公开(公告)号：US4202929A

公开(公告)日：1980-05-13

申请号：US949316

申请日：1978-10-06

申请人： Armand de Montigny ,  Hans Toepsch ,  Werner Buchner

发明人： Armand de Montigny ,  Hans Toepsch ,  Werner Buchner

IPC分类号： C08J7/04 ,  B05D5/08 ,  B05D7/04 ,  B05D7/24 ,  B32B27/00 ,  C08G18/61 ,  C08G77/388 ,  C08L83/04 ,  D21H19/32 ,  C08G47/02 ,  B32B9/04

CPC分类号： D21H19/32 ,  C08G18/61 ,  C08G77/388 ,  C08L83/04 ,  C08G77/16 ,  C08G77/24 ,  Y10S528/901 ,  Y10T428/31663

摘要： In the production of non-adherent coated paper substrate by applying to the substrate a solvent-containing mixture comprising (A) an .alpha.,.omega.-polyorganosiloxanediol, (B) an organosiloxane containing Si-H groups, (C) an alkyl- or alkenyl-triacetoxysiloxane, (D) an organic isocyanate with more than two isocyanate radicals and (E) a hardening catalyst, and then heating the substrate to harden the coating, the improvement which comprises including in the mixture applied to the substrate a reaction product (F) of a chloromethylpolymethylsiloxane of the formulaClCH.sub.2 (CH.sub.3).sub.2 Si[OSi(CH.sub.3)CH.sub.2 Cl].sub.n OSi(CH.sub.3).sub.2 Clwherein n is from 2 - about 200, with at most an equivalent molar amount of a primary alkyl, alkenyl or cycloalkyl amine with about 4-18 carbon atoms, e.g. butylamine, hexylamine, cyclohexylamine, 2-ethylhexylamine and allylamine. The coating hardens in a very short time in a drying oven but at normal temperatures the mass has a relatively long pot life.

摘要翻译： 在通过向基材施加含有（A）α，ω-聚有机硅氧烷二醇，（B）含Si-H基的有机硅氧烷，（C）烷基 - 或烯基 （D）具有多于两个异氰酸酯基团的有机异氰酸酯和（E）硬化催化剂，然后加热基材以使涂层硬化，其改进包括在施加到基材上的混合物中加入反应产物（F ）式ClCH 2（CH 3）2 Si [OSi（CH 3）CH 2 Cl] nOSi（CH 3）2 Cl的氯甲基聚甲基硅氧烷，其中n为2-约200，最多等摩尔量的伯烷基，烯基或环烷基胺与 约4-18个碳原子，例如 丁胺，己胺，环己胺，2-乙基己基胺和烯丙胺。 涂层在干燥炉中在很短的时间内硬化，但在常温下，使用寿命较长。

公开(公告)号：US4366286A

公开(公告)日：1982-12-28

申请号：US204680

申请日：1980-11-05

申请人： Hans Friemann ,  Hans-Heinrich Moretto ,  Heinrich Alberts ,  Armand de Montigny ,  Hans Toepsch

发明人： Hans Friemann ,  Hans-Heinrich Moretto ,  Heinrich Alberts ,  Armand de Montigny ,  Hans Toepsch

IPC分类号： C09J7/02 ,  C08F283/00 ,  C08L51/00 ,  C08L51/02 ,  C08L83/00 ,  C08L83/04 ,  C09D183/04 ,  D21H19/32 ,  C08L51/08

CPC分类号： D21H19/32 ,  C08L83/04 ,  C08G77/16 ,  C08G77/20 ,  C08G77/26 ,  C08G77/42 ,  C08G77/46 ,  C08G77/70

摘要： In a sheet coated on both surfaces with non-stick coatings, one of the coatings being more non-stick than the other, the improvement which comprises employing as the lesser non-stick coating a composition according to claim 1 by weight consisting essentially of(A) about 10 parts of a polyorganosiloxane with hydroxyl end groups and with a viscosity of 10.sup.2 to 5.10.sup.4 Pas,(B) 0.5-5 parts of at least one cross-linking agent of the formulaRSiX.sub.3whereinX is a hydrolyzable group andR is an alkyl, alkenyl, aryl or aminoalkyl group with 1-12 C atoms,(C) 0.1-2 parts of an organic tin compound as the catalyst and(D) 100-500 parts by weight of an organic solvent, the improvement which comprises additionally including, and(E) 0.1-20 parts of a graft copolymer comprising(i) 25-75% of an essentially linear polyorganosiloxane with hydroxyl end groups and with a viscosity of 100 to 500,000 mPas and(ii) 10-70% of at least one organic polymer with a molecular weight of 500 to 100,000, linked to (i) via bridges formed on polymerization of(iii) 10-60% of one or more monomers containing at least one aliphatic double bond.

摘要翻译： 在涂覆有具有不粘涂层的两个表面上的片材中，一个涂层比另一个涂层更粘不粘，其改进包括使用根据权利要求1所述的组合物作为较小不粘涂层，该组合物基本上由（ A）约10份具有羟基端基的聚有机硅氧烷，粘度为102〜5.104Pa·s，（B）0.5-5份至少一种式RSiX 3的交联剂，其中X为可水解基团，R为 具有1-12个碳原子的烷基，烯基，芳基或氨基烷基，（C）0.1-2份作为催化剂的有机锡化合物和（D）100-500重量份的有机溶剂，其改进包括 另外包括和（E）0.1-20份的接枝共聚物，其包括（i）25-75％的具有羟基端基的基本上线性的聚有机硅氧烷和粘度为100-500,000mPas，和（ii）10-70％ 至少一种分子量为500至100,000的有机聚合物，与（ i）通过在（iii）10-60％的一种或多种含有至少一个脂族双键的单体的聚合上形成的桥。

公开(公告)号：US4251596A

公开(公告)日：1981-02-17

申请号：US948935

申请日：1978-10-06

申请人： Armand de Montigny ,  Hans Toepsch

发明人： Armand de Montigny ,  Hans Toepsch

IPC分类号： B05D5/08 ,  B05D7/02 ,  B05D7/24 ,  C08G77/388 ,  C08L83/04 ,  D21H19/32 ,  B32B9/04

CPC分类号： D21H19/32 ,  C08G77/388 ,  C08L83/04 ,  C08G77/12 ,  C08G77/16 ,  C08G77/24 ,  Y10T428/31663

摘要： In the production of non-adherent coated paper substrate by applying to the substrate a solvent-containing mixture comprising (A) 100 parts by weight of an .alpha.,.omega.-dihydroxypolydimethylsiloxane having a viscosity between 10.sup.5 and 5. 10.sup.7 cP at 20.degree. C., (B) about 1 to 20 parts by weight of a polyorganosiloxane which is terminally blocked with trimethylsiloxy groups, contains Si-bonded hydrogen and has about 10 to 40 CH.sub.3 Si(H)O units, and (C) about 1 to 20 parts by weight of a heavy metal carboxylate or dialkyl-tin carboxylate, and then heating the substrate to harden the coating, the improvement which comprises including in the mixture applied to the substrate (D) about 0.5 to 10 parts by weight of disilamorpholinesiloxane which is obtained by reacting a chloromethylpolymethylsiloxane of the formulaClCH.sub.2 (CH.sub.3)SiO[Si(CH.sub.3)CH.sub.2 ClO].sub.n Si(CH.sub.3).sub.2 CH.sub.2 Clin which n denotes a value between 2 and 200, with at most an equivalent amount of a primary C.sub.4-18 alkyl or alkenyl or cycloalkylamine, e.g. butylamine, hexylamine, cyclohexylamine, 2-ethylhexylamine and allylamine. The coating hardens in a very short time in a drying oven but at normal temperatures the mass has a relatively long pot life.

摘要翻译： 在通过向基材施加含有（A）100重量份在20℃下粘度为105至5×10 7 cP的α，ω-二羟基聚二甲基硅氧烷的含溶剂的混合物来生产非粘附的涂布纸基材。 ，（B）约1至20重量份用三甲基甲硅烷氧基封端的聚有机硅氧烷含有Si键合的氢，并具有约10至40个CH 3 Si（H）O单元，和（C）约1至20份 重金属羧酸盐或二烷基锡羧酸盐的重量，然后加热基材以使涂层硬化，其改进包括在施加到基材（D）的混合物中包含约0.5至10重量份的二硅氧烷，其由 使式ClCH 2（CH 3）SiO [Si（CH 3）CH 2 ClO] n Si（CH 3）2 CH 2 Cl的氯甲基聚甲基硅氧烷，其中n表示2和200之间的值，最多等同量的伯C4-18烷基或烯基或 环烷基胺，例如 丁胺，己胺，环己胺，2-乙基己胺和烯丙胺。 涂层在干燥炉中在很短的时间内硬化，但在常温下，使用寿命较长。

公开(公告)号：US4043977A

公开(公告)日：1977-08-23

申请号：US670583

申请日：1976-03-25

申请人： Armand deMontigny ,  Kurt-Wilhelm Eichenhofer ,  Hans Toepsch ,  Reinhard Schliebs

发明人： Armand deMontigny ,  Kurt-Wilhelm Eichenhofer ,  Hans Toepsch ,  Reinhard Schliebs

IPC分类号： C08L83/00 ,  C08G77/04 ,  C08K5/34 ,  C08L83/04 ,  C08L83/07 ,  C09D183/04 ,  D06M15/643 ,  D21H19/00 ,  D21H19/32

CPC分类号： D21H19/32 ,  C08G77/045 ,  C08L83/04 ,  D06M15/6436 ,  C08G77/12 ,  C08G77/20 ,  C08G77/70 ,  Y10T428/31663

摘要： A composition for coating paper, films and fiber materials, comprisingA. 4 parts by weight of a linear polyorganosiloxane with ends stopped by vinyl groups and having a viscosity of up to about 500 cP (20.degree. C) andB. about 0.5 to 1.5 parts by weight of a crosslinking agent containing Si-vinyl units and SiH units and comprising molecules with a maximum of about 10 Si atoms bonded to one another via oxygen, and wherein the two reactive groups are present in adjacent positions in one and the same molecule and the remaining valencies of the Si atom are saturated by methyl groups and the SiH groups are present in a ratio of about 1:1 to 2.5:1 to the total amount of all Si-vinyl units present in the composition,C. a platinum metal complex, the amount of metal being up to about 0.01 part by weight -- based on 100 parts by weight of total composition, andD. a diaziridine, the amount of diaziridine being about 75 to 250 times the weight of metal.The compositon has a viscosity of about 150 cP -- the increase of the initial viscosity over a period to of at least 24 hours being less than 1 cP -- easy application from existing equipment.The present invention relates to a coating agent based on polyorganosiloxanes which is suitable for the manufacture on non-stick films or coatings on paper, films, fabric tapes and similar materials, without the use of solvents.The application of non-stick polysiloxane coatings from water or organic solvents onto paper or similar materials has in itself been known for a long time (compare, for example, Noll, Chemie und Technologie der Silicone (Chemistry and Technology of the Silicones), 2nd edition, 1968, Verlag Chemie, Weinheim, page 520) and is extensively carried out in industry. The apparatuses suitable for the application of such coatings are in general designed to apply a coating material which contains solvent and are therefore adjusted to deal with viscosities of less than 150 cP or even of less than 100 cP. Such low viscosities have the advantage that they can be adjusted very precisely by means of the solvent. In addition, dilute solutions can be processed better, and the substrate is generally wetted better. In spite of these advantages, such coating systems containing solvents still suffer from considerable shortcomings. The main disadvantage is that about 92-97% of the mixture applied must again be removed. This requires high expenditure of energy. Furthermore, for reasons of protection of the environment and reasons of profitability, it is necessary either to recover the solvent removed in this way or, if recovery is not possible, to destroy the solvent, for example by combustion. However, this requires considerable expenditure on energy or apparatuses in every case.For these reasons there has been a constantly increasing demand for a coating without solvents, but of course it is a prerequisite that with a solvent-free coating system the advantage must not be achieved at the expense of a series of other disadvantages. Admittedly, some processes have already been disclosed (compare, for example, DT-OS (German Published Specification) No. 2,210,380 and DT-OS (German Published Specification No.) 2,321,879), in which the attempt to manage without solvents has been made. However, these systems in every case still suffer from a series of disadvantages so that they are unable satisfactorily to fulfil the demands made of them. Above all, it is in respect of their viscosity behavior -- such systems are required to have a high degree of constancy of the viscosity -- that the previously known systems have only been partially satisfactory.A further aspect of the viscosity problem which also still awaits a satisfactory solution in spite of the previously known processes and compositions is the initial viscosity.As is known to those skilled in the art, a mixture of a siloxane polymer with a crosslinking agent cannot directly be brought to a lower viscosity by shortening the siloxane chains of the polymer. Short-chain rubber molecules give a hard, crumbly film of low suppleness and poor mechanical properties. Applied to paper coating, this means that the film is not abrasion-resistant, and the inadequate abrasion resistance does not necessarily relate to the breaking of the bond between the substrate and the film but to the film itself breaking. Hence it is not surprising that all examples in the known publications relate to polymers of which the viscosity is in part many times higher than 150 cP.Accordingly, it is the object of the present invention to provide a coating system or coating process which makes it posible to achieve, by means of the applicator units of the state of the art, thin, commercially acceptable films of which the uniformity and mechanical properties are such as to give constant release properties and migration properties which meet practical requirements. In detail, this means that such a process must resort to compositions which in spite of the low initial viscosities are able to give films which withstand mechanical strain and repel adhesives, while the original viscosity must remain constant for at least 24 hours under conditions resembling those encountered in practice.This object is realized in accordance with the present invention pursuant to which there is provided a composition for coating paper, films and fiber materials, comprisinga. 4 parts by weight of a linear polyorganosiloxane with ends stopped by vinyl groups and having a viscosity of up to about 500 cP (20.degree. C),b. about 0.5 to 1.5 parts by weight of a crosslinking agent containing Si-vinyl units and SiH units, comprising molecules with a maximum of about 10 Si atoms bonded to one another via oxygen, and wherein the two reactive groups are present in adjacent positions in one and the same molecule and the remaining valencies of the Si atom are saturated by methyl groups and the SiH groups are present in a ratio of 2.5:1 to the total amount of all Si-vinyl units present in the composition,c. a platinum metal complex, the amount of metal being up to about 0.01 part by weight - based on 100 parts by weight of the composition, andd. a diaziridine, the amount of diaziridine being about 75 to 250 times the weight of metal.Accordingly, it was possible to achieve the present object by making 4 parts by polyorganosiloxane with ends stopped by vinyl groups and having a viscosity of at most 500 cP/20.degree. C with 0.5 to 1.5 parts of a crosslinking agent carrying Si-vinyl groups and SiH groups; the molecular size of the crosslinking agent should not exceed 10 Si atoms which are bonded via oxygen and of which the remaining valencies are saturated by methyl groups, where they are not occupied by the above reactive groups, and the viscosity of the polyorganosiloxane is so chosen that it is more than 50 cP and that the viscosity of the total mixture does not exceed 150 cP. The SiH:Si-vinyl ratio in the mixture may vary between the ratios of 1:1 and 2.5:1. The crosslinking agent used is such that it consists of one type of molecule and carries, in addition to SiH groups, a sufficient number of Si-vinyl groups that the above conditional ratios are observed.While the linear polyorganosiloxane has a viscosity which may be as high as 500 cP/20.degree. C, it is blended with such an amount of crosslinking agent that the overall composition has a viscosity from about 50 to 150 cP/20.degree. C.In the sense of the invention, polyorganosiloxanes with ends stopped by vinyl groups are polydiorganosiloxanes which terminate in CH.sub.2 .dbd.CH-Si(CH.sub.3).sub.2 O.sub.1/2 units and of which the organo groups consist to the extent of at least about 70 % of methyl groups, the remainder optionally consisting of higher alkyl groups, preferably containing up to about 6 carbon atoms, or phenyl groups. The viscosity of these polymers, which can be prepared easily according to the state of the art, should not be less than about 50 cP. Now the upper limit of viscosity is determined by the total viscosity of the mixture, which should be less than 150 cP; accordingly, the polymer viscosity should not significantly exceed a value of 500 cP.The crosslinking agent consists, for example, of a co-hydrolysate which contains both vinyl-Si and H-Si groups in the same molecule. The following compounds would be typical representatives of this category of crosslinking agent, for example with the chain length remaining the same:(CH.sub.3).sub.3 SiOX.sub.n Y.sub.n' Si(CH.sub.3).sub.3(ch.sub.3).sub.3 siOX.sub.n Y.sub.n' Si(CH.sub.3).sub.2 H(ch.sub.3).sub.3 siOX.sub.n Y.sub.n' Si(CH.sub.3).sub.2 CH.dbd.CH.sub.2ch.sub.2 .dbd.ch(ch.sub.3).sub.2 siOX.sub.n Y.sub.n' Si(CH.sub.3).sub.2 CH.dbd.CH.sub.2ch.sub.2 .dbd.ch(ch.sub.3).sub.2 ox.sub.n Y.sub.n' Si(CH.sub.3).sub.2 HandHSi(CH.sub.3).sub.2 OX.sub.n Y.sub.n' Si(CH.sub.3).sub.2 Hwherein ##STR1## n+n' is at most about 8.These compounds are readily available and are obtained in high yields by co-hydrolysis according to the state of the art. In principle, the crosslinking agent would be allowed to possess more than 10 Si atoms bonded via O without the crosslinking reaction or the properties of the film being impaired. However, it is to be borne in mind that this would increase the viscosity of the crosslinking agent and hence also the viscosity of the mixture. In order to counteract this effect brought about by the crosslinking agent the polymer would have to be made correspondingly short. In the viscosity ranges concerned, which are in any case already low, this would not be of advantage since an over-drastic shortening of the chains would be at the expense of the mechanical properties. It has been found that the film which results from the mixture described above adheres well to its substrate, is abrasion-resistant and exhibits perfect release properties and migration properties.It is a further characteristic of the present invention that Pt catalyst known from the literature, such as the reaction product of H.sub.2 PtCl.sub.6 with octanol (Lamoreaux catalyst) or Pt compounds such as have been disclosed, for example, in DT-OS (German Published Specification No.) 2,251,297 (the disclosure of which is incorporated herein by reference) are deactivated by bringing them into contact, at room temperature, with a diaziridine of the formula ##STR2## whereinR.sub.1 and R.sub.2 represent a radical which contains up to6 C atoms (for example an alkyl radical) and whereinR.sub.1 + R.sub.2 can together form a ring system. Examples of both liquid and solid diaziridines which can be used for this purpose are dimethyldiaziridine, methylethyldiaziridine, diethyldiaziridine, methylisopropyldiaziridine, methylpropyldiaziridine, dipropyldiaziridine, pentamethylenediaziridine and hexamethylenediaziridine. The reaction is best carried out "in situ", that is to say a sufficient amount of diaziridine is added to the polymer with ends stopped by vinyl groups and the platinum catalyst is then added. It has been found that up to about 100, preferably about 10 to 12 ppm, of Pt, relative to the total amount, suffice for catalysis so that reliable curing is achieved at temperatures between 120.degree. and 150.degree. C.As can furthermore be shown in the examples which follow, good deactivation of the catalyst is achieved if the amount of diaziridine added is up to about 250 times the amount of Pt. The amount of diaziridine should not be significantly less than 75 times the amount of the Pt catalyst since in that case an increase in viscosity of 5 cP is already found over a period of 24 hours. If the diaziridine content is well matched to the amount of Pt catalyst, pot lives of over 120 hours can be achieved, without difficulties, under conditions resembling practical requirements. A main advantage of the low viscosity is that it permits the application of thin, economical films.At this point it should further be mentioned that the delaying action of the reaction products of platinum complexes with diaziridines need not be restricted to systems of low viscosity such as those described here.

摘要翻译： 一种用于涂布纸，薄膜和纤维材料的组合物，包括A. 4通过乙烯基团停止并具有高达约500 CP（20℃）和B的粘度的直链多聚硅氧烷的重量的组分。约0.5至1.5 包含Si-乙烯基单元和SiH单元并含有最多约10个Si原子的分子通过氧彼此键合的交联剂的重量份数，并且其中两个反应性基团存在于同一分子中的相邻位置 并且Si原子的剩余价数被甲基饱和，并且SiH基以与组合物中存在的全部Si-乙烯基单元的总量的比例为约1:1至2.5:1存在.C.A铂 金属复合物，金属含量高达0.01重量份 - 以100重量份的总组成，D。DIAZIRIDINE，DIAZIRIDINE的量约为75至250次金属重量。