• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    SUMMARY A novel urethane acrylate is disclosed which is a reaction product of a raw material composition comprising at least (A) a diol component, (B) a component which has acrylic feed and (C) an isocyanate component. Said component (A) comprises at least one alkoxylated 2,4,8,1 O-tetraoxaspiro [5,5] undecane-3,9-dialkanol, component (B) comprises at least one hydroxyalkyl acrylate, hydroxyalkyl methacrylate and / or hydroxyalkyl methyl acrylate, and / or comprises acrylic acid, methacrylic acid and / or a methyl acrylic acid and / or a corresponding alkyl ester of said acrylic acid, and said component (C) comprises at least one di- or polyisocyanate or a derivative thereof.
    公开号:SE1300292A1
    申请号:SE1300292
    申请日:2013-04-22
    公开日:2014-10-23
    发明作者:David James；Linda Nilsson
    申请人:Perstorp Ab；
    IPC主号:
    专利说明:

    The present invention relates to a novel urethane acrylate which is a reaction product of at least one diol component, an acrylate-saturated component and an isocyanate component, said diol component comprising at least one alkoxylated 2,4,8,10-tetraoxaspiro-3 [5.5]. , 9-dialkanol.
    Radiation curing, as well as UV curing, coatings for industrial applications have for many years been constantly increasing. Less productive and / or less environmentally unusual systems have been gradually replaced by radiation technology and a number of new applications for radiation-curing surface coatings have been found. Radiation-curing polyurethane acrylates have been the choice for more than two decades. The most common are based on urethane acrylate or methacrylate oligomers, which make up the majority of coatings widely used in industry. These coatings are used for protective purposes such as in applications such as heat and / or radiation hardening coatings, inks and adhesives. Hardened surface coatings typically give films with, for example, a good combination of strength and elasticity. Urethane acrylates make up the majority of the compositions and thus determine the properties of saval liquid as a hardened product.
    However, despite the large amount of commercially available urethane acrylates and derivatives, depending on, for example, environmental considerations and legislation and / or new areas of application, there is a constant demand for new, safer, more efficient and / or more usable urethane acrylates.
    An important demand is for substitutes for urethane acrylates based on bisphenol A. Bisphenol A is known as an endocrine disruptor associated with irritation of the respiratory system, risk of serious damage to the eyes and nervous system, risk of sensitization through skin contact and risk of reduced fertility, avoiding skin contact. Hydrogenated bisphenol A has been proposed as a substitute for bisphenol A in the production of urethane acrylates. However, there are significant disadvantages with the use of hydrogenated bisphenol A. Disadvantages are, for example, the fact that hydrogenated bisphenol A is a solid substance with a high melting point and thus an answer to handle in a factory environment and the fact that reactions between liquid substances and solid substances with a high melting point is answer to moderate. It would thus be unfortunate to have a diol which gives the properties of the high diol melting point but with reduced process problems.
    One aspect of the present invention is to provide a novel urethane acrylate which has at least one acrylic, methacrylic and / or methyl acrylic double bond. Another aspect is to provide a suitable substitute for the corresponding urethane acrylates based on bisphenol A and / or hydrogenated bisphenol A.
    It has now been quite unexpectedly found that an alkoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-dialkanol is a compound useful in most applications including urethane acrylates. The novel urethane acrylate of the present invention can further advantageously replace urethane acrylates based on bisphenol A and / or hydrogenated bisphenol A as a product which is safer to handle and more environmentally friendly.
    The novel urethane acrylate of the present invention is a reaction product of a tharu composition comprising at least (A) a diol component, (B) an acrylate-saturated component and (C) an isocyanate component. Said component (A) comprises at least one alkoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-dialkanol of the formula H [O (CHDA- ° ** CH 2 R Wherein the substituent R is individually a lin * or branched C1-C8 alkyl group and m, n, p and q are individually integers and at least 1, said component (B) comprises at least one hydroxyalkyl acrylate, hydroxyalkyl methacrylate and / or hydroxyalkyl methyl acrylate, wherein hydroxyalkyl is preferably hydroxy-C 1 -C 12 alkyl, and may be exemplified by hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropanide (meth) acrylate and pentaerythritol tri (meth) acrylate, and / or include acrylic acid, and / or a methyl acrylic acid, such as crotonic acid or isocrotonic acid, or a corresponding alkyl ester thereof, and wherein said component (C) comprises at least one di- or polyisocyanate or a derivative thereof.
    In preferred embodiments of the name alkoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-dialkanol, m and p, in the above formula, are individual integers between 1 and 6, such as between 1 and 4, and n and q is an individual integer between 1 and 10, such as between 1 and 8, between 1 and 6 or between 1 and 4. The substituent R in the above formula is in likewise preferred embodiments an alkyl group of the formula CH 3 -C- I CH 3 3 The most preferred The embodiments of the name alkoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-dialkanol include alkoxylated, such as methoxylated, ethoxylated, propoxylated and / or butoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane -3,9-diethanol.
    Particularly preferred embodiments of alkoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol are ethoxylated and / or propoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9- diethanol with 1-10, such as 1-6, 1-5, 1-4, 1-3 or 1-2, ethoxy and / or propoxy units / hydroxyl group.
    Name component (A) comprises, in preferred embodiments of flatland fly urethane acrylate according to the present invention, 50-100% by weight of name alkoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-dialkanol, as named methoxylated, ethoxylated, propoxylated and / or butoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-dialkanol. In equally preferred embodiments, said component (B) comprises 50-100% by weight of the name at least hydroxyalkyl acrylate, hydroxyalkyl methacrylate and / or hydroxyalkyl methyl acrylate and / or 50-100% by weight of said acrylic acid, methacrylic acid and / or a methyl acrylic acid and / or a corresponding alkyl ester. Furthermore, in similarly preferred embodiments, component (C) comprises 50-100% by weight of said di- or polyisocyanate.
    Said di or polyisocyanate is preferably and advantageously besta.ende from the group of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, dicyclohexylmethane diisocyanate, furandiisocyanat, tetrahydrofurandiisocyanat, cyclohexylene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, nonantriisocyanat and / or triphenylmethane.
    Said ravaru composition may additionally comprise one or more carboxylic acids, such as octanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, secanoic acid and / or trimethylhexanoic acid.
    It is understood that one skilled in the art without further explanation, by using the description above, may take full advantage of the present invention. The following preferred specific embodiments are to be construed as merely illustrative and not restrictive of the foregoing description. In the following, 1 and 2 embodiments of the present process and Example 3 show a comparative product based on ethoxylated bisphenol A. Example 4 relates to curing the products of Examples 2 and 3. Table 1 presents analysis results based on products obtained in Examples 2 and 3. Example 1 An adduct between isophorone diisocyanate and hydroxyethyl acrylate was prepared for the preparation of urethane acrylates shown in Examples 2 and 3 (Comparison). 175.0 parts by weight of isophorone diisocyanate and 0.6 parts by weight of methoxyphenol, as inhibitor, were charged to a reaction vessel equipped with heating, temperature control, stirrer, air supply and condenser. 86.8 parts by weight of hydroxyethyl acrylate were successively charged over 10 minutes and 0.03 parts by weight of dibutyltin laurate as catalyst were then charged to the reaction mixture. The temperature was now allowed to slowly rise to 60-70 ° C and the reaction was allowed to continue until the theoretical NCO number was reached. The resulting reaction product was finally cooled to room temperature. ), 0.2 parts by weight of methoxyphenol, as inhibitor, and 133.0 parts by weight of toluene, as azeotropic solvent, were charged to a reaction vessel equipped with heating, temperature control, stirrer, air supply and reflux. 100.0 parts by weight of the adduct obtained in Example 1 was now slowly charged to the reaction mixture followed by the addition of 0.03 parts by weight of dibutyltin laurate as catalyst. The temperature was rapidly raised to 65 ° C and maintained until an NCO number tiara 0 was reached. Toluene was now driven off and the remaining reaction product was cooled to room temperature. Analysis results are given in Table 1.
    Example 3 (Comparison) Example 2 was repeated with the difference that 52.4 parts by weight of a bisphenol A ethoxylate with an average of 4 ethoxy units / phenolic hydroxyl group (Sigma Aldrich Co) were charged instead of 54.5 parts by weight of ethoxylated 2,4,8,10 tetraoxaspiro [5,5] decane-3,9-dietanol with an average of 4-5 ethylene oxide units / hydroxyl group (pentaerythritol spiroglycol ethoxylate, Perstorp Specialty Chemicals AB). Analysis results are given in Table 1.
    Example 4 The products obtained in Examples 2 and 3 (Comparison) were cured, after the addition of 1.0 part by weight of resin 500 (photoinitiator, Ciba Specialty Chemicals Inc.) and application to glass and steel panels, at a dry film thickness of 40 microns.
    Coated panels were first placed in an oven for 30 minutes at 50 ° C, cooled to room temperature and then UV cured. UV curing is challenged with a UV lamp of 80 W / cm2 and at a strip speed of 20 m / min. The varnishes had to pass under the UV lamp 4 times. The samples were conditioned after curing for 24 hours at 23 ± 2 ° C and 50 + 5% relative humidity, followed by film hardness, flexibility and gloss feeds.
    Measured results: Example 2 Example 3 Hardness, Konig sec.214200 Erichsen flexibility, mm0.42.6 Gloss at 60 ° 8994 Table 1 Example 2 Example 3 Hydroxyl number, mg KOH / g 4 Acid number, mg KOH / g 0.1 0.3 Molecular weight Mw, g / mol 2 200 2 400 Acrylic concentration lR 1.1.42 Polydispersity 1.4 1.4 6
    权利要求:
    Claims (17)
    [1]
    A urethane acrylate which is a reaction product of a raw material composition comprising at least (A) a diol component, (B) a component having acrylate saturation and (C) an isocyanate component characterized in that said component (A) comprises at least one alkoxylated 2.4, 8,10-Tetraoxaspiro [5,5] undecane-3,9-dialkanol of the formula H [O (CHDP] q - ° C112R R, O - [(CH2) m0] nfl CH2 0 <0 0 0 van in each substituent R is individually a linear or branched C 1 -C 8 alkyl group and in. n, p and q are individually integers and at least 1, that said component (B) comprises at least one hydroxyalkyl acrylate, hydroxyalkyl methacrylate and / or hydroxyalkyl methyl acrylate, and / or comprises acrylic acid, methacrylic acid and / or a methyl acrylic acid and / or a corresponding alkyl ester of a named acrylic acid, and that said component (C) comprises at least one dieller polyisocyanate or a derivative thereof.
    [2]
    The urethane acrylate according to claim 1, wherein said hydroxyalkyl is hydroxy-C
    [3]
    The urethane acrylate according to claim 1 or 2, wherein said component (B) comprises hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropanide (meth) acrylate or pentaerythritol tri (meth) acrylate.
    [4]
    4. The urethane acrylates according to any one of the terms 1-3 k dun et e c kn ad a v, that in and p individually are integers between 1 and 6, as well as between 1 and 4.
    [5]
    5. The urethane acrylates according to any one of claims 1-4 may be that n and q are individually integers between 1 and 10, such as between 1 and 8, between 1 and 6 or between 1 and 4.
    [6]
    The urethane acrylate according to any one of claims 1-5, wherein the substituent R is a group of the formula CH 3 CH 3 7
    [7]
    The urethane acrylate according to any one of claims 1-6 may be characterized in that said alkoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-dialkanol is an alkoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol.
    [8]
    The urethane acrylate according to any one of claims 1-7, characterized in that the name alkoxylated is methoxylated, ethoxylated, propoxylated and / or butoxylated.
    [9]
    9. The urethane acrylates according to any one of claims 1-8, characterized in that said component (A) comprises 50-100% by weight of said alkoxylated 2,4,8,10-tetraoxaspiro [5,51 undecane-3,9-dialkanol.
    [10]
    The urethane acrylate according to any one of claims 1-9 may be characterized in that said alkoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol is an ethoxylated and / or propoxylated 2,4,8,10- tetraoxaspiro [5.5] undecane-3,9-diethanol which has 1-10, such as 1-6, 1-5, 1-4, 1-3 or 1-2, ethoxy and / or propoxy units / hydroxyl group.
    [11]
    The urethane acrylate according to any one of claims 1-10, characterized in that said component (B) comprises 50-100% by weight of said hydroxyalkyl acrylate, hydroxyalkyl methacrylate and / or hydroxyalkyl methyl acrylate.
    [12]
    The urethane acrylate according to any one of claims 1-11, characterized in that said component (B) comprises 50-100% by weight of said acrylic acid, methacrylic acid and / or a methyl acrylic acid and / or an alkyl ester of a named acrylic acid.
    [13]
    The urethane acrylate according to any one of claims 1-12, characterized in that said component (C) comprises 50-100% by weight of said di- or polyisocyanate.
    [14]
    14. Uretanakrylaten of any of claims 1-13 k ann et ecknad, that said di- or polyisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, dicyclohexylmethane diisocyanate, furandiisocyanat, tetrahydrofurandiisocyanat, cyclohexylene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, nonantriisocyanat and / or triphenylmethane .
    [15]
    The urethane acrylate according to any one of claims 1 to 14, characterized in that said raw material composition further comprises at least one carboxylic acid.
    [16]
    The urethane acrylate according to claim 15, characterized in that said carboxylic acid is octanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, cecanoic acid and / or trimethylhexanoic acid. 8
    [17]
    The urethane acrylate according to any one of claims 1 to 16, characterized in that said component (A) comprises an ethoxylated 2,4,8,10-tetraox asp in ro [5.5] undecane-3,9-diethanol which on average bore 3 -6 ethoxy units / hydroxyl group, that said component (B) comprises hydroxyethyl acrylate and that said component (C) comprises isophorone diisocyanate.
    类似技术:
    公开号 | 公开日 | 专利标题
    JP6480176B2|2019-03-06|Urethane adhesive
    EP2066718B1|2012-03-07|Radiation-curable formulation which forms flexible coatings with increased corrosion protection on metallic substrates
    EP2342251B1|2014-01-15|Radiation curable adhesive
    AU2006265229B2|2011-09-01|Method for producing radiation curable formulations with increased corrosion protection on metal substrates, and formulations of this type
    CN101824299B|2012-10-03|Method for preparing single-component high-solid content water-based polyurethane adhesive
    EP3024901B1|2017-03-22|Coating materials containing a compound having at least two cyclic carbonate groups and a siloxane group
    KR20130140537A|2013-12-24|Radical-curable hot-melt urethane resin composition and moldings for optical use
    JP5715914B2|2015-05-13|Ink binder, ink and ink cured product
    JP2007523227A|2007-08-16|adhesive
    CN101798492B|2012-01-25|Preparation method of ultraviolet light curing composite binding agent
    KR101963671B1|2019-03-29|Radiation curable coating compositions for metal
    EP2546273B1|2014-05-21|Low-viscosity urethane system
    TWI617640B|2018-03-11|Uv-curing hot melt adhesive containing low content of oligomers
    SE1300292A1|2014-10-23|New urethane acrylate
    KR20060121834A|2006-11-29|Radiation-hardening unsaturated polyester urethane resin
    JP2011522067A|2011-07-28|Curing accelerator for anaerobic curable compositions
    CN113166341A|2021-07-23|Curable heat seal adhesive for bonding polymers
    JP2021063186A|2021-04-22|Resin composition for active energy ray-curable adhesive, and adhesive sheet
    TW201723005A|2017-07-01|Curable resin and curing composition comprising the same
    CN111072910A|2020-04-28|Nonionic polyurethane acrylate and preparation method and application thereof
    JP2002308955A|2002-10-23|Photocurable resin composition
    EP3722346A1|2020-10-14|2-component polyurethane coatings with improved pot life without lost weathering stability
    TW201247728A|2012-12-01|Amino and hydroxyl functional polyesters
    同族专利:
    公开号 | 公开日
    JP2016522183A|2016-07-28|
    EP2989138A4|2016-11-30|
    KR20160002985A|2016-01-08|
    EP2989138B1|2018-08-01|
    US20170320887A1|2017-11-09|
    WO2014175802A1|2014-10-30|
    EP2989138A1|2016-03-02|
    SE537631C2|2015-08-25|
    CN105263980A|2016-01-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS558013A|1978-06-30|1980-01-21|Fujitsu Ltd|Semiconductor device manufacturing method|
    US4260703A|1979-10-26|1981-04-07|Union Carbide Corporation|Novel urethane-acrylate and radiation curable compositions|
    JPH0147477B2|1980-12-16|1989-10-13|Mitsubishi Gas Chemical Co|
    JPH0428753B2|1982-08-30|1992-05-15|Nippon Polyurethane Kogyo Kk|
    JPH0585555B2|1984-07-16|1993-12-07|Sanyo Kokusaku Pulp Co|
    JPH0149370B2|1984-08-14|1989-10-24|Sanyo Kokusaku Pulp Co|
    JPS6230640A|1985-07-30|1987-02-09|Nitto Electric Ind Co Ltd|Coating material for optical glass fiber|
    JP3292268B2|1994-07-21|2002-06-17|東亞合成株式会社|Active energy ray-curable ink composition|
    JP3367301B2|1995-09-30|2003-01-14|凸版印刷株式会社|Electron beam-curable monofunctional urethane acrylate oligomer and electron beam-curable adhesive composition containing the same|
    DE19810793A1|1998-03-12|1999-09-16|Basf Ag|Curable polyurethane polymer, dispersion based on this polymer, process for its preparation and its use|
    JP2000034441A|1998-07-21|2000-02-02|Dainippon Ink & Chem Inc|Active energy radiation-curing coating composition|
    JP2010519369A|2007-02-20|2010-06-03|ビーエーエスエフソシエタス・ヨーロピア|High refractive index monomers, their compositions and uses|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE1300292A|SE537631C2|2013-04-22|2013-04-22|A urethane acrylate which is a reaction product of a diol component A, a component B with acrylic saturation and an isocyanate component C, wherein A comprises alkoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-dialkanol.|SE1300292A| SE537631C2|2013-04-22|2013-04-22|A urethane acrylate which is a reaction product of a diol component A, a component B with acrylic saturation and an isocyanate component C, wherein A comprises alkoxylated 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-dialkanol.|
    CN201480022877.9A| CN105263980A|2013-04-22|2014-03-11|Urethane acrylates based on 2,4,8,10-tetraoxospiro[5.5]undecane-3,9-dialkanols|
    US14/784,421| US20170320887A1|2013-04-22|2014-03-11|Urethane acrylates based on 2,4,8,10-tetraoxospiro[5.5]-undecane-3,9-dialkanols|
    PCT/SE2014/000024| WO2014175802A1|2013-04-22|2014-03-11|Urethane acrylates based on 2,4,8,10-tetraoxospiro[5.5]undecane-3,9-dialkanols|
    EP14788269.0A| EP2989138B1|2013-04-22|2014-03-11|Urethane acrylates based on 2,4,8,10-tetraoxospiro[5.5]undecane-3,9-dialkanols|
    JP2016510651A| JP2016522183A|2013-04-22|2014-03-11|Urethane acrylate based on 2,4,8,10-tetraoxospiro [5.5] undecane-3,9-dialkanol|
    KR1020157033112A| KR20160002985A|2013-04-22|2014-03-11|Urethane acrylates based on 2,4,8,10-tetraoxospiro[5.5]undecane-3,9-dialkanols|
    [返回顶部]