EP2225338A1 - Beschichtungsmassen mit verbesserten eigenschaften - Google Patents

Beschichtungsmassen mit verbesserten eigenschaften

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Publication number
EP2225338A1
EP2225338A1 EP08863745A EP08863745A EP2225338A1 EP 2225338 A1 EP2225338 A1 EP 2225338A1 EP 08863745 A EP08863745 A EP 08863745A EP 08863745 A EP08863745 A EP 08863745A EP 2225338 A1 EP2225338 A1 EP 2225338A1
Authority
EP
European Patent Office
Prior art keywords
groups
crosslinker
functional groups
coating composition
spacer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08863745A
Other languages
German (de)
English (en)
French (fr)
Inventor
Michael Kutschera
Lydie Tuchbreiter
Nick Gruber
Rüdiger STARK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP08863745A priority Critical patent/EP2225338A1/de
Publication of EP2225338A1 publication Critical patent/EP2225338A1/de
Withdrawn legal-status Critical Current

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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the present invention relates to coating compositions which give coatings with high hardness and at the same time high flexibility and / or high scratch resistance.
  • the disadvantage is that the investigations there relate only to radiation-curable (meth) acrylates as coating compositions which have a different curing behavior than other coating compositions, for example two-component coating compositions.
  • the object of the present invention was to develop coating compositions which bring about high hardness combined with high flexibility and / or high scratch resistance in the coatings obtained therefrom.
  • a coating composition comprising at least one crosslinker (A) which carries a multiplicity of functional groups FG and at least one binder (B) which carries groups which are reactive with the functional groups FG of the crosslinker (A) in which the functional groups FG are isocyanate groups (-NCO),
  • the coating compositions of the invention are crosslinker (A) - binder (B) combinations, ie two-component coating compositions.
  • the crosslinker (A) has functional groups (FG) which are reactive with the groups of the binder (B).
  • the functional groups (FG) of the crosslinker (A) are isocyanate groups (-NCO)
  • the binder component (B) has groups complementary to the functional groups (FG) of the binder (A).
  • These complementary groups of the binder (A) are preferably hydroxy (-OH), primary amino (-NH 2) and / or secondary amino groups (-NHR 1 ), preferably hydroxy groups.
  • C 1 -C 4 -alkyl is methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl, ethyl, isopropyl, n-propyl, n-butyl and tert-butyl, more preferably methyl, ethyl, n-butyl and tert-butyl, most preferably methyl, ethyl and n-butyl and especially methyl.
  • the crosslinker (A) is constructed according to the invention from a spacer and at least two head groups arranged terminally on the spacer, which each carry at least two functional groups FG.
  • the number of functional groups FG per head group may preferably be up to 10, particularly preferably up to 8, very particularly preferably up to 6 and in particular up to 5.
  • head group is defined in the context of the present invention as follows:
  • the number of headgroups can be on a statistical average preferably up to 10, particularly preferably up to 8, very particularly preferably up to 5, in particular up to 4 and especially up to 3. In a particular embodiment, the number of headgroups per crosslinker is exactly 2.
  • the functionality of the crosslinkers can be calculated from the number of head groups multiplied by the number of functional groups per head group and thus corresponds to the total number of functional groups in the crosslinker molecule.
  • the total density of the functional groups FG in the crosslinking agent (A) is at least 2.0, preferably at least 2.5 mol / kg and can particularly preferably from 2.5 mol / kg to 8 mol / kg, very particularly preferably from 3 to 6 mol / kg.
  • a simplified statement of the present invention is that the number and density of the functional groups (FG) in the crosslinker (A) affects the hardness of the resulting coating, whereas the nature and length of the spacer affects the flexibility of the resulting coating.
  • the skilled person can adjust the properties of the resulting coating by adjusting these sizes in the context of this invention.
  • spacer is defined in the context of the present invention as follows: the region inside the crosslinker (A), the
  • - Is substantially acyclic, ie at least 80% of the spacer atoms forming and atomic groups are components of acyclic structures, and - is essentially composed of at least 50 and up to 2000 interconnected by single bonds atoms and atomic groups each independently selected from the group consisting of -CH 2 -, -CHR 3 -, -CR 3 R 4 -, -C ( O) -, -O-, -NH- and -NR 3 -, ie not more than 10 bonds of the spacer are multiple bonds and / or component of a ring system.
  • the spacer is essentially free of functional groups FG, which means that not more than 10% of all functional groups FG contained in the crosslinker are bound to the spacer, preferably not more than 5%, particularly preferred are no functional groups FG to the spacer bound.
  • the spacer is essentially acyclic, which means in the context of the present invention that at least 80%, preferably at least 85%, more preferably at least 90%, most preferably at least 95% and especially 100% of the spacer atoms and atomic groups constituents of acyclic structures.
  • substantially interconnected by single bonds means that not more than 10% of the spacers' bonds are multiple bonds and / or part of a ring system, preferably not more than 8%, more preferably not more than 5%, most preferably not more than 3% and in particular none.
  • R 3 and R 4 are independently of one another Ci to Cis-alkyl, C ⁇ to Ci2-aryl or Cs to Ci 2 -cycloalkyl, preferably Ci to Cis-alkyl, and particularly preferably Ci to C 4 - alkyl.
  • Spacer and head groups are chemically linked.
  • the first non-acyclic atom beyond the spacer is already part of the head group.
  • spacer and head group carry complementary, mutually reactive groups, preferably a group FG, which is preferably located on the head group, and a complementary thereto
  • the skeleton of the spacer is selected from the group consisting of polyethers, polyesters, hydrocarbons and polyurethane polyols, preferably selected from the group consisting of polyethers, polyesters and polyurethane polyols, more preferably selected from the group consisting of polyethers and polyesters and most preferably it is a polyether.
  • Suitable spacers are, for example, polyetherols which are prepared by addition of ethylene oxide, propylene oxide or butylene oxide to H-active components. Likewise, polycondensates of butanediol are suitable. The functionality of the polyether olene usually corresponds to the number of head groups which are to be bound to the spacer.
  • H-active components are ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol , 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol , 1, 6-hexanediol, 2-methyl-1, 5-pentanediol, 2-ethyl-1, 4-butanediol, 2-ethyl-1, 3-hexanediol,
  • the polyether is preferably polyTHF having a molecular weight between 700 and 4500, preferably 800 to 2000, poly-1,3-propanediol or polypropylene glycol having a molecular weight between 134 and 2000 or polyethylene glycol having a molecular weight between 238 and 2000, more preferably a poly THF.
  • spacers are polyesterols, as obtainable by condensation of polycarboxylic acids, in particular dicarboxylic acids with polyols, in particular diols.
  • polycarboxylic acids in particular dicarboxylic acids
  • polyols in particular diols.
  • triols, tetrols, etc., as well as triacids, etc. are also used in part.
  • Polyesterpolyols are known, for example, from Ullmanns Encyklopadie der ischen Chemie, 4th Edition, Volume 19, pages 62 to 65. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated.
  • Examples include: Oxalic, maleic, fumaric, succinic, glutaric, adipic, sebacic, dodecanedioic, o-phthalic, isophthalic, terephthalic, trimellitic, azelaic, 1,4-cyclohexanedicarboxylic or tetrahydrophthalic, hydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, dimer fatty acids, their isomers and hydrogenation products and esterifiable derivatives, such as anhydrides or dialkyl esters, for example C 1 -C 4 -alkyl esters, preferably methyl, ethyl or n-butyl esters, of the acids mentioned Among these, preferred are the aliphatic carboxylic acids and their derivatives.
  • dicarboxylic acids of the general formula HOOC- (CH 2) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, very particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  • polyesterols 1, 2-propanediol, ethylene glycol, 2,2-dimethyl-1, 2-ethanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, poly-THF having a molecular weight between 162 and 4500, preferably 250 to 2000, poly-1,3-propanediol having a molecular weight between 134 and 1 178, poly-1,2-propanediol having a molecular weight between 134 and 898, polyethylene glycol having a molecular weight between 106 and 458, Neopentyl glycol, hydroxypiva
  • Alcohols of the general formula HO- (CH 2 ) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • Preferred are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol.
  • lactone-based polyesterdiols which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules.
  • Preferred lactones are those which are derived from compounds of the general formula HO- (CH 2) ⁇ -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit is also represented by a C 1 to C 4 alkyl radical may be substituted.
  • Examples are ⁇ -caprolactone, ⁇ -propiolactone, gamma-butyrolactone and / or methyl- ⁇ -caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivolactone, and mixtures thereof.
  • Suitable starter components are, for example, the Hend as a structural component for the polyester polyols called low molecular weight dihydric alcohols.
  • the corresponding polymers of ⁇ -caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • polyesterols generally corresponds to the number of head groups which are to be bound to the spacer.
  • the hydrocarbons may, for example, be polyisobutenes or polyolefin waxes which have been modified with reactive groups such that they are chemically bound to the head groups.
  • isobutene can be cationically polymerized or oligomerized with polyisobutenes using different catalyst systems.
  • BF3 and AICI3 as well as TiCU and BCI3 have gained importance, with TiCl 4 and BCb being used in so-called "living cationic polymerization”.
  • isobutene can be subjected to controlled cationic polymerization or oligomerization under certain conditions.
  • This procedure is referred to in the literature as "living cationic polymerization” (see, eg, Kennedy and Ivan, Designed Polymers by Carbocationic Macromolecular Engineering, Hanser Publishers (1992) and the literature cited therein).
  • Detailed information can also be found in W0-A1 01/10969, there especially p. 8, Z. 23 to p. 11, Z.23.
  • the molecular weight distribution M w / M n is in the range of 1.05-10, polymers from the "living" polymerization usually having values between 1.05 and 2.0. Depending on the application, low (such as for example, 1, 1-1, 5, preferably by 1, 3) average (such as 1, 6-2.0, preferably by 1, 8) or high (such as 2.5-10, preferably 3-5) values be beneficial.
  • polyisobutenes in a molecular weight range M n of about 700 to about 100,000 daltons, with molecular weights of about 1000 to 60,000 daltons being preferred.
  • polyisobutenes having an approximate number average molecular weight M n of from 1500 to 32,000 daltons, very particularly preferably from 2000 to 25,000 and in particular from 2300 to 18,000 daltons.
  • polyethylene waxes have long been known. These are essentially linear, mostly non-functional, hydrophobic polymers. However, a functionalization of such polyolefin waxes is required to allow the attachment of the head groups.
  • a functionalization can be carried out, for example, by copolymerization of a comonomer which carries a corresponding functional group, or by subsequent modification of the polyolefin waxes, for example by graft polymerization with monomers carrying functional groups.
  • the number-average molecular weight M n of the polyolefin waxes which can be used according to the invention is up to 20,000, preferably up to 18,000 and particularly preferably up to 15,000 g / mol.
  • the preparation of polyolefin waxes can be carried out in high-pressure stirred autoclaves or in high-pressure tubular reactors. Production in stirred high pressure autoclave is preferred.
  • the high-pressure stirred autoclaves used for this purpose are known per se, a description can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996.
  • the polyurethane polyols which can be used as spacers are generally reaction products of diisocyanates or polyisocyanates, preferably diisocyanates, with diols or polyols, the reaction being conducted in such a way that the products have the desired length and functionality.
  • the diisocyanates used may be aromatic, aliphatic or cycloaliphatic, preferably aliphatic or cycloaliphatic, which is referred to in this document as (cyclo) aliphatic, particularly preferred are aliphatic isocyanates.
  • Aromatic isocyanates are those which contain at least one aromatic ring system, ie both purely aromatic and also araliphatic compounds.
  • Cycloaliphatic isocyanates are those containing at least one cycloaliphatic ring system.
  • Aliphatic isocyanates are those which contain exclusively straight or branched chains, ie acyclic compounds.
  • higher isocyanates having on average more than 2 isocyanate groups are also considered.
  • triisocyanates such as triisocyanato, 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4'-triisocyanato-diphenyl ether or the mixtures of di-, tri- and higher polyisocyanates suitable for example by phosgenation of corresponding aniline / Formaldehyde condensates are obtained and represent methylene bridges Polyphenylpolyiso- cyanate.
  • the monomeric isocyanates are preferably isocyanates having 4 to 20 C atoms.
  • customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4, 1, 3 or 1, 2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5-
  • Isophorone diisocyanate is usually present as a mixture, namely the cis and trans isomers, usually in the ratio of about 60:40 to 80:20 (w / w), preferably in the ratio of about 70:30 to 75:25 and most preferably in the ratio of about 75:25.
  • Dicyclohexylmethane-4,4'-diisocyanate may also be present as a mixture of the different cis and trans isomers.
  • the average NCO functionality of such compounds is generally at least 1.8, and may be up to 8, preferably 2 to 5 and more preferably 2.4 to 4.
  • the polyisocyanates are preferably the following compounds:
  • isocyanurate polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate.
  • the isocyanurates present are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl
  • Isocyanurates which are cyclic trimers of diisocyanates, or mixtures with their higher, more than one isocyanurate homologues.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 8.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the polyisocyanates containing uretdione groups are obtained in the context of this invention in a mixture with other polyisocyanates, in particular those mentioned under 1).
  • the diisocyanates can be reacted under reaction conditions under which both uretdione groups and the other polyisocyanates are formed, or first the uretdione groups formed and these are then reacted to the other polyisocyanates or the diisocyanates first to the other polyisocyanates and these then to uretdione groups-containing Products are implemented.
  • biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, especially tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues.
  • These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 6.
  • diisocyanate for example hexamethylene diisocyanate or isophorone diisocyanate
  • monohydric or polyhydric alcohols monohydric or polyhydric alcohols.
  • These urethane and / or allophanate-containing polyisocyanates generally have an NCO content of 12 to 24 wt .-% and an average NCO functionality of 2.5 to 4.5.
  • Such urethane and / or allophanate-containing polyisocyanates can uncatalyzed or preferably in
  • catalysts such as ammonium carboxylates or hydroxides, or allophanatization catalysts, e.g. Zn (I I) compounds, each in the presence of mono-, di- or polyvalent, preferably monohydric alcohols produced.
  • oxadiazinetrione-containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates are accessible from diisocyanate and carbon dioxide.
  • polyisocyanates containing iminooxadiazinedione groups preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • iminooxadiazine-dione-containing polyisocyanates can be prepared from diisocyanates by means of special catalysts.
  • Hyperbranched polyisocyanates as are known, for example, from EP-A 1134246, EP-A 1134247, EP-A 1167413 and EP-A 1026185.
  • the polyisocyanates 1) -11), preferably 1), 3), 4) and 6) may, after their preparation, comprise polyisocyanates having aryl, cycloaliphatic or aliphatic bound groups in biuret group or urethane / allophanate groups, preferably (cyclo) aliphatically bound isocyanate groups are transferred.
  • the biurizing of biuret groups is carried out, for example, by adding water or
  • urethane and / or allophanate groups by reaction with mono-, di- or polyhydric, preferably monohydric alcohols, optionally in the presence of suitable catalysts.
  • These biuret or urethane / allophanate-containing polyisocyanates generally have an NCO content of 18 to 22% by weight and a mean
  • NCO functionality from 2.8 to 6 on.
  • Hydrophilic modified polyisocyanates i. Polyisocyanates which, in addition to the groups described under 1-12, contain those which formally form by addition of molecules with NCO-reactive groups and hydrophilicizing groups to the
  • Isocyanate groups of the above molecules are formed.
  • the latter are nonionic groups such as alkyl polyethylene oxide and / or ionic, which are derived from phosphoric acid, phosphonic acid, sulfuric acid or sulfonic acid, or their salts.
  • Modified Polyisocyanates for Dual Cure Applications i. Polyisocyanates which contain, in addition to the groups described under 1-12, those which formally arise from the addition of molecules with NCO-reactive groups and groups crosslinkable by UV or actinic radiation to the isocyanate groups of the above molecules. These molecules are, for example, hydroxyalkyl (meth) acrylates and other hydroxy-vinyl compounds.
  • the polyisocyanate is selected from the group consisting of isocyanurates, biurets, urethanes and allophanates, preferably from the group consisting of isocyanurates, urethanes and allophanates, particularly preferably from the group consisting of isocyanurates and allophanates, in particular is an isocyanurate group-containing polyisocyanate.
  • the polyisocyanate is isocyanurate group-containing polyisocyanates of 1,6-hexamethylene diisocyanate.
  • the polyisocyanate is a mixture of isocyanurate-containing polyisocyanates of 1,6-hexamethylene diisocyanate and of isophorone diisocyanate.
  • Suitable di- or polyols for the preparation of polyurethane polyols as spacers are, for example, the abovementioned polyetherols or polyesterols, but preferably 1,2-propanediol, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3-propanediol , 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1, 3-diol, 2,4-diethyloctane-1, 3-diol , 1, 6-hexanediol, poly-THF having a molecular weight between 162 and 4500, preferably 250 to 2000, poly-1, 3-propanediol having a molecular weight between 134 and 1 178, poly-1, 2-propanediol with a molecular weight between
  • One possibility for preparing the crosslinkers according to the invention consists in reacting one or more of the abovementioned spacers selected from the group consisting of polyethers, polyesters, polycarbonates, hydrocarbons and polyurethane polyols with at least one polyisocyanate as head group such that a crosslinker reacts with the inventive Characteristics is obtained.
  • Polyisocyanates suitable for this purpose are, for example, the polyisocyanates 1) to 14) listed above under the polyurethane polyols, of these preferred are isocyanurate-containing polyisocyanates 1) and / or hyperbranched polyisocyanates 9), particularly preferably those polyisocyanates consisting of 1,6-hexamethylene diisocyanate and / or or isophorone diisocyanate.
  • polyisocyanates are preferred via urethane, allophanate, urea or biuret groups or their analogous thio compounds, preferably via urethane groups and / or allophanate groups connected to the spacer. Likewise, mixtures with respect to the connection are possible.
  • a preferred embodiment of the present invention are crosslinkers (A) whose head groups have a high density of functionality of at least 2.5 mol / kg, ie at least 2.5 moles of functional groups per kg of isolated head group prior to linking with the spacer, especially preferably at least 3 mol / kg, very particularly preferably at least 4.5 mol / kg and in particular at least 5 mol / kg.
  • the functionality density of the head groups can be up to 10 mol / kg, preferably up to 8 and particularly preferably up to 7 mol / kg.
  • Another object of the present invention is the use of crosslinkers (A) in coating compositions for simultaneously increasing the hardness and flexibility and / or high scratch resistance of the resulting coatings.
  • Another object of the present invention is a process for simultaneously increasing the hardness and flexibility and / or scratch resistance of coatings, by adding at least one crosslinker (A) to the coating compositions from which the coatings are obtained.
  • crosslinker (A) in general, it is sufficient to replace at least 3% by weight, based on the total amount of crosslinker, by the crosslinker (A) according to the invention, preferably at least 5% by weight. In most cases not more than 30% by weight are required, preferably up to 20% and more preferably up to 15% by weight.
  • the simultaneous increase in hardness and flexibility and / or scratch resistance is preferably determined by adding a coating composition with a conventional crosslinker, that is a crosslinker other than the crosslinkers (A), and binder (B) with the same type of functional groups FG and the like Binder made. From the conventional crosslinker are based on the functional
  • the scratch resistance is preferably determined as follows: a nonwoven (Scotchbrite®, 7448 type S ultrafine) was applied to a 500 g fitters hammer on the head with double-sided adhesive tape. The hammer was held with two fingers at the end of the handle and moved with uniform double strokes without jamming and without additional pressure application on a line over the paint film back and forth.
  • the gloss measurement was carried out with a gloss meter Mikro TRI-Gloss at 20 ° and / or 60 ° angle of incidence.
  • the binder (B) depends on the choice of the crosslinker (A) and has complementary groups to the groups FG.
  • the binders (B) have a functionality of at least 2, preferably at least 3, more preferably at least 4 and most preferably at least 6. Upwards, the functionality is not limited and may preferably be up to 100, more preferably up to 75 and most preferably up to 50.
  • the number average molecular weight M n of the binder (B) is usually at least 1000, more preferably at least 2000 and most preferably at least 5000 g / mol.
  • the molecular weight M n may be, for example, up to 200,000, preferably up to 100,000, particularly preferably up to 80,000 and very particularly preferably up to 50,000 g / mol. In some cases, the molecular weights may be even higher.
  • the binders are, for example, polyacrylate polyols, polyester polyols, polyether polyols, polyurethane polyols; polyurea; Polyesterpolyacrylatpolyole; Polyesterpolyurethane polyols; Polyurethane polyacrylate polyols, polyurethane modified alkyd resins; Fatty acid-modified polyester polyurethane polyols, copolymers with allyl ethers, graft polymers from the substance groups mentioned with, for example, different glass transition temperatures, and mixtures of said binders. Preference is given to polyacrylate polyols, polyester polyols and polyether polyols.
  • Preferred OH numbers of the binders are 40-350 mg KOH / g solid resin for polyester, preferably 80-180 mg KOH / g solid resin, and 15-250 mg KOH / g solid resin for polyacrylatols, preferably 80 -160 mg KOH / g.
  • the binders may have an acid number according to DIN EN ISO 3682 up to 200 mg KOH / g, preferably up to 150 and particularly preferably up to 100 mg KOH / g.
  • Polyacrylate polyols as binders preferably have a molecular weight M n of at least 1000, particularly preferably at least 2000 and very particularly preferably at least 5000 g / mol.
  • the molecular weight M n may in principle be unlimited upwards, preferably up to 200,000, particularly preferably up to 100,000, very particularly preferably up to 80,000 and in particular up to 50,000 g / mol.
  • polymerizable monomers are copolymerized with hydroxy-functional monomers.
  • the latter can be, for example, monoesters of ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid (referred to in this document as "(meth) acrylic acid”), with diols or polyols, which preferably have 2 to 20 C atoms and have at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 1-dimethyl-1, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1, 4-butanediol, 1,5-pentanediol, neopentyl glycol, neopentyl glycol hydroxypivalate, 2-ethyl
  • the hydroxyl-containing monomers are used in the copolymerization in admixture with other polymerizable, preferably free-radically polymerizable monomers, preferably those which contain at least 10% by weight, more preferably at least 25% by weight and most preferably at least 50% by weight C 1 -C 20, preferably C 1 -C 4 -alkyl (meth) acrylate, (meth) acrylic acid, vinylaromatics having up to 20 C atoms, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl halides, non-aromatic hydrocarbons having 4 to 8 C atoms and 1 or 2 double bonds, unsaturated nitriles and mixtures thereof exist.
  • Particular preference is given to the polymers which consist of more than 60% by weight of C 1 -C 10 -alkyl (meth) acrylates, styrene and its derivatives, vinylimidazole or mixtures thereof.
  • the polymers may contain hydroxy-functional monomers corresponding to the above hydroxy group content and optionally other monomers, e.g. (Meth) acrylic acid glycidyl epoxyesters, ethylenically unsaturated acids, in particular carboxylic acids, acid anhydrides or acid amides.
  • monomers e.g. (Meth) acrylic acid glycidyl epoxyesters, ethylenically unsaturated acids, in particular carboxylic acids, acid anhydrides or acid amides.
  • Further binders (B) are e.g. Polyesterols, as obtainable by condensation of polycarboxylic acids, in particular dicarboxylic acids with polyols, in particular diols.
  • polyesterols as obtainable by condensation of polycarboxylic acids, in particular dicarboxylic acids with polyols, in particular diols.
  • triols, tetrols, etc., as well as triacids, etc. are also used in part.
  • Polyester polyols are e.g. from Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pp. 62-65. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic or heterocyclic and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include:
  • anhydrides or dialkyl esters for example C 1 -C 4 -alkyl esters, preferably methyl, ethyl or n-but
  • dicarboxylic acids of the general formula HOOC- (CH 2) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  • polyesterols 1, 2-propanediol, ethylene glycol, 2,2-dimethyl-1, 2-ethanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, poly-THF having a molecular weight between 162 and 4500, preferably 250 to 2000, poly-1,3-propanediol having a molecular weight between 134 and 1178, poly-1,2-propanediol having a molecular weight between 134 and 898, polyethylene glycol having a molecular weight between 106 and 458, neopentyl glycol , Hydroxy
  • Alcohols of the general formula HO- (CH 2 ) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • Preferred are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol.
  • polycarbonate diols as binders (B), e.g. can be obtained by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for the polyesterpolyols.
  • lactone-based polyesterdiols which are homopolymers or copolymers of lactones, preferably hydroxyl-terminated addition products of lactones to suitable difunctional starter molecules.
  • Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit by a Cr to C 4 alkyl may be substituted.
  • Examples are ⁇ -caprolactone, ⁇ -propiolactone, gamma-butyrolactone and / or methyl- ⁇ -caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivolactone, and mixtures thereof.
  • Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols.
  • the corresponding polymers of ⁇ -caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • polymers of lactones it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.
  • binders are polyetherols which are prepared by addition of ethylene oxide, propylene oxide or butylene oxide to H-active components.
  • polycondensates of butanediol are suitable.
  • hydroxy-functional carboxylic acids for example dimethylolpropionic acid or dimethylolbutanoic acid.
  • the polymers may of course also be compounds with primary secondary amino groups.
  • crosslinker (A) and binder (B) in a stoichiometric ratio of, for example, 5: 1 to 1: 5, preferably 3: 1 to 1: 3, more preferably 2: 1 to 1: 2, very particularly preferably 1, 5: 1 to 1: 1, 5 and in particular 1, 1: 1 to 1: 1, 2 mixed.
  • the coating composition a solvent (C) and / or further typical paint additives (D) are added.
  • solvents (C) are esters, ester alcohols, ethers, ether alcohols, aromatic and / or (cyclo) aliphatic hydrocarbons and mixtures thereof and halogenated hydrocarbons. Alcohol can also be introduced into the mixtures via the amino resins.
  • alkanoic acid alkyl esters Preference is given to alkanoic acid alkyl esters, alkyl alkanoate ethers, alkoxylated alkaneklarealkyl esters and mixtures thereof.
  • Esters are, for example, n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate, and the mono- and diacetyl esters of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol, for example butylglycol acetate. Further examples are also carbonates, such as preferably 1, 2-ethylene carbonate, 1, 2-propylene carbonate or 1, 3-propylene carbonate.
  • Ethers are, for example, tetrahydrofuran (THF), dioxane and the dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
  • THF tetrahydrofuran
  • dioxane dioxane
  • dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
  • Alkanoic acid ester ethers are, for example, poly (C 2 to C 3) alkylene glycol (C 1 to C 4) monoalkyl ether acetates.
  • Ether alcohols are, for example, poly (C 2 to C 3) alkylene glycol di (C 1 to C 4) alkyl ethers, dipropylene glycol dimethyl ethers, preferably butyl glycol dialkyl ethers.
  • Aromatic hydrocarbon mixtures are those which comprise predominantly aromatic C7- to Ci4-hydrocarbons and may comprise a boiling range from 1 10 to 300 0 C, more preferably toluene, o-, m- or p-xylene, Trimethylben- zolisomere, tetramethylbenzene, ethylbenzene , Cumene, tetrahydronaphthalene and mixtures containing such.
  • Examples include the Solvesso® brands of ExxonMobil Chemical, especially Solvesso® 100 (CAS No. 64742-95-6, predominantly Cg and Cio-aromatics, boiling range about 154-178 0 C), 150 (boiling range about 182 207 0 C) and 200 (CAS No. 64742-94-5), as well as the Shellsol® brands of the company Shell, Caromax® brands of the company Petrochem Carless, eg Caromax® 18, or products of the company DHC, Hydrocarbon mixtures of paraffins, cycloparaffins and aromatics are also known under the designations crystal oil (for example crystal oil 30, boiling range about 158-198 0 C or crystal oil 60: CAS No.
  • crystal oil for example crystal oil 30, boiling range about 158-198 0 C or crystal oil 60: CAS No.
  • the aromatic content of such hydrocarbon mixtures is generally more than 90% by weight, preferably more than 95, more preferably more than 98% and very particularly preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.
  • the density at 20 0 C in accordance with DIN 51757 of the hydrocarbons may be less than
  • the content of aliphatic hydrocarbons is generally less than 5, preferably less than 2.5 and more preferably less than 1% by weight.
  • Examples of (cyclo) aliphatic hydrocarbons include decalin, alkylated decalin and isomer mixtures of straight-chain or branched alkanes and / or cycloalkanes.
  • n-butyl acetate Preference is given to n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2, 2-methoxyethyl acetate, and mixtures thereof.
  • Such mixtures can be prepared in a volume ratio of 10: 1 to 1:10, preferably in a volume ratio of 5: 1 to 1: 5 and more preferably in a volume ratio of 1: 1, where appropriate still in the reaction mixture of the transetherification solvent, in particular the alcohols R 1 OH and R 2 OH are not counted.
  • Preferred examples are butyl acetate / xylene, methoxypropyl acetate / xylene 1: 1, butyl acetate / solvent naphtha 100 1: 1, butyl acetate / Solvesso® 100 1: 2 and crystal oil 30 / Shellsol® A 3: 1.
  • additives (D) for example, antioxidants, stabilizers, activators (accelerators), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents can be used.
  • chelating agents e.g. Ethylenediamine and their salts and ß-diketones are used.
  • Suitable fillers include silicates, e.g. B. obtainable by hydrolysis of silicon tetrachloride, such as Aerosil ® from silicates. Degussa, siliceous earth, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.
  • silicates e.g. B. obtainable by hydrolysis of silicon tetrachloride, such as Aerosil ® from silicates. Degussa, siliceous earth, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin ® grades from Ciba-Spezialitatenchemie) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. B. bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate used. Stabilizers are usually used in amounts of 0.1 to 5.0% by weight, based on the solid components contained in the preparation.
  • suitable radical scavengers for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. B. bis (2,2,6,6-te
  • Pigments may also be included. Pigments are according to CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995 with reference to DIN 55943 particulate "practically insoluble in the application medium, inorganic or organic, colored or achromatic colorants".
  • practically insoluble means a solubility at 25 ° C. of less than 1 g / 1000 g of application medium, preferably less than 0.5, more preferably less than 0.25, very preferably less than 0.1 and in particular less than 0.05 g / 1000 g of application medium.
  • pigments include any systems of absorption and / or effect pigments, preferably absorption pigments. Number and selection of the pigment components are not subject to any restrictions. You can choose the respective Requirement, for example, the desired color impression, be adjusted as desired.
  • Effect pigments are to be understood as meaning all pigments which have a platelet-like structure and impart special decorative color effects to a surface coating.
  • the effect pigments are, for example, all effect pigments which can usually be used in vehicle and industrial coating.
  • Examples of such effect pigments are pure metal pigments; such as. Aluminum, iron or copper pigments;
  • Interference pigments such as e.g. titanium dioxide coated mica, iron oxide coated mica, mixed oxide coated mica (e.g., with titanium dioxide and Fe2O3 or titanium dioxide and O2O3), metal oxide coated aluminum, or liquid crystal pigments.
  • the coloring absorption pigments are, for example, customary organic or inorganic absorption pigments which can be used in the coatings industry.
  • organic absorption pigments are azo pigments, phthalocyanine, quinacridone and pyrrolopyrrole pigments.
  • inorganic absorption pigments are iron oxide pigments, titanium dioxide and carbon black.
  • the coating compositions of the invention are suitable for coating substrates such as wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials such as cement blocks and fiber cement boards, or metals or coated metals, preferably of plastics or metals, in particular Form of films, more preferably metals.
  • the coating compositions according to the invention are suitable as or in internal coatings, preferably also as or in exterior coatings, ie those applications which are exposed to daylight, building components, coatings on vehicles and aircraft and for industrial applications.
  • the coating compositions according to the invention are described as or in automotive clear, base and automotive
  • topcoat (s) or primers used are used. Further preferred fields of use are can coating and coil coating.
  • the coating compositions are particularly suitable for applications in which particularly high application safety, outdoor weathering resistance, appearance, scratch resistance, solvent resistance and / or chemical resistance are required.
  • the coating of the substrates with the coating compositions according to the invention is carried out by customary methods known to the person skilled in the art, it being possible to use at least one Inventive coating agent or a paint formulation on the substrate to be coated in the desired thickness applies and the volatile constituents of the coating agent, optionally with heating, removed (drying). If desired, this process can be repeated one or more times.
  • the application to the substrate can in a known manner, for. B. by spraying, filling, doctoring, brushing, rolling, rolling or pouring done.
  • the coating thickness is generally in a range of about 3 to 1000 g / m 2 and preferably 10 to 200 g / m 2 .
  • the curing is generally carried out so that, after application of the coating compositions to the substrates optionally at a temperature up to 140 0 C, preferably room temperature to 120 0 C and more preferably room temperature to 100 0 C over a period of up to 72 hours , preferably up to 48 hours, more preferably up to 24 hours, most preferably up to 12 and in particular up to 6 hours under an oxygen-containing atmosphere, preferably air, or dried and / or cured under inert gas.
  • a temperature up to 140 0 C preferably room temperature to 120 0 C and more preferably room temperature to 100 0 C over a period of up to 72 hours , preferably up to 48 hours, more preferably up to 24 hours, most preferably up to 12 and in particular up to 6 hours under an oxygen-containing atmosphere, preferably air, or dried and / or cured under inert gas.
  • Lacquer curing takes place in dependence on the amount of coating material applied and the enmeshed crosslinking energy via high-energy radiation, heat transfer from heated surfaces or via convection of gaseous media over a period of seconds, for example in strip coating in combination with NIR drying, up to 5 hours
  • thick-film systems on temperature-sensitive materials usually not less than 10 minutes, preferably not less than 15, more preferably not less than 30, and most preferably not less than 45 minutes. Drying removes substantially any solvent present and, in addition, a reaction with the binder may already take place, whereas the curing essentially involves the reaction with the binder.
  • the curing can also be carried out in addition to or instead of the thermal curing by IR and NIR radiation, wherein NIR radiation here electromagnetic radiation in the wavelength range of 760 nm to 2.5 microns, preferably from 900 to 1500 nm is designated.
  • Curing takes place in a period of 1 second to 60 minutes, preferably from 1 minute to 45 minutes.
  • Suitable substrates for the coating compositions according to the invention are, for example, thermoplastic polymers, in particular polymethyl methacrylates, polybutyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyvinylidene fluorides, polyvinyl chlorides, polyesters, polyolefins, acrylonitrile-ethylene-propylene-diene-styrene copolymers (A-EPDM), polyetherimides, polyether ketones, polyphenylene sulfides, polyphenylene ethers or mixtures thereof.
  • thermoplastic polymers in particular polymethyl methacrylates, polybutyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyvinylidene fluorides, polyvinyl chlorides, polyesters, polyolefins, acrylonitrile-ethylene-propylene-diene-styrene copolymers (A-EPDM), polyetherimides, polyether
  • polyethylene polypropylene, polystyrene, polybutadiene, polyesters, polyamides, polyethers, polycarbonate, polyvinyl acetal, polyacrylonitrile, polyacetal, polyvinyl alcohol, polyvinyl acetate, phenolic resins, urea resins, melamine resins, alkyd resins, epoxy resins or polyurethanes, their block or graft copolymers and blends of it.
  • ABS ABS
  • AES AMMA
  • ASA ASA
  • EP EPS
  • EVA EVAL
  • HDPE HDPE
  • LDPE LDPE
  • MABS MABS
  • MBS MF
  • PA PA6, PA66
  • PAN PB
  • PBT PBTP
  • PC PE
  • PEC PEEK
  • PEI PEK
  • PEP PES
  • PET PETP
  • PF PI
  • PIB PMMA
  • POM POM
  • PP PPS
  • PS PSU
  • PUR PVAC
  • PVAL PVAC
  • PVAL PVDC
  • PVP UP plastics
  • SAN SAN
  • SMS UF
  • UP plastics abbreviated to DIN 7728
  • aliphatic polyketones abbreviated to DIN 7728
  • Particularly preferred substrates are polyolefins, e.g. PP (polypropylene), which may optionally be isotactic, syndiotactic or atactic and optionally non-oriented or oriented by uni- or bis-axial stretching, SAN (styrene-acrylonitrile copolymers), PC (polycarbonates), PVC (polyvinyl chlorides), PMMA (Polymethyl methacrylates), PBT (poly (butylene terephthalate) s), PA (polyamides), ASA (acrylonitrile-styrene-acrylic ester copolymers) and ABS (acrylonitrile-butadiene-styrene copolymers), as well as their physical blends. Particularly preferred are PP, SAN, ABS, ASA and blends of ABS or ASA with PA or PBT or PC. Very particular preference is given to polyolefins, PMMA and PVC.
  • ASA in particular according to DE 196 51 350 and the blend ASA / PC.
  • PMMA polymethyl methacrylate
  • impact modified PMMA impact modified PMMA.
  • a further preferred substrate for coating with the coating compositions according to the invention are metals. These are in particular those which have already been coated with another lacquer layer, for example with an E-coat, filler, primer or basecoat. These may be solvent-, water- or powder coating-based, crosslinked, partially crosslinked or thermoplastic, fully cured or applied "wet-on-wet"
  • the type of metal can in principle be any metals.
  • these are metals or alloys which are usually used as metallic construction materials and which have to be protected against corrosion.
  • they are surfaces of iron, steel, Zn, Zn alloys, Al or Al alloys.
  • These may be the surfaces of bodies made entirely of said metals or alloys.
  • the bodies can also be coated only with these metals and themselves consist of different materials, for example of other metals, alloys, polymers or composite materials. It may be surfaces of castings, galvanized iron or steel. In a preferred embodiment of the present invention are steel surfaces.
  • Zn or Al alloys are known to the person skilled in the art. Depending on the desired application, the skilled person will select the type and amount of alloying components. Typical components of zinc alloys include in particular Al, Pb, Si, Mg, Sn, Cu or Cd. Typical constituents of aluminum alloys include, in particular, Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti. These may also be Al / Zn alloys in which Al and Zn are present in approximately the same amount , Steel coated with such alloys is commercially available. The steel may contain the usual alloying components known to those skilled in the art.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
EP08863745A 2007-12-21 2008-12-11 Beschichtungsmassen mit verbesserten eigenschaften Withdrawn EP2225338A1 (de)

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US20120279566A1 (en) * 2011-05-02 2012-11-08 Basf Se Photovoltaic element with increased long-term stability
CN102408824B (zh) * 2011-10-27 2013-07-17 中国海洋石油总公司 一种直升机旋翼用聚酯聚氨酯涂料及其制备方法
CN103421171B (zh) * 2013-07-31 2016-01-20 南华大学 色浆通用型超支化树脂及其制备方法
CN104130691B (zh) * 2014-07-22 2016-07-06 无锡卡秀堡辉涂料有限公司 一种溶剂型双组份弹性聚酯/聚氨酯抗风沙火车涂料及其制备方法
TWI521037B (zh) * 2015-04-10 2016-02-11 博威電子股份有限公司 光學膠組成物、光學膠膜以及光學積層板
CN110093099B (zh) * 2019-03-25 2022-01-04 江苏铁锚玻璃股份有限公司 一种飞机有机玻璃用聚氨酯涂层及其制备方法
ES3042143T3 (en) * 2019-06-07 2025-11-18 Swimc Llc Polymer composition for thin coatings
JP7497178B2 (ja) * 2020-03-17 2024-06-10 第一工業製薬株式会社 二次電池セパレータ用ポリウレタン樹脂水分散体、二次電池セパレータ及び二次電池

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