WO2012145857A1 - Dispersion aqueuse de polymères de (méth)acrylate contenant de préférence de la benzophénone pour revêtement pour cuir - Google Patents

Dispersion aqueuse de polymères de (méth)acrylate contenant de préférence de la benzophénone pour revêtement pour cuir Download PDF

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Publication number
WO2012145857A1
WO2012145857A1 PCT/CN2011/000720 CN2011000720W WO2012145857A1 WO 2012145857 A1 WO2012145857 A1 WO 2012145857A1 CN 2011000720 W CN2011000720 W CN 2011000720W WO 2012145857 A1 WO2012145857 A1 WO 2012145857A1
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WO
WIPO (PCT)
Prior art keywords
weight
dispersion according
acrylate
dispersion
component
Prior art date
Application number
PCT/CN2011/000720
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English (en)
Inventor
Zhengfeng Zhang
Lina Xue
Gerold Schmitt
Wolfgang Klesse
Original Assignee
Evonik Röhm Gmbh
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 Evonik Röhm Gmbh filed Critical Evonik Röhm Gmbh
Priority to PCT/CN2011/000720 priority Critical patent/WO2012145857A1/fr
Publication of WO2012145857A1 publication Critical patent/WO2012145857A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—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

Definitions

  • the present invention relates to an aqueous dispersion of preferably benzophenone-containing (meth)acrylate polymers and its application in leather coating.
  • Dispersions of this type have long been used for coating various substrates to seal and protect them.
  • One exemplary application relates to the sealing of mineral substrates, such as brick, concrete, concrete roof tiles, conventional tiles and the like (cf. US patent 4,511 ,699 and also GB patent 1 41 1 268).
  • EP 0 355 028 Al discloses a process wherein substrates are coated on their surfaces with aqueous polyacrylate dispersions and the coatings are subsequently dried at elevated temperature.
  • the coating utilizes a mixture of A) a 20% to 65% by weight aqueous dispersion of a copolymer of a) 20% to 70%, based on the weight of the copolymer, of (meth)acrylic esters of alkanols which contain 3 to 20 carbon atoms and have a tertiary CH group, b) 30% to 60%, based on the weight of the copolymer, of styrene, alphamethylstyrene, methyl methacrylate, tert- butyl (meth)acrylate and/or (meth)acrylonitrile, and c) 0.2% to 7%, based on the weight of the copolymer, of mono- and/or dicarboxylic acids of 3 to 5 carbon atoms and/or their amides which may
  • Useful aromatic ketones according to EP 0 355 028 Al include, for example, benzophenone and benzophenone derivatives such as 3,3'- dimethyl-4-methoxybenzophenone, 3- and 4-hydroxybenzophenone, benzophenone-2-carboxylic acid, benzophenone-3-carboxylic acid, benzophenone-4-carboxylic acid and the like and also 2-, 3- and 4- phenylbenzophenone, 2-, 3- and 4-alkylbenzophenones having 1 to 10 carbon atoms in the alkyl radicals, such as 2-, 3- and 4- methylbenzophenone, 2-, 3-, 4-nonylbenzophenone, dialkylbenzophenones and also olefinically unsaturated as well as water- soluble benzophenone derivatives.
  • benzophenone and benzophenone derivatives such as 3,3'- dimethyl-4-methoxybenzophenone, 3- and 4-hydroxybenzophenone, benzophenone-2-carboxylic acid,
  • Benzophenone and low molecular weight benzophenone derivatives are customary photoinitiators. Irradiation leads to the formation of free radicals which can effectuate the polymerization or crosslinking of ethylenically unsaturated monomers.
  • Copolymers of acryloyloxybenzophenone with menthyl acrylate, methyl aery late or 1- aery loyloxy-2-ethoxy ethane are disclosed.
  • the copolymers described include about 10 to 90 mol% of acryloyloxybenzophenone units and are useful for photoinitiating the polymerization.
  • the molecular weight of the photo initiators described is not precisely specified in the paper in question.
  • US 5,900,472 A describes copolymerizable benzophenone photoinitiators.
  • benzophenone derivatives having 2 to 4 (meth)acrylate groups and also UV-curable coatings, obtainable by reacting the polyfunctional benzophenone derivatives with (meth)acrylate under the action of radiation.
  • the coatings obtainable using the polyfunctional benzophenones are superior to existing coatings involving known photoinitiators in that they display a reduced tendency to leach, bleed or migrate. Unconsumed photoinitiator hitherto tended to be prone to this phenomenon, which limited its use to a few possibilities, which did not include use for leather application.
  • WO 2002100912 describes UV-curable aqueous dispersions for coating cellulose, particularly adapted to hygiene articles. The purpose here is to improve the resistance to water. This system is not applicable to leather because the material requirements are completely different and the purpose of the coating is completely different.
  • WO2010108752 describes a benzophenone-containing (meth)acrylate polymer and its use as polymer-bonded UV initiators or additive to UV- curable resins. The possibility for leather application is not explored.
  • Aqueous dispersions for leather coating shall have good adhesion, good low temperature flexibility, non-tackiness at room temperature, and good mechanical properties. It is difficult to fulfill all the needs together.
  • aqueous dispersion itself shall be very simple to use.
  • the aqueous dispersion shall fully comply with workplace regulations and, more particularly, also be recognized as very safe to health.
  • the coatings shall be very quick to cure and/or dry very fully and the leather materials processed shall have a comparatively long service life. For this, curing shall bring about very effective, i.e. complete and intensive, crosslinking of the coating. Summary of the invention
  • the present invention provides an aqueous dispersion of preferably benzophenone-containing (meth)acrylate polymers which can be used for leather coating.
  • the present invention also provides the use of the aqueous dispersion of the present invention for leather coating.
  • the present invention further provides a process for coating leather with the aqueous dispersion of the present invention.
  • the present invention further provides a leather material obtained by the process of the present invention.
  • the aqueous dispersion of the present invention contains one or more (meth)acrylate polymers containing one or more compounds of the general formula (I) in polymerized form and obtainable by emulsion polymerization of a monomer composition comprising a) 0.1% to 25.0% by weight of at least one compound of the general formula (I)
  • R 1 is hydrogen or methyl
  • R 2 is oxygen or NH
  • R 3 is a radical of the general formula II
  • R 7 , R 8 and R 9 are each independently hydrogen or methyl
  • n is an integer from zero to two hundred
  • o and p are each independently an integer from zero to two, subject to the proviso that R is a bond when the sum total of n and o and p is zero, R 4 is a bond, oxygen or 0-CO-O,
  • R 5 is hydrogen, halogen or a radical which contains one to twenty carbon atoms and is optionally substituted with oxygen, nitrogen and/or sulphur, where m is an integer from one to five, and
  • R 6 is an aryl or heterocyclyl radical, substituted or unsubstituted and b) a mixture of further compounds comprising
  • R 1 is methyl.
  • R is oxygen
  • R 4 is a bond
  • R 6 is phenyl. In one embodiment of the present invention, R 5 is hydrogen.
  • component a) used is one or compounds conforming to the general formula (J).
  • component a) comprises at least one benzophenone (meth)acrylate of the general formula J):
  • R 1 and R 5 and also m are each as defined above for the formulae (I).
  • the meanings of R 10 are analogous to those of R 5 and those of q are analogous to those of m. It is very particularly advantageous to use benzophenone methacrylate as component a) to produce the polymer for aqueous dispersion according to the invention.
  • the compounds of formulae (I) and (J) are either commercially available or obtainable by literature methods. Possible methods of preparation include for example the transesterification of (meth)acrylates with the corresponding alcohols.
  • component a) represents 0.1% to 10.0% by weight, more preferably 0.1% to 5% by weight, more preferably 0.5% to 1.0% by weight of the polymerizable constituents of the monomer composition.
  • component b) of the monomer composition of the aqueous dispersion of the present invention preferably comprises:
  • acrylamides and/or methacrylamides and/or acrylonitrile and/or methacrylonitrile and/or hydroxyalkyl acrylates and/or hydroxyalkyl methacrylates 0% to 5.0% by weight of one or more acrylamides and/or methacrylamides and/or acrylonitrile and/or methacrylonitrile and/or hydroxyalkyl acrylates and/or hydroxyalkyl methacrylates.
  • Acrylates herein are all functionalized or non functionalized acrylates other than a). Preference is given to ethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate or mixtures thereof. Methacrylates herein are all functionalized or nonfunctionalized methacrylates other than a). Preference is given to methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate or mixtures thereof.
  • the acrylamides and/or methacrylamides of component b) comprise acrylamide, N-methylol acrylamide, methacrylamide, N- methylol methacrylamide or mixtures thereof.
  • component b) of the monomer composition of the aqueous dispersion of the present invention comprises:
  • component b) of the monomer composition of the aqueous dispersion of the present invention is preferably chosen such that the (meth)acrylate polymers used according to the invention have a glass transition temperature below 15°C, preferably below 5°C and more preferably below -5°C.
  • the pH of the dispersion of the present invention is 6.0 to 9.0.
  • the polymers in the dispersions used according to the invention are generally obtained through free-radical polymerization.
  • the customary free-radical polymerization is exhaustively described in Ullmanns' Encyclopaedia of Industrial Chemistry, Sixth Edition, as well as elsewhere.
  • the polymerization can be started using at least one polymerization initiator for free radical polymerization.
  • This includes redox systems widely known among those skilled in the art.
  • a preferably redox system consists of ammonium peroxodisulphate, sodium hydroxymethanefulinate and FeS0 4 .
  • the polymerization to obtain the polymers of the invention can be carried out at atmospheric pressure, subatmo spheric pressure or superatmospheric pressure.
  • Polymerization temperature is similarly uncritical. Generally, however, it is in the range form -20 to 200°C, preferably in the range of 0-180°C, more preferably in the range of 50- 180°C, even more preferably in the range of 50-130°C and yet even more preferably in the range of 60-120°C.
  • Such an aqueous dispersion permits in a not readily foreseeable manner the creation of coatings on leather with advantageous properties through incorporation of polymer-attached UV curable (meth)acrylate polymers in conventional dispersions.
  • One advantage of the system in relation to the coating of leather with the aqueous dispersion of the invention resides in that no additional photo initiators are required for the UV curing and no migration of the UV-active species is likely, since the UV active substance is incorporated as a copolymerized monomer in the corresponding coating.
  • Processing the dispersions of the invention for coating leather takes the form of applying the aqueous dispersion to the leather sheet material, then drying and a subsequent UV cure which is usually carried out continuously in a belt apparatus.
  • a delay period is inserted between the drying step and the UV-curing step to complete the filming of the coating. This generally takes within a few minutes or even within a few seconds.
  • the applying comprises spread coating, roll coating, printing, spraying, saturating or padding.
  • the process of the invention which involves a UV-curing step, is advantageous over the prior art thermal curing, in several respects.
  • the energy requirements are distinctly lower;
  • the equipment needed for the padding and subsequent curing can be made distinctly more space-saving and technically less complex.
  • a distinctly more long-winded thermal cure naturally requires more space than a short unit for UV curing.
  • the dispersions of the invention are observed to be distinctly less prone to coagulate than the prior art dispersions.
  • the materials display better shear stability and hence better and potentially also faster processibility.
  • the preferably benzophenone-containing compounds in the composition of the present invention comprise monomers which effectuate a cure via UV crosslinking, instead of polymeric photoinitiators. This constitutes a significant difference from prior art.
  • UV curing lamp Philips TL20W/05* 2
  • EA Ethyl Acrylate
  • MMA Methyl Methacrylate
  • GMAA Methyacrylic Acid
  • the temperature of the mixture was cooled to and maintained at 70 °C for 2 hours. Then 0.06 g of APS in 6 g of deionized water was added. The temperature of the mixture was maintained at 70 °C another 3 hours. The temperature of the mixture was then cooled to room temperature and the result mixture was filtered to remove any coagulum.
  • the total amount of the raw material used was 888 g.
  • the content of all the monomers was 40 % by weight.
  • aqueous dispersions were prepared. For each batch, the total amount of the raw material used was also 888 g and the content of all the monomers was also 40 % by weight. The process for preparing these aqueous dispersions was the same as Example 1 except the ratio of monomers which is reported in Table 1. Percentages in the table are all by weight unless otherwise indicated. The original pH of the dispersion is around 2-3. For Examples 10-13, a portion of the dispersion was taken out and their pH value was adjusted to 8-9 with aqueous ammonia.
  • Tg, coagulum weight, viscosity, pH, solid content and particle size of Examples 1-13 were calculated or measured. The results are reported in Table 1.
  • the dispersions of Examples 1-13 were put in open containers and dried at 60 °C overnight. The dried films were further exposed to a weak UV source (Philips TL20W/05 *2 ) for a fixed time of Oh, 0.5h, lh, 2h and 3h or to a stronger UV source (GY UV 2kW/2, WANGYI) for a fixed time of 2s, 5s and 10s.
  • a weak UV source Philips TL20W/05 *2
  • GY UV 2kW/2, WANGYI a stronger UV source for a fixed time of 2s, 5s and 10s.
  • the brittleness test of the film samples was conducted according to QB/T 2223-96 with the focus that whether the film is still flexible at -18 °C after long time storage at that temperature (8 hours or 16 hours - two cycles).
  • the prepared film was kept at least for 24 hours at room temperature. Then the film was tested with finger. The tackiness was judged by the feeling. The above performance of the films is reported in Table 2.
  • Table 1 shows that BPMA contributes to gel weight reduction. More BPMA in the recipe, less coagulum could be formed. Table 2 shows BPMA also contributes film tackiness reduction. More BPMA, less tacky the resultant film could be.
  • the emulsion should not contain much coagulum, preferably less than 1 wt.%, or even less than 0.5 wt.%.
  • the resultant film should be non-tacky at room temperature. But on the other hand, it should be flexible enough, that means, even at very low temperature (-18°C) it is not brittle and without any fold remained. Ideally, it would be better if the elongation at break is within 300% to 500% at room temperature while keeping enough tensile strength.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

La présente invention concerne une dispersion aqueuse de polymères de (méth)acrylate contenant de préférence de la benzophénone et son utilisation dans un revêtement pour cuir. Les avantages de la présente invention sont qu'aucun photoinitiateur supplémentaire n'est nécessaire pour effectuer un durcissement sous UV et qu'il n'y a pas de libération de formaldéhyde pendant le durcissement sous UV.
PCT/CN2011/000720 2011-04-25 2011-04-25 Dispersion aqueuse de polymères de (méth)acrylate contenant de préférence de la benzophénone pour revêtement pour cuir WO2012145857A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2011/000720 WO2012145857A1 (fr) 2011-04-25 2011-04-25 Dispersion aqueuse de polymères de (méth)acrylate contenant de préférence de la benzophénone pour revêtement pour cuir

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2011/000720 WO2012145857A1 (fr) 2011-04-25 2011-04-25 Dispersion aqueuse de polymères de (méth)acrylate contenant de préférence de la benzophénone pour revêtement pour cuir

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WO2012145857A1 true WO2012145857A1 (fr) 2012-11-01

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107384081A (zh) * 2017-08-29 2017-11-24 安徽乐踏鞋业有限公司 一种改善皮革耐低温干燥环境的涂饰剂
US10221270B2 (en) 2016-07-14 2019-03-05 Rohm And Haas Company Latex functionalized with phosphorus acid and photoinitiator groups
US11186726B2 (en) 2017-04-01 2021-11-30 Dow Global Technologies Llc Aqueous polymer dispersion and aqueous coating composition comprising the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1796421A (zh) * 2004-12-29 2006-07-05 国家淀粉及化学投资控股公司 用于压敏粘合剂的光引发剂和uv交联丙烯酸聚合物
WO2010108762A1 (fr) * 2009-03-24 2010-09-30 Evonik Röhm Gmbh Composition comprenant, sous forme d'une dispersion aqueuse, des polymères de (méth)acrylate renfermant de préférence de la benzophénone, en mélange avec des polymères de (méth)acrylate différents de ceux-ci, et utilisation de ladite composition
WO2010108752A1 (fr) * 2009-03-24 2010-09-30 Evonik Röhm Gmbh Polymères de (méth)acrylate et leur utilisation en tant qu'initiateurs uv liés à des polymères, ou en tant qu'additifs à des résines durcissables aux uv
TW201105758A (en) * 2009-03-30 2011-02-16 Evonik Roehm Gmbh Coating composition, (meth) acrylic polymer and monomer mixture for preparing the (meth) acrylic polymer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1796421A (zh) * 2004-12-29 2006-07-05 国家淀粉及化学投资控股公司 用于压敏粘合剂的光引发剂和uv交联丙烯酸聚合物
WO2010108762A1 (fr) * 2009-03-24 2010-09-30 Evonik Röhm Gmbh Composition comprenant, sous forme d'une dispersion aqueuse, des polymères de (méth)acrylate renfermant de préférence de la benzophénone, en mélange avec des polymères de (méth)acrylate différents de ceux-ci, et utilisation de ladite composition
WO2010108752A1 (fr) * 2009-03-24 2010-09-30 Evonik Röhm Gmbh Polymères de (méth)acrylate et leur utilisation en tant qu'initiateurs uv liés à des polymères, ou en tant qu'additifs à des résines durcissables aux uv
TW201105758A (en) * 2009-03-30 2011-02-16 Evonik Roehm Gmbh Coating composition, (meth) acrylic polymer and monomer mixture for preparing the (meth) acrylic polymer

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10221270B2 (en) 2016-07-14 2019-03-05 Rohm And Haas Company Latex functionalized with phosphorus acid and photoinitiator groups
US11186726B2 (en) 2017-04-01 2021-11-30 Dow Global Technologies Llc Aqueous polymer dispersion and aqueous coating composition comprising the same
CN107384081A (zh) * 2017-08-29 2017-11-24 安徽乐踏鞋业有限公司 一种改善皮革耐低温干燥环境的涂饰剂

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