WO2018033634A1 - Procédé de polymérisation de monomères vinyliques, procédé de préparation d'une composition adhésive, composition adhésive et feuille adhésive sensible à la pression - Google Patents

Procédé de polymérisation de monomères vinyliques, procédé de préparation d'une composition adhésive, composition adhésive et feuille adhésive sensible à la pression Download PDF

Info

Publication number
WO2018033634A1
WO2018033634A1 PCT/EP2017/070958 EP2017070958W WO2018033634A1 WO 2018033634 A1 WO2018033634 A1 WO 2018033634A1 EP 2017070958 W EP2017070958 W EP 2017070958W WO 2018033634 A1 WO2018033634 A1 WO 2018033634A1
Authority
WO
WIPO (PCT)
Prior art keywords
solvent
adhesive composition
tmthf
polymerization
pressure
Prior art date
Application number
PCT/EP2017/070958
Other languages
English (en)
Inventor
Greet Bossaert
Charly HOEBERS
Bart Forier
Fergal BYRNE
Andrew John HUNT
Thomas James FARMER
James Hanley Clark
Original Assignee
Nitto Belgium Nv
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nitto Belgium Nv filed Critical Nitto Belgium Nv
Publication of WO2018033634A1 publication Critical patent/WO2018033634A1/fr

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
    • 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
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Definitions

  • the present invention relates to a process for the polymerization of vinyl monomers, a process for preparing an adhesive composition, an adhesive composition and a pressure sensitive adhesive sheet. More specifically, the present invention relates to a suitable solvent as replacement for toluene wherein radical polymerization can be performed, which at the same time is a suitable solvent for the other components that are combined with the produced polymer to form an adhesive, that is easy to remove (evaporation) and that has a low carbon number (low C0 2 emission upon combustion). More specifically, the present invention relates to a biomass-based solvent for the preparation of acrylic adhesive compositions.
  • Acrylic adhesive compositions are commonly used. For instance, in producing an acrylic pressure-sensitive adhesive, usually, a monomer mixture that includes an acrylic monomer in an organic solvent is solution-polymerized into a polymer solution. Then a tackifying resin, a crosslinking agent, etc., are compounded with the polymer solution formed to obtain an adhesive composition. This may be coated on a substrate, with subsequent removal of (a large amount of) the organic solvent by heating to obtain an adhesive sheet or tape.
  • Radical polymerization in particular of vinyl monomers such as acrylic monomers, is well known.
  • the polymerization usually begins with the addition of an initiator, which is or generates a free radical species that is capable of reacting with the monomer.
  • the initiating free radical may also be generated by exposure to heat, to UV radiation or to high-energy radiation.
  • the initiation phase starts with the reaction of the free radical species with a monomer.
  • Polymerization then proceeds by successive addition of further monomers to the active end of a growing chain. This process is generally referred to as propagation.
  • the process whereby the activity of the growing chain end is destroyed is known as termination. Termination may occur through combination of two radical species, or by disproportionation.
  • the molecular weight and molecular weight distribution is moreover affected by the presence of inhibitors, retarders and chain transfer agents.
  • the polymerization may be carried out in solution, using a solvent. In each of these phases, the solvent plays a role.
  • the role may be a direct role, e.g., lack of solubility of the growing polymer may lead to termination, or an indirect role, temperature control of the reaction performed at reflux conditions.
  • the selection of the solvent is therefore important, as it affects the degree of polymerization, the solubility of the polymer and other components, and even the tack of the adhesive so produced.
  • polymers are required with a number-average molecular weight of up from 30,000.
  • the number-average molecular weight as described above is a value which can be determined by GPC (Gel Permeation Chromatography) using a calibration curve based on mono-disperse polystyrene standards, in accordance with ASTM 3536.)
  • Toluene has proven itself a suitable solvent for solution polymerization of vinyl monomers, in particular acrylic monomers. It has also proven itself a suitable solvent for compositions based on radical polymers, in particular adhesive compositions based on acrylic polymers.
  • a typical solution polymerization method is carried out by adding the monomers, a suitable solvent, and an optional chain transfer agent to a reaction vessel, adding a free radical initiator, purging with nitrogen, and maintaining the reaction vessel at an elevated temperature, typically in the range of about 40 to 100 °C until the reaction is completed, typically in about 1 to 20 hours, depending upon the batch size and temperature.
  • the solvent are methanol, tetrahydrofuran, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, and an ethylene glycol alkyl ether.
  • the pressure-sensitive adhesive composition of that invention may be prepared by dissolving specific amounts of the poly(meth)acrylate compound, an optional base polymer, and optional additives in an appropriate solvent.
  • the solvent examples include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, propyl acetate, and butyl acetate; ether solvents such as 1 ,2-dimethoxyethane, tetrahydrofuran, and 1 ,4-dioxane; halogenated solvents such as chloroform, carbon tetrachloride, and chlorobenzene; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; amide solvents such as ⁇ , ⁇ -dimethylformamide, N,N- dimethylacetamide, and N-methylpyrrolidone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic hydrocarbon solvents such as cyclopen
  • Hexamethyldisiloxane is another option, however its synthesis from biomass is not easy and upon combustion forms large quantities of ash.
  • R 1 , R 2 , R 3 , and R 4 are independently chosen from the group hydrogen and C1 - C4 linear or branched alkyl with the proviso that at least one of R 1 , R 2 , R 3 , and R 4 is not H; polymerizing the reaction mixture; and removing, by distillation, unreacted monomers, the alkyl substituted THF solvent, and any low boiling volatile reaction products.
  • 2-methyltetrahydrofuran (MeTHF) was used as (co-)solvent. The authors of this reference found that the use of MeTHF lowered the molecular weight (GPC). Values in the range of 3894 - 18,599 were found.
  • a process for preparing graft copolymers is known.
  • chain transfer agents may be added to the reaction system
  • the chain transfer agent to be used includes five member cyclic ethers such as tetrahydrofuran and its derivatives.
  • a person skilled in the art will therefore not expect a specific alkyl substituted THF to be a suitable solvent for preparing polymers with an average number molecular weight (by GPC) of 30,000 or more.
  • EP2990454 relates to a pressure-sensitive adhesive composition containing an acrylic polymer prepared using an alcohol solvent as the polymerization solvent, and a pressure-sensitive adhesive sheet which uses the pressure-sensitive adhesive composition.
  • Bio-ethanol is used.
  • acrylic polymers are synthesized using an alcohol solvent as the polymerization solvent, because chain transfer to the alcohol solvent is significant, it is difficult to increase the molecular weight of the polymer, and achieving satisfactory adhesive performance is problematic.
  • the invention provides a process for the polymerization of vinyl monomers in a solvent comprising the following steps, performed at a temperature ranging from the freezing point of the reaction mixture comprising the monomers and solvent to no more than 10 °C above the boiling point of the lowest boiling monomer or solvent and for a duration from 1 up to 100 hours:
  • the solvent is at least 99, preferably at least 99.5, more preferably at least 99.95 wt% pure 2,2,5,5, tetramethyltetrahydrofuran (TMTHF) with an olefinic content, defined by the bromine index (determined by ASTM D1492) of less than 30 mg Br/100 gr.
  • the solvent is biomass-based TMTHF.
  • the present invention provides a process for preparing an adhesive composition, comprising the following steps:
  • step B either dissolving usual adhesive components, other than the polymer prepared in step A, (1 ) in the product of step IV and/or (2) in a separate solvent, and
  • step C combining the polymer prepared in step A with the dissolved adhesive components prepared in step B(2) and optionally removing the solvent or part of the solvent to formulate the adhesive composition
  • TMTHF 2,2,5,5, tetramethyltetrahydrofuran
  • the solvent in step B(2) is biomass-based TMTHF.
  • the present invention provides an adhesive composition and a pressure-sensitive adhesive sheet, prepared according to the processes described herein, wherein at least part of the solvent is TMTHF.
  • Suitable monomers for the preparation of acrylic polymers are selected from monomers having one ethylenic unsaturated bond per molecule.
  • Examples of the monomer having one ethylenic unsaturated bond per molecule include (meth)acrylic acid,
  • (meth)acrylate esters or (meth)acrylate, and (meth)acrylic acid salts means both acrylate ester monomer and methacrylate ester monomer.
  • Examples of the monomer having one ethylenic unsaturated bond per molecule and also having a carboxyl group include (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, crotonic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid and mesaconic acid.
  • the above monomers having a carboxyl group may be in a state of being neutralized, e.g. by amine compound.
  • alkyl (meth)acrylate ester monomer in which the alkyl group of the ester portion has a carbon number of 1 to 20 include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl
  • alkyl acrylate ester monomers in which the alkyl group of the ester portion has a carbon number of 1 to 10 are preferred, and butyl acrylate and 2-ethylhexyl acrylate are particularly preferred as they facilitate a reduction in the glass transition temperature of the acrylic polymer, and enable favourable adhesive performance to be obtained.
  • methacrylate monomers having two or more ethylenic unsaturated bonds per molecule. This results in a branched structure.
  • methacrylate monomer (B) having two ethylenic unsaturated bonds per molecule include dimethacrylates such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1 ,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1 ,6- hexanediol dimethacrylate, 1 ,9-nonanediol dimethacrylate, 1 ,10-decanediol dimethacrylate and tricyclodecane dimethylol dimethacrylate.
  • dimethacrylates such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1
  • An acrylic pressure-sensitive adhesive is generally produced by copolymerizing an acrylic acid alkyl ester having 2 to 14 carbon atoms in the alkyl moiety as the main component and, if necessary, a small amount of a polar component such as acrylic acid, etc., and a monomer having a high glass transition temperature, such as styrene, vinyl acetate, etc., to balance peeling characteristics, tack, etc. Also, the copolymer may be crosslinked for the purposes of improving heat resistance and cohesive force.
  • the conditions for radical polymerization are also well known.
  • the initiation phase may start by the decomposition of some other molecule termed an initiator, although it may also be possible to form the initiating species by heat, ultraviolet or high energy radiation of the monomer or one of the monomers.
  • organic compounds such as peroxides, hydroperoxides and azo compounds are used as initiators that form the initiating species upon thermal decomposition.
  • free radical initiator include e.g.
  • Suitable initiation concentrations are between about 0.001 to about 5.0% moles of initiator to total moles of monomer.
  • the preferred range of initiator concentration is between about 0.01 to about 3.0% moles of initiator to total moles of monomer.
  • the most preferred range of initiator concentration is between about 0.1 to about 2.0% moles of initiator to total moles of monomer.
  • Initiators should be chosen based on the temperature to be employed in the polymerization.
  • the reaction requires dissolving the monomers in a suitable solvent. This may be done at e.g. room temperature or elevated temperature, e.g., up to the boiling point of the solvent or slightly above in pressurized systems.
  • the polymerization may take place at any temperature suitable for the particular reactivity of the monomers and initiators employed, that is above the freezing point of the reaction mixture and no more than generally about 10 °C above the boiling point of the lowest boiling monomer or solvent. It is preferred that the polymerization process takes place at a temperature controlled to 50 to 130 °C, e.g., 70 to 130 °C, preferably in the range between about 60 to about 120 °C.
  • the polymerization time may range from about 1 hour to about 100 hours, provided it is maintained long enough to achieve the desired average molecular weight. Generally, monomer concentrations are monitored to determine the completion of polymerization. This may vary depending on the monomers employed. Preferred reaction times are from about 1 to about 48 hours (e.g., 2 days), preferably from 4 to about 12 hours. Termination may be performed by the usual mechanisms, combination of polymer chains, radical disproportionation, combination of an active chain with an initiator radical or preferably by interaction with an inhibitor, such as oxygen and the like.
  • TMTHF TMTHF of a purity that is at least 99, preferably at least 99.5, more preferably at least 99.95 %wt and an olefinic content, defined by the bromine index (determined by ASTM D1492) of less than 30 mg Br/100 gr.
  • TMTHF has been suggested as solvent for low molecular weight polymers and even as chain transfer agent. It has therefore clearly not been noted that specifically TMTHF is an excellent substitute for toluene, provided the mandatory purity requirement is met. This may be achieved conventionally.
  • This invention therefore relates to the use of a non-peroxide-forming, low-boiling, low-polarity solvent that can potentially replace traditional hydrocarbon solvents such as toluene and hexane, and that can be produced from biomass (or in other words: is bio- based): 2,2,5,5-tetramethyltetrahydrofuran (TMTHF).
  • TMTHF has a low boiling point of ⁇ 1 1 1 °C and low ETN value of 0.1 1 1 , both comparable to toluene.
  • TMTHF is an ether by definition as it contains an R-O-R' group (where R and R' are alkyl groups), it does not possess the peroxide-forming potential of other ethers such as THF or 2-MeTHF. This is due to the absence of a proton in the oposition relative to the ethereal oxygen.
  • the oproton in traditional ethers is readily removed by low energy light, forming radicals. Oxygen from the air can react with the radicals to form explosive peroxides.
  • the rate of peroxide forming potential in ethers increases with increasing radical stability: primary a-carbon « secondary a-carbon ⁇ tertiary a-carbon.
  • TMTHF does not contain any a-protons due to it containing two quaternary ethereal carbons, the potential to form peroxides is removed.
  • TMTHF rare low-boiling, low-polarity molecule which does not possess peroxide-forming potential and can be easily produced from biomass.
  • TMTHF Methods of producing TMTHF from a precursor molecule comprising contacting the precursor with a catalyst have been reported in literature. Especially catalytic methods with 2,5-dimethylhexane-2,5-diol as a precursor have been described. Since 2,5-dimethylhexane- 2,5-diol may be made from biomass, TMTHF may be biomass-based as well. Use of biomass-based TMTHF is preferred to keep the environmental impact low.
  • the present invention also provides a process for preparing an adhesive composition, comprising the following steps:
  • step C combining the polymer prepared in step A with the dissolved adhesive components prepared in step B(2) and optionally removing the solvent or part of the solvent to formulate the adhesive composition
  • TMTHF 2,2,5,5, tetramethyltetrahydrofuran
  • the solvent in step B(2) is biomass-based TMTHF.
  • the usual additives or a selection thereof may be dissolved directly into the product of step IV. Subsequently at least part of the solvent is removed. However, it is more common to dissolve the usual additives in a separate solvent, for reasons of process control and issues with the viscosity of the product of step IV.
  • the separate solvent is TMTHF or at least in part TMTHF. This will allow recycle of the solvent in each of the process steps.
  • additives typically used in adhesive compositions which may be added according to need, including tackifying resins, a crosslinking agents, plasticizers,
  • additives include antioxidants, ultraviolet absorbers, stabilizers, levelling agents, chemical agents, fillers, pigments and dyes. These additives may be used individually, or combinations of two or more additives may be used, and there are no particular limitations on the amounts used of these additives.
  • structural adhesive compositions as well as pressure sensitive adhesive compositions may be made.
  • a laminated product hereafter referred to as a "pressure-sensitive adhesive sheet" formed from a pressure-sensitive adhesive layer and a sheet-like substrate can be obtained.
  • Suitable additives for instance include
  • the basic layer configuration of the pressure-sensitive adhesive sheet may be either a single-sided pressure-sensitive adhesive sheet with a configuration such as film-like substrate / pressure-sensitive adhesive layer / releasable film, or a double-sided pressure-sensitive adhesive sheet with a configuration such as releasable film / pressure-sensitive adhesive layer / film-like substrate / pressure- sensitive adhesive layer / releasable film.
  • a single-sided pressure-sensitive adhesive sheet with a configuration such as film-like substrate / pressure-sensitive adhesive layer / releasable film
  • a double-sided pressure-sensitive adhesive sheet with a configuration such as releasable film / pressure-sensitive adhesive layer / film-like substrate / pressure- sensitive adhesive layer / releasable film.
  • the pressure-sensitive adhesive composition requires not only tack for the pressure-sensitive adhesive layer in the instant that the pressure-sensitive adhesive layer makes contact with the adherent, but unlike other adhesives besides pressure-sensitive adhesive compositions (hereafter simply referred to as "adhesives"), also requires that the composition does not completely harden during adhesion, but rather retains tack and an appropriate level of hardness, and has sufficient cohesion to retain a state of tackiness. This cohesion is dependent upon the molecular weight of the acrylic polymer and the monomers used.
  • the releasable film examples include cellophane, various plastic films, and films prepared by subjecting the surface of a film-like substrate such as a paper to a release treatment with a silicone compound or a fluorine compound.
  • the film-like substrate may be either a substrate of a single layer, or a multilayer substrate prepared by laminating a plurality of substrates.
  • polynorbornene-based resin films polyarylate-based resin films, propenoic acid-based resin films, polyphenylene sulfide resin films, polyethenylbenzene resin films, vinyl-based resin films, polyamide-based resin films, polyimide-based resin films and oxirane-based resin films.
  • the pressure-sensitive adhesive composition is coated onto the releasable film using an appropriate conventional method, and in those cases where the pressure-sensitive adhesive composition contains a liquid medium such as an organic solvent or water, the liquid medium is then removed by heating or the like, whereas in those cases where the pressure-sensitive adhesive composition contains no liquid medium that requires
  • the molten state resin layer is cooled and solidified, thus forming a pressure- sensitive adhesive layer on the releasable film.
  • the thickness of the pressure-sensitive adhesive layer is preferably within a range from 1 ⁇ to 100 ⁇ , and is more preferably from 1 ⁇ to 50 ⁇ . If the thickness is less than 1 ⁇ , then satisfactory adhesive strength may be unobtainable, whereas even if the thickness exceeds 100 ⁇ , there is usually no further improvement in properties such as the adhesive strength.
  • the method used for coating the pressure- sensitive adhesive composition of the present invention onto the releasable film includes various coating methods using a Meyer bar, applicator, brush, spraying, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, or spin coater or the like.
  • the drying method there are no particular limitations on the drying method, and hot-air drying, or drying using infrared radiation or reduced pressure can be used. The drying conditions vary depending on the state of cross-linking, if any, within the pressure-sensitive adhesive composition, the film thickness and the amount of TMTHF used as solvent, but hot-air drying at a temperature of about 60 to 180°C is usually sufficient.
  • the pressure-sensitive adhesive sheet obtained using the method described above exhibits favourable adhesive strength to all manner of adherents, and can therefore be used for applications including label stickers, double-sided tape and masking tape.
  • the present invention is not limited to pressure sensitive adhesive sheets; also in non- pressure sensitive applications may the adhesive of the present invention be used.
  • the average molecular weight was determined by GPC (Gel Permeation Chromatography) using a calibration curve based on mono-disperse polystyrene standards such as is done according to ASTM 3536.
  • the molecular weight of polymers measured using GPC so calibrated are styrene equivalent molecular weights.
  • the detector used is preferably a combination ultraviolet and refractive index detector.
  • the molecular weight was measured by gel permeation chromatography, and the
  • Example 1 Synthesis of Poly (butyl acrylate-co-acrylic acid) in TMTHF.
  • butyl acrylate (100 g) and acrylic acid (5 g) are mixed together with dibenzoylperoxide (0.382 g), and 2,2,5,5-tetramethyltetrahydrofuran (26.35 g, with purity measured by GC analysis of 99.5% and with an olefinic content, defined by the bromine index (determined by ASTM D1492) of less than 30 mg Br/100 gr).
  • dibenzoylperoxide 0.382 g
  • 2,2,5,5-tetramethyltetrahydrofuran 26.35 g, with purity measured by GC analysis of 99.5% and with an olefinic content, defined by the bromine index (determined by ASTM D1492) of less than 30 mg Br/100 gr).
  • the mixture is purged with nitrogen for at least 1 h.
  • the mixture is heated to 70°C and stirred under nitrogen atmosphere.
  • Example 1 is repeated, but this time in toluene.
  • the results are combined in Table 1.
  • TMTHF is capable of providing results similar to what is achieved when toluene is used.
  • a pressure sensitive adhesive composition is made from the product of Example 1 .
  • Example 1 Accordingly the product of Example 1 (73.39 g, at a solid content of 27.25 %) is mixed with polyisocyanate (1 .07 g, at a solid content of 75 %) and melamine resin (0.52 g, at a solid content of 58 %), dissolved in TMTHF. Subsequently the solids content is reduced to 20 %.
  • This composition was applied with a knife coater at a thickness about 25 ⁇ onto a polyester film. The composition was dried to obtain a pressure sensitive adhesive sheet.
  • Example 3 is repeated, but this time in toluene.
  • Example 1 was to be repeated, but this time in THF. This experiment could not be performed because of the risk of peroxide formation. Moreover, with a boiling point of only 66 °C it cannot replace toluene without significant changes of the reaction conditions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un procédé de polymérisation de monomères vinyliques, un procédé de préparation d'une composition adhésive, la composition adhésive ainsi produite et une feuille adhésive sensible à la pression préparée à partir de la composition adhésive, du tétraméthyltétrahydrofurane (TMTHF), de préférence du TMTHF à base de biomasse, étant utilisé en tant que solvant.
PCT/EP2017/070958 2016-08-19 2017-08-18 Procédé de polymérisation de monomères vinyliques, procédé de préparation d'une composition adhésive, composition adhésive et feuille adhésive sensible à la pression WO2018033634A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL2017339 2016-08-19
NL2017339 2016-08-19

Publications (1)

Publication Number Publication Date
WO2018033634A1 true WO2018033634A1 (fr) 2018-02-22

Family

ID=56889176

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2017/070958 WO2018033634A1 (fr) 2016-08-19 2017-08-18 Procédé de polymérisation de monomères vinyliques, procédé de préparation d'une composition adhésive, composition adhésive et feuille adhésive sensible à la pression

Country Status (1)

Country Link
WO (1) WO2018033634A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2255229A (en) 1938-02-18 1941-09-09 Gen Aniline & Film Corp Solvent for organic film-forming materials
US2345427A (en) 1938-02-18 1944-03-28 Gen Aniline & Film Corp Solvent for organic film-forming materials
GB1307044A (en) 1970-02-07 1973-02-14 Kansai Paint Co Ltd Process for preparing graft-copolymers
WO2003080688A1 (fr) * 2002-03-19 2003-10-02 Arch Specialty Chemicals, Inc. Nouveau procede de production de polymeres contenant un anhydride pour compositions sensibles au rayonnement
EP1990390A1 (fr) 2006-02-28 2008-11-12 Lintec Corporation Feuille protectrice pour film de revetement
US20090029161A1 (en) 2007-07-17 2009-01-29 Lintec Corporation Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet
WO2009129087A1 (fr) 2008-04-14 2009-10-22 3M Innovative Properties Company Composition adhésive de (méth)acrylate de 2-octyle
EP2990454A1 (fr) 2013-04-25 2016-03-02 Toyo Ink SC Holdings Co., Ltd. Composition adhésive autocollante et feuille adhésive autocollante l'utilisant

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2255229A (en) 1938-02-18 1941-09-09 Gen Aniline & Film Corp Solvent for organic film-forming materials
US2345427A (en) 1938-02-18 1944-03-28 Gen Aniline & Film Corp Solvent for organic film-forming materials
GB1307044A (en) 1970-02-07 1973-02-14 Kansai Paint Co Ltd Process for preparing graft-copolymers
WO2003080688A1 (fr) * 2002-03-19 2003-10-02 Arch Specialty Chemicals, Inc. Nouveau procede de production de polymeres contenant un anhydride pour compositions sensibles au rayonnement
US20030225233A1 (en) 2002-03-19 2003-12-04 Arch Specialty Chemicals, Inc. Novel process for producing anhydride-containing polymers for radiation sensitive compositions
EP1990390A1 (fr) 2006-02-28 2008-11-12 Lintec Corporation Feuille protectrice pour film de revetement
US20090029161A1 (en) 2007-07-17 2009-01-29 Lintec Corporation Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet
WO2009129087A1 (fr) 2008-04-14 2009-10-22 3M Innovative Properties Company Composition adhésive de (méth)acrylate de 2-octyle
EP2990454A1 (fr) 2013-04-25 2016-03-02 Toyo Ink SC Holdings Co., Ltd. Composition adhésive autocollante et feuille adhésive autocollante l'utilisant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHERWOOD ET AL., GREEN CHEM., vol. 18, 2016, pages 3990

Similar Documents

Publication Publication Date Title
WO2013181030A1 (fr) Compositions adhésives liquides optiques
TWI673289B (zh) 可紫外線固化丙烯酸共聚物
WO2012060364A1 (fr) Composition de résine acrylique, adhésif acrylique, feuille adhésive, feuille adhésive double face, adhésif pour électrodes transparentes, pour écran tactile et pour dispositif d'affichage d'images, ainsi que procédé de production de stratifiés contenant la couche adhésive
JP6723638B2 (ja) 粘着剤組成物および粘着シート
KR20210060662A (ko) 자외선 경화성 감압성 접착제
JP2017519848A (ja) 硬化性接着剤組成物およびその使用
WO2014175341A1 (fr) Composition adhésive autocollante et feuille adhésive autocollante l'utilisant
KR20160148457A (ko) 점착제 조성물
KR20120093210A (ko) 이중 가교 점착부여된 감압 접착제
JP2012012562A (ja) アクリル樹脂組成物
JP3539765B2 (ja) 粘着付与樹脂組成物
EP2734558B1 (fr) Procédé de préparation de compositions durcissables à rayonnement
JP2003277709A (ja) 粘着剤組成物および粘着製品
US11466105B2 (en) Photocurable acrylic resin, adhesive composition including the same, and adhesive film formed using the adhesive composition
JP4267329B2 (ja) （メタ）アクリル系粘着剤用ポリマー溶液及びその製造方法、（メタ）アクリル系粘着剤、並びに（メタ）アクリル系粘着テープ
WO2018033634A1 (fr) Procédé de polymérisation de monomères vinyliques, procédé de préparation d'une composition adhésive, composition adhésive et feuille adhésive sensible à la pression
JP2003128714A (ja) アクリル系部分重合体組成物の製造方法、当該製造方法により得られるアクリル系部分重合体組成物および当該組成物を紫外線重合させてなる粘着剤組成物
JP2005029774A (ja) 活性エネルギー線硬化用組成物
JP2019504149A (ja) 硬化性接着剤組成物及び接着テープ並びにそれらから製造される製品
JP2004143344A (ja) 紫外線吸収能を有する架橋性樹脂組成物
JP5333975B2 (ja) （メタ）アクリル酸エステル共重合体およびこれを含んでなる粘着剤組成物ならびに（メタ）アクリル酸エステル共重合体の製造方法
JP2004051812A (ja) 粘着剤組成物及び粘着シート
JP2015003959A (ja) 光学粘着剤組成物および光学粘着製品
WO2005040241A1 (fr) Composition de revetement a durcissement rapide comprenant un hydroxydiester non sature
CN112898478A (zh) 一种紫外光固化聚合物及其制备方法与应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17752403

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17752403

Country of ref document: EP

Kind code of ref document: A1