Fluoride-modified additive for cementitious products, process for its preparation and use thereof
1 Assignment
0 Petitions
Accused Products
Abstract
A fluoromodified admixture containing isocyanate and urethane and/or urea groups is described. Surprisingly, it has been found that the fluoromodified admixture according to the invention is outstandingly suitable even at a very low dosage for the permanent hydrophobic and/or oleophobic and/or dirt-repellent in-bulk finishing of products based on inorganic or hydraulic or mineral binders, without the fundamental property profile (e.g. compressive and flexural tensile strengths) of these products being substantially influenced. Moreover, it was not to be foreseen that in the case of the products treated with the fluoromodified admixtures according to the invention (e.g. hardened building material compositions) a markedly lower water absorption (avoidance of frost damage and corrosion) and a suppression of bleeding on the surfaces (avoidance of visual impairment) are to be observed. Furthermore, it could not be expected that in spite of the high fluorine modification an adequate self-dispersibility is afforded.
24 Citations
54 Claims
-
1-27. -27. (canceled)
-
28. A fluoromodified admixture for cementitious products comprising
(i) a1) 1 to 100 parts by weight of at least one fluoromodified (polymeric) hydrophobization and oleophobization component (A) having a polymer bound fluorine content of 0.5 to 90% by weight a (blocked) isocyanate content of 0.5 to 50% by weight, at least one of a (cyclo)aliphatic isocyante group or an aromatic isocyanate group, and a molecular mass of 275 to 100,000 Dalton of at least one of formula (I)
[CF3—- (CF2)x—
(CH2)y]m—
R1—
(NCO)n
(I),formula (II)
[CF3—
(CF2)x—
(CH2)y—
O-Az]m-R1—
(NCO)n
(II),or formula (III)
[CF3—
CF2—
CF2—
(O—
CF(CF3)—
CF2)x—
O—
CF(CF3)]m—
R1—
(NCO)n
(III);wherein x is from 3 to 20; y is from 1 to 6; z is from 1 to 100; m is from 1 to 3; n is from 1 to 6; R1 is at least one of an inorganic or organic, (cyclo)aliphatic or aromatic radical and has from 1 to 100 C atoms, from 0 to 100 N atoms, from 0 to 100 O atoms and 0 to 100 Si atoms; A is CRiRii—
(CRiiiRiv)p—
O,Ri, Rii, Riii, Riv are independently selected from H, a (cyclo)aliphatic or aromatic organic radical having 1 to 20 C atoms, and p is 1 to 20, wherein the polyalkylene oxide structural unit Az is a homopolymer, copolymer or block copolymer of an alkylene oxide; and b1) 1 to 100 parts by weight of at least one water-emulsifiable or water-soluble (polymeric) hydrophilization component (B) having a polymer bound ethylene oxide content of 0.5 to 90% by weight, an isocyanate content of 0.5 to 50% by weight, at least one of a (cyclo)aliphatic isocyante group or an aromatic isocyanate group, and a molecular mass of from 101 to 100,000 Dalton of formula (IV)
(R3—
O-Az′
)m′
-R2—
(NCO)n′
(IV)wherein z′
is from 1 to 50;m′
is from 1 to 3;n′
is from 1 to 6;R2 is at least one of an inorganic or organic, (cyclo)aliphatic or aromatic radical having from 1 to 100 C atoms, from 0 to 100 N atoms, from 0 to 100 O atoms and from 0 to 100 Si atoms; R3 is from H, a (cyclo)aliphatic or aromatic organic radical having 1 to 20 C atoms; and optionally c1) 1 to 100 parts by weight of at least one fluoromodified and amphiphilic (polymeric) hydrophobization and oleophobization component (C) having a polymer bound fluorine content of 0.5 to 90% by weight, a polymer bound ethylene oxide content of 0.5 to 90% by weight, a (blocked) isocyanate content of 0.5 to 50% by weight, at least one of a (cyclo)aliphatic or aromatic isocyanate group and a molecular mass of from 275 to 100,000 Dalton of formula (V);
[(CF3—
(CF2)x—
(CH2)y)]m(R3—
O-Az′
)m′
-R4—
(NCO)n″
(V),or formula (VI)
[(CF3—
(CF2)x—
(CH2)y)—
O-Az]m(R3—
O-Az′
)m′
-R4—
(NCO)n″
(VI),or formula (VII)
[CF3—
CF2—
CF2—
(O—
CF(CF3)—
CF2)x—
O—
CF(CF3)]m(R3—
O-Az′
)m′
-R4—
(NCO)n″
(VII);wherein n″
is from 1 to 6,R4 is an inorganic or organic, (cyclo)aliphatic or aromatic radical having from 1 to 100 C atoms, from 0 to 100 N atoms, from 0 to 100 O atoms or and from 0 to 100 Si atoms; and R3, m, m′
, x, y and Az′
are as defined above,and optionally d1) from 1 to 50 parts by weight of at least one polyisocyanate component (D), comprising at least one diisocyanate, polyisocyanate, polyisocyanate derivative or polyisocyanate homolog having two or more of (cyclo)aliphatic or aromatic isocyanate groups, or both (cyclo)aliphatic and aromatic isocyanate groups, and a molecular mass of 100 to 2,500 Dalton, or (ii) a2) from 1 to 100 parts by weight of at least one component (A), and c2) from 1 to 100 parts by weight of at least one component (C), and d2) optionally from 1 to 50 parts by weight of at least one component (D), or (iii) b3) from 1 to 100 parts by weight of at least one component (B), and C3) from 1 to 100 parts by weight of at least one component (C), and d3) optionally from 1 to 50 parts by weight of at least one component (D), or (iv) c4) from 1 to 100 parts by weight of at least one component (C), and d4) 1 to 50 parts by weight of at least one component (D), and e) from 0 to 100 parts by weight of at least one water-emulsifiable, hydrophobic or amphiphilic antiefflorescence component (E), comprising 10 to 90% by weight of a (polymer) bound fatty acid ester having two or three hydroxyl groups based on (un)saturated fatty acids and (cyclo)aliphatic or aromatic epoxy resins or polyepoxides having two or three epoxy groups reactive to fatty acids and a molecular mass of from 500 to 50,000 Dalton or a 1,2-dihydroxyalkanediol having from 5 to 50 carbon atoms having two hydroxyl groups reactive to polyisocyanates and 90 to 10% by weight of further polymer bound constituents, f) from 0 to 50 parts by weight of a catalyst component (K), g) from 0 to 50 parts by weight of a solvent component (L), and h) from 0 to 50 parts by weight of a formulation component (F); wherein the fluoromodified admixture has a mean isocyanate functionality <
3, a content of aliphatic or (cyclo)aliphatic isocyanate groups of 0.1 to 10% by weight, a content of at least one of urethane groups or urea groups of 2.5 to 25% by weight, a polymer bound fluorine content of 0.5 to 60% by weight and a content of ethylene oxide monomers bound within polyether chains of 30 to 90% by weight. - View Dependent Claims (29, 30, 31, 32, 33, 34, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 49, 50, 51, 53, 54)
- (CF2)x—
-
35. The admixture as claimed in 38, wherein solvent component (L) comprises at least one plasticizer selected from the group consisting of dialkyl adipates, dialkyl phthalates, cyclic alkylenecarbonates, biodiesel and rapeseed oil methyl ester.
-
52. The composition of claim 48, further comprising at least one of a filler, a pigment, a colorant or a nanoparticle.
Specification