, make it to carry out addition reaction in 1 hour under 230 ℃, add, mix 0.3 part 2 then, 6-two-tertiary butyl-p-cresol is as antioxidant.
, take out the resin of molten state, put and be chilled to room temperature, obtain modified petroleum resin A thereafter.Measure vinylbenzene unit vol, weight-average molecular weight, softening temperature and the acid number of modified petroleum resin A, its result is as shown in table 1.
(synthesis example 2)
Except changing to composition of monomer shown in the table 1 and maleic anhydride amount,, obtain modified petroleum resin B with synthesis example 1 the same operation.Measure vinylbenzene unit vol, weight-average molecular weight, softening temperature and the acid number of modified petroleum resin B, its result is as shown in table 1.
(synthesis example 3)
86 parts of pentamethylene, 14 parts of cyclopentenes and 1 part of aluminum chloride are added in the reactor, are warming up to 50 ℃ then.Subsequently, to contain 14 parts of cyclopentenes, 44 part 1, the surplus monomer mixture of the chain monoene (containing 1-amylene, 2-butylene, methyl butene etc.) of 3-pentadiene, 18 parts of vinylbenzene and 10 parts of carbonatoms 4-6 was added in the reactor continuously with 60 minutes, carried out polymerization simultaneously.Further, continue reaction 10 minutes down at 50 ℃, the mixture with methyl alcohol and ammoniacal liquor is added in the reactor then, stops polyreaction.The polymerisation conversion in this moment is 85%.
The throw out that will stop generating because of polymerization after removing by filter, is packed resulting polymers solution in the still pot into, heats under nitrogen atmosphere, removes polymer solvent and unreacted monomer.Next, with temperature more than 240 ℃, be blown into saturated steam and remove low-molecular-weight oligopolymer composition simultaneously.
Next, with respect to the resin of 100 parts of molten states, add, mix 0.3 part 2,6-two-tertiary butyl-p-cresol is as antioxidant., take out the resin of molten state, put and be chilled to room temperature, obtain petroleum resin C thereafter.Measure vinylbenzene unit vol, weight-average molecular weight, softening temperature and the acid number of petroleum resin C, its result is as shown in table 1.
(synthesis example 4)
86 parts of pentamethylene, 14 parts of cyclopentenes and 1 part of aluminum chloride are added in the reactor, are warming up to 50 ℃ then.Subsequently, to contain 7 parts of cyclopentenes, 22 part 1, the surplus monomer mixture of the chain monoene (containing 1-amylene, 2-butylene, methyl butene etc.) of 3-pentadiene, 18 parts of vinylbenzene and 39 parts of carbonatoms 4-6 was added in the reactor continuously with 60 minutes, carried out polymerization simultaneously.Further, continue reaction 10 minutes down at 50 ℃, the mixture with methyl alcohol and ammoniacal liquor is added in the reactor then, stops polyreaction, and the polymerisation conversion in this moment is 76%.
The throw out that will stop generating because of polymerization after removing by filter, is packed resulting polymers solution in the still pot into, heats under nitrogen atmosphere, removes polymer solvent and unreacted monomer.
Next, with respect to the resin of 100 parts of molten states, add 3.49 parts of maleic anhydrides, make it to carry out addition reaction in 1 hour under 230 ℃, add, mix 0.3 part 2 then, 6-two-tertiary butyl-p-cresol is as antioxidant.
, take out the resin of molten state, put and be chilled to room temperature, obtain modified petroleum resin D thereafter.Measure vinylbenzene unit vol, weight-average molecular weight, softening temperature and the acid number of modified petroleum resin D, its result is as shown in table 1.
Table 1
| Synthesis example | ||||
| 1 | 2 | 3 | 4 | |
| Monomer is formed (% quality) cyclopentenes 1,3-pentadiene isoprene vinylbenzene chain monoene | 28 44 - 18 10 | 14 - 26 36 24 | 28 44 - 18 10 | 21 22 - 18 39 |
| Polymerisation conversion | 85 | 85 | 85 | 76 |
| Addition reaction maleic anhydride (part) | 2.97 | 1.4 | - | 3.49 |
| Modified petroleum resin vinylbenzene unit vol (%) weight-average molecular weight softening temperature (℃) acid number (KOHmg/g) | A 21 3,000 102 17 | B 43 2,200 95 8 | C 21 3,000 100 ＜0.1 | D 19 800 20 20 |
(embodiment 1)
100 parts of modified petroleum resin A are being dissolved in the solution of 60 parts of toluene gained, interpolation is dissolved in the aqueous solution of gained in 100 parts of water with 4 parts of anionic emulsifiers (Sodium dodecylbenzene sulfonate), uses homogenizer under 80 ℃, with 1500rpm rotating speed emulsification 1 hour.Further, use go-リ Application homogenizer, under 90 ℃,, obtain the emulsification of homogeneous particle diameter gained emulsification emulsification 10 minutes.
, by underpressure distillation remove toluene in emulsification, use 150 order stainless steel metal net filtrations then, next use 500 order stainless steel metal net filtrations, obtain containing solid component concentration and be the resin emulsion A1 of 50% modified petroleum resin A thereafter.Measure volume average particle size and the above modified petroleum resin particulate number ratio of 30 μ m of resin emulsion A1, its result is as shown in table 2.
With respect to 100 parts of solids components that with the butyl acrylate units are the acrylic polymers emulsion (aqueous-based adhesive: ACHEM TECHNOLOGYCORPORATION makes) of the solid component concentration 50% of main component, mixing is counted 15 parts of resin emulsion A with solids component, the preparation acrylic pressure-sensitive adhesive compositions.
Use the experiment apparatus for coating, be coated on the gained acrylic pressure-sensitive adhesive compositions on the thick polyester film of 25 μ m and carry out drying, making dried thickness is 25 μ m, obtains adhesive tape.
Measure this adhesive tape to poly peel adhesion strength, confining force and initial adhesion strength.The result is as shown in table 2.
(embodiment 2)
Operate similarly to Example 1 the modified petroleum resin A except replacing, obtain resin emulsion B1 with modified petroleum resin B.Measure volume average particle size and the above modified petroleum resin particulate number ratio of 30 μ m of resin emulsion B1, its result is as shown in table 2.
Operate similarly to Example 1 the resin emulsion A1 except replacing, obtain adhesive tape with resin emulsion B1.Measure this adhesive tape to poly peel adhesion strength, confining force and initial adhesion strength.The result is as shown in table 2.
(embodiment 3)
Except the consumption of resin emulsion B1 changed to shown in the table 2, operation obtained adhesive tape similarly to Example 2.Measure this adhesive tape to poly peel adhesion strength, confining force and initial adhesion strength.The result is as shown in table 2.
(embodiment 4)
With 500 order Stainless Steel Wire Meshes resin emulsion A1 is filtered once more, do not contained the above modified petroleum resin particulate resin emulsion A2 of 30 μ m.Measure volume average particle size and the above modified petroleum resin particulate number ratio of 30 μ m of resin emulsion A2, its result is as shown in table 2.
Operate similarly to Example 1 the resin emulsion A1 except replacing, obtain adhesive tape with resin emulsion A2.Measure this adhesive tape to poly peel adhesion strength, confining force and initial adhesion strength.The result is as shown in table 2.
(comparative example 1)
Operate similarly to Example 1 the modified petroleum resin A except replacing, obtain resin emulsion C1 with petroleum resin C.Measure volume average particle size and the above modified petroleum resin particulate number ratio of 30 μ m of resin emulsion C1, its result is as shown in table 2.
Operate similarly to Example 1 the resin emulsion A1 except replacing, obtain adhesive tape with resin emulsion C1.Measure this adhesive tape to poly peel adhesion strength, confining force and initial adhesion strength.Its result is as shown in table 2.
(comparative example 2)
Operate similarly to Example 1 the modified petroleum resin A except replacing, obtain resin emulsion D1 with modified petroleum resin D.Measure volume average particle size and the above modified petroleum resin particulate number ratio of 30 μ m of resin emulsion D1, its result is as shown in table 2.
Operate similarly to Example 1 the resin emulsion A1 except replacing, obtain adhesive tape with resin emulsion D1.Measure this adhesive tape to poly peel adhesion strength, confining force and initial adhesion strength.Its result is as shown in table 2.
(comparative example 3)
Except replacing operating similarly to Example 1 the modified petroleum resin A, obtain resin emulsion E1 with aromatic resins (" Ha ィ レ ジ Application #90 ", Dong Bang KCC make).Measure volume average particle size and the above modified petroleum resin particulate number ratio of 30 μ m of resin emulsion E1, its result is as shown in table 2.
Operate similarly to Example 1 the resin emulsion A1 except replacing, obtain adhesive tape, measure this adhesive tape poly peel adhesion strength, confining force and initial adhesion strength with resin emulsion E1.The result is as shown in table 2.
(comparative example 4)
Except replacing the modified petroleum resin A with rosin based hydrocarbon resin (" high ester (ス-パ-エ ス テ Le)-A100 ", waste river KCC make), operation obtains resin emulsion F1 similarly to Example 1.Measure volume average particle size and the above modified petroleum resin particulate number ratio of 30 μ m of resin emulsion F1, its result is as shown in table 2.
Operate similarly to Example 1 the resin emulsion A1 except replacing, obtain adhesive tape with resin emulsion F1.Measure this adhesive tape to poly peel adhesion strength, confining force and initial adhesion strength.The result is as shown in table 2.
(comparative example 5)
Do not use the technology of metal mesh filter during except preparation resin emulsion C1, operate equally, obtain resin emulsion C2 with comparative example 1.Measure volume average particle size and the above modified petroleum resin particulate number ratio of 30 μ m of resin emulsion C2, its result is as shown in table 2.
Operate similarly to Example 1 the resin emulsion A1 except replacing, obtain adhesive tape with resin emulsion C2.Measure this adhesive tape to poly peel adhesion strength, confining force and initial adhesion strength.The result is as shown in table 2.
Table 2
| Embodiment | Comparative example | ||||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | 4 | 5 | |
| The modified petroleum resin particulate number ratio (%) that the volume average particle size of resin emulsion family tree lipoprotein emulsion (μ m) 30 μ m are above | A1 0.35 003 | B1 0.41 0.02 | B1 0.41 0.02 | A2 0.35 0.00 | C1 0.53 0.02 | D1 0.29 0.02 | E1 0.38 0.02 | F1 035 0.02 | C2 0.53 1.2 |
| Mix acrylic polymers emulsion (part) resin emulsion (part) | 100 15 | 100 15 | 100 5 | 100 15 | 100 15 | 100 15 | 100 15 | 100 15 | 100 15 |
| Bonding rerum natura peel adhesion strength (N/m) confining force (minute) initial adhesion strength (mm) | 480 1220 140 | 540 1700 140 | 400 1930 100 | 480 1400 120 | 280 1200 150 | 350 60 100 | 280 1400 160 | 320 280 120 | 240 1500 160 |
Following as shown in Table 2 situation.
Added the acrylic pressure-sensitive adhesive compositions of comparative example 1 of the resin emulsion C1 of acid number less than 0.1%, confining force and initial adhesion strength are poor slightly, and be poor to poly peel adhesion strength.
Having added softening temperature is the acrylic pressure-sensitive adhesive compositions of the comparative example 2 of the resin emulsion D1 below 30 ℃, and confining force is extremely low, and is poor to poly peel adhesion strength.
Added the acrylic pressure-sensitive adhesive compositions of the comparison 3 of the commercially available resin emulsion E1 that contains aromatic resins, though confining force than more excellent, poor to poly peel adhesion strength, initial adhesion strength is insufficient.
Added the acrylic pressure-sensitive adhesive compositions of the comparison 4 of the commercially available resin emulsion F1 that contains the rosin based hydrocarbon resin, though initial adhesion strength is poorer to poly peel adhesion strength and confining force than more excellent.
Added the acrylic pressure-sensitive adhesive compositions of the comparative example 5 of the high resin emulsion C2 of the above modified petroleum resin particulate number ratio of acid number less than 0.1% and 30 μ m, when on carrier, being coated with, the air spots of binder composition, can not get the homogeneous film because of producing flake, peel adhesion strength and initial adhesion strength are poor.
With respect to above-mentioned comparative example, added the embodiment 1,2 of resin emulsion A1 of the present invention, B1 or A2 or 4 acrylic pressure-sensitive adhesive compositions, to poly peel adhesion strength excellence, excellence aspect the balance of confining force and initial adhesion strength.And, even reduce the addition of resin emulsion B1, also can obtain to poly peel adhesion strength excellence the acrylic pressure-sensitive adhesive compositions of excellence (embodiment 1-3) aspect the balance of confining force and initial adhesion strength.
Industrial applicability
Acrylic pressure-sensitive adhesive compositions of the present invention and adhesive tape are such as applicable to amenities such as disposable paper diaper, sanitary napkins; The packagings for foodstuff such as frozen food, fresh food, dessert; The section such as auto parts, machine components material packing; The electric products such as TV, audio frequency goods, refrigerator packing; The bookbinding such as subpoena, books, goods catalogue purposes; The bag purposes such as brown paper bag, polypropylene bag, polyethylene bag; The dress material purposes such as bonding on the applying of flap mouth, leather and the cloth of large clothing, stamen ground etc.
Claims (7)
1. one kind contains the modified petroleum resin emulsion that modified petroleum resin is made, described modified petroleum resin contains the ethylenically unsaturated hydrocarbons monomeric unit of the carbonatoms 7-11 of the ethylenically unsaturated hydrocarbons monomeric unit of carbonatoms 4-6 of 10-100% quality and 0-90% quality, softening temperature is more than 30 ℃, and acid number is 0.1-100KOHmg/g.
2. the modified petroleum resin emulsion of claim 1, wherein modified petroleum resin contains the ethylenically unsaturated hydrocarbons monomeric unit of the carbonatoms 7-11 of the ethylenically unsaturated hydrocarbons monomeric unit of carbonatoms 4-6 of 40-95% quality and 5-60% quality.
3. claim 1 or 2 modified petroleum resin emulsion, wherein modified petroleum resin particulate volume average particle size is 0.1-1 μ m.
4. each modified petroleum resin emulsion among the claim 1-3 is in the modified petroleum resin particle of 4-64 μ m at particle diameter wherein, and particle diameter is that the modified petroleum resin particulate number ratio of 30-64 μ m is below 1%.
5. acrylic pressure-sensitive adhesive compositions, said composition contain among acrylic polymers emulsion and the claim 1-4 each modified petroleum resin emulsion.
6. the acrylic pressure-sensitive adhesive compositions of claim 5 wherein with respect to the solids component of 100 mass parts acrylic polymers emulsions, contains with solids component and counts 0.1-50 mass parts modified petroleum resin emulsion.
7. adhesive tape, this adhesive tape is made by the acrylic pressure-sensitive adhesive compositions of coating claim 5 on carrier or 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004055895 | 2004-03-01 | ||
| JP055895/2004 | 2004-03-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1910209A true CN1910209A (en) | 2007-02-07 |
| CN100503656C CN100503656C (en) | 2009-06-24 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800025262A Expired - Fee Related CN100503656C (en) | 2004-03-01 | 2005-02-28 | Modified petroleum resin emulsion and acrylic adhesive compositions containing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4940946B2 (en) |
| CN (1) | CN100503656C (en) |
| TW (1) | TWI357910B (en) |
| WO (1) | WO2005082953A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10508161B2 (en) | 2015-09-29 | 2019-12-17 | Zeon Corporation | Modified hydrocarbon resin, method for producing the resin, and hot-melt adhesive composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5856390B2 (en) * | 1976-01-31 | 1983-12-14 | 日本ゼオン株式会社 | New emulsion adhesive |
| JPS52137009A (en) * | 1976-05-07 | 1977-11-16 | Arakawa Kagaku Kougiyou Kk | Sizing agent for paper |
| JPS6037150B2 (en) * | 1977-12-28 | 1985-08-24 | 財団法人接着剤研究所 | Chloroprene latex adhesive |
| JPH0651738B2 (en) * | 1983-05-18 | 1994-07-06 | シルバケム コ−ポレ−シヨン | Composition useful for tackifying latex of elastomer |
| JPS61268778A (en) * | 1985-05-23 | 1986-11-28 | Aica Kogyo Co Ltd | Aqueous dispersion-type pressure-sensitive adhesive agent |
| EP0300624A3 (en) * | 1987-07-21 | 1990-03-28 | Reichhold Chemicals, Inc. | Water dispersible tackifier resins |
-
2005
- 2005-02-28 CN CNB2005800025262A patent/CN100503656C/en not_active Expired - Fee Related
- 2005-02-28 JP JP2006510499A patent/JP4940946B2/en not_active Expired - Fee Related
- 2005-02-28 WO PCT/JP2005/003274 patent/WO2005082953A1/en active Application Filing
- 2005-03-01 TW TW094105994A patent/TWI357910B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2005082953A1 (en) | 2007-11-15 |
| CN100503656C (en) | 2009-06-24 |
| JP4940946B2 (en) | 2012-05-30 |
| TWI357910B (en) | 2012-02-11 |
| TW200613350A (en) | 2006-05-01 |
| WO2005082953A1 (en) | 2005-09-09 |
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