Organic pigments
Abstract
Disclosed are novel organic pigments adapted particularly for use as fillers for paper. The organic pigments are finely divided particles obtained by graft copolymerizing an ethylenically unsaturated monomer, such as styrene, onto a watersoluble cationic prepolymer in an aqueous solution and in the presence of a free-radical polymerization initiator.

Term
No projected expiry on record.
- Priority
- Filed
- Granted
- Today
9 claims: 3 independent, 6 dependent
- 1CLAIMS PATENTKRAV 1. 1. Latex av vattenolösliga ymppolymerpartiklar med en halt av fast substans av 15 - 60 %, vilka partiklar består av en friradikalkatalyserad ymppolymerisationsprodukt av (1) minst en eteniskt omättad monomer ooh (2) en vattenlöslig Latex of water-insoluble graft polymer particles having a solids content of 15 - 60%, which particles consist of a free radical-catalyzed graft polymerization product of (1) at least one ethylenically unsaturated monomer and (2) a water-soluble 5 cationic prepolymer having a RSV, reduced specific viscosity, of 0.1 - 2.5 (1 M NaCl, 1%, 25 ° C), wherein the prepolymer portion of the graft polymer particle is present on the surface of the particles, characterized in that the monomer (1) is monomer with the formula c = ch2(Y)n wherein R is hydrogen or methyl, Y is methyl or chlorine, and n is 0, 1, 2 or 3, and the prepolymer (2) is the addition polymerization product of (i) 5 - 100 mole percent of at least one cationic monomer selected from that of (I) 5 katjonisk förpolymer med en RSV, reducerad specifik viskositet, av 0,1 - 2,5 (IM NaCl, 1 %, 25°C), varvid förpolymerdelen av ymppolymerpartikeln finns närvarande på partiklarnas yta, kännetecknad av att monomeren (1) är monomer med formeln c=ch2(Y)n vari R betecknar väte eller metyl, Y betecknar metyl eller klor, och n är 0, 1, 2 eller 3, och förpolymeren (2) är additionspolymerisationsprodukten av (i) 5 - 100 molprocent av minst en katjonisk monomer, som är vald ur den av (I) CH2= CCOOC2hrs4N --- R2 CH2=CCOOC2H4N---R2 25 is hydrogen or methyl, R2 represents alkyl with 25 vari R^ betecknar väte eller metyl, R2 betecknar alkyl med 1-4 kolatomer, Rg betecknar väte, alkyl med 1-4 kolatomer, Represents hydrogen, alkyl of 1-4 carbon atoms, OH OH -CH2CHCH2y wherein Y represents hydroxyl or halogen, and and X represents an anion, -ch2chch2y vari Y betecknar hydroxyl eller halogen, och och X betecknar en anjon, 7910339 (II) wherein R 2, R 9 and X have the meaning given under formula (I), (III) 7910339(II) vari R2, Rg och X har den under formeln (I) angiven betydelsen, (III) (I) angivna beunder formeln (I) (I) given the formula (I) X har den vari Rg och angivna betydelsen, r2 fl +Z2 X is the one in which R 9 and the meaning given, r2 al +Z2 CH2=CC0NH(CH2)nN —R2R3 CH2CC0NH = (CH2)nN —R2R3 X X 7910339-6 vari R^, R?, Rg och X- har den under formeln (I) angivna betydelsen och n är ett heltal 1, 2 eller 3 och (VI) R1 7910339-6 wherein R 1, R?, Rg and X- has the meaning given by formula (I) and n is an integer 1, 2 or 3 and (VI) R1 I1 +/ IN1 +/ CH2= CCOOCH2CHCH2N ^ - r2 CH2=CCOOCH2CHCH2N^— r2 OH ^ R3 wherein R1? R2, Rg and X- has the meaning given by formula (I), consisting of the group and (ii) 95-0 mole percent of at least one ethylenically unsaturated nonionic monomer with amide functionality, the amount of prepolymer (2) used in preparing the graft polymer particles being 1 to 25 parts by weight for every 100 parts by weight of monomer used (1). OH ^R3 vari R1? R2, Rg och X- har den under formeln (I) angivna betydelsen, bestående gruppen och (ii) 95-0 molprocent av minst en eteniskt omättad nonjonisk monomer med amidfunktionalitet, varvid mängden förpolymer (2), som användes vid framställning av ymppolymerpartiklarna, är 1 - 25 viktdelar för varje 100 viktdelar av använd monomer (1).
- 8Förfarande för framställning av en latex av ymppolymerpartiklar, vilket förfarande innefattar ymppolymerisering i vattenhaltigt medium och i närvaro av en vattenlöslig friradikalinitiator av (1) minst en eteniskt omättad monomer och (2) en vattenlöslig katjonisk förpolymer med en RSV av 0,1 - 2,5 (IM NaCl, 1 %, 25°C), kännetecknat av att monomeren (1) är en monomer med formeln Eighth A process for preparing a latex of graft polymer particles, which process comprises graft polymerization in aqueous medium and in the presence of a water-soluble free-radical initiator of (1) at least one ethylenically unsaturated monomer and (2) a water-soluble cationic prepolymer having an RSV of 0.1-2. (1%, 25 ° C), characterized in that the monomer (1) is a monomer of the formula C = CH2 (Y) wherein R is hydrogen or methyl, Y is methyl or chlorine, and n is 0, 1, 2 or 3, and the prepolymer (2) is the addition polymerization product of (i) 5 to 100 mole percent of at least one cationic monomer which is selected from the by C=CH2 (Y) vari R betecknar väte eller metyl, Y betecknar metyl eller klor, och n är 0, 1, 2 eller 3, och förpolymeren (2) är additionspolymerisationsprodukten av (i) 5 - 100 molprocent av minst en katjonisk monomer, som är vald ur den av 7910339-6 Ri ^2 7910339-6 Ri ^2 I1 + / IN1 + / CH2= CCOOC2hrs1|N;—— R.2R3 x ~ wherein R ^ represents hydrogen or methyl, R.2 represents alkyl of 1-4 carbon atoms, Rg represents hydrogen, alkyl of 1-4 carbon atoms. CH2=CCOOC2H1|N;—- R2R3 x~ vari R^ betecknar väte eller metyl, R2 betecknar alkyl med 1-4 kolatomer, Rg betecknar väte, alkyl med 1-4 kolatomer. OH OH -CH26hch2y -ch26hch2y vari R<2 , wherein R <2 , Rg and X have the meaning given by formula (I), Rg och X har den under formeln (I) angivna betydelsen, 7910339-6 (III) 7910339-6 (III) N + wherein R2, R3 and X has the formula (I) specified in formula (I) N+ vari R2, R3 tydelsen, och X har den under formeln (I) angivna be(IV) H · HRS · I IN C = CH2 wherein Rg and X are as defined in formula (I), C=CH2 vari Rg och X har den under formeln (I) angivna betydelsen, I1+ X (V) CH„=CCONH(CH„)N -— R_ X IN1+ X (V) CH + = CCONH (CH +) N -— R_ X Z z nl R3 wherein R ^, R.2, Rg and X are as defined in formula (I), and n is an integer of 1, 2 or 3 and Z z nl R3 vari R^, R2, Rg och X har den under formeln (I) angivna betydelsen, och n är ett heltal 1, 2 eller 3 och R-R l1+ RR l1+ CH2= CCOOCH2j) HCH2N:-— R.2 CH2=CCOOCH2j)HCH2N:-— R2 0H \ r3 (WE) 0H \r3 (VI) 7910339-6 vari R., R„, R„ och X~ har den under formeln (I) angivna J. L 0 betydelsen, bestående gruppen, och (ii) 95-0 molprocent av minst en eteniskt omättad nonjonisk monomer med amidfunktionalitet, varvid mängden förpolymer (2), som användes 5 vid framställning av ymppolymerpartiklarna, är 1 - 25 viktdelar för varje 100 viktdelar använd monomer (1). 7910339-6 wherein R 1, R 2, R 2 and X 1 have the meaning of the formula (I) represented by the group consisting of the group, and (ii) 95-0 mole percent of at least one ethylenically unsaturated nonionic monomer having amide functionality, wherein the amount of prepolymer (2) used in preparing the graft polymer particles is 1 to 25 parts by weight for every 100 parts by weight of monomer used (1).
- 9Användning av latexen enligt något av patentkraven 9th Use of the latex according to any of the claims 1-7 in the preparation of paper using an opacifier to obtain opacity in the final paper product, either by coating or by adding to the pulp, characterized in that at least part of the opacifier is used the latex of the water-insoluble graft polymer particles. 1-7 vid framställning av papper, varvid ett opacitetsmedel användes för erhållande av opacitet i den slutliga 10 pappersprodukten, antingen med hjälp av en bestrykning eller med hjälp av tillsats till pappersmassan, kännetec'k n a d av att som minst en del av opacitetsmedlet användes latexen av de vattenolösliga ymppolymerpartiklarna. 7910339-6 7910339-6 SAMMANDRAG SUMMARY The invention relates to the latex of water-insoluble graft polymer particles, a process for preparing this and its use as a filler for paper. The water-insoluble graft polymer particles are obtained by graft polymerization of an ethylenically unsaturated monomer, e.g. styrene, on a water-soluble cationic prepolymer, which is the addition product of 5 - 100 mol% of a cationic monomer and 95-0 mol% of an ethylenically unsaturated nonionic monomer with amide functionality, in aqueous solution and in the presence of a water-soluble initiator for free radical polymerization. The prepolymer portion of the graft polymer particle is present on the surface of the particles. The latex has a content of 15 - 60% solids. Uppfinningen avser latex av vattenolösliga ymppolymerpartiklar, ett förfarande för framställning av denna ooh användning av denna som fyllmedel för papper. De vattenolösliga ymppolymerpartiklarna är erhållna genom ymppolymerisering av en etenisk omättad monomer, t.ex. styren, på en vattenlöslig katjonisk förpolymer, som är additionsprodukten av 5 - 100 molprocent av en katjonisk monomer och 95-0 molprocent av en eteniskt omättad nonjonisk monomer med amidfunktionalitet, i vattenlösning och i närvaro av en vattenlöslig initiator för friradikalpolymerisation. Förpolymerdelen av ymppolymerpartikeln finns närvarande på partiklarnas yta. Latexen har en halt av 15 - 60 % fast substans. The invention also relates to a process for preparing this latex by graft polymerization in aqueous medium and in the presence of a water-soluble free radical initiator of an ethylenically unsaturated monomer and a water-soluble cationic prepolymer, and to use the resulting latex in the preparation of paper as an opacifier. Uppfinningen avser även ett förfarande för framställning av denna latex genom ymppolymerisation i vattenhaltigt medium och i närvaro av en vattenlöslig friradikalinitiator av en eteniskt omättad monomer och en vattenlöslig katjonisk förpolymer, samt användning av den erhållna latexen vid framställning av papper som opacitetsmedel.
Independent claims3
820 paragraphs in 48 sections, as filed
(54) Title: Latex of water-insoluble graft polymer particles, process for its preparation and use as filler in paper (56) Published publications: EP A1 000 922 D21H 3/40, DE A1 2,343,261 D21H 3/38 DE A1 2,500 494 C08F 257/02, US A 3 639 208 162-168, US A 4 056 432 162-168 US A 4 152 200 162-168 NA (57) Summary:
The invention relates to the latex of water-insoluble graft polymer particles, a process for making them and using them as paper fillers. The water-insoluble graft polymer particles are obtained by graft polymerization of an ethylenically unsaturated monomer, e.g. styrene, on a water-soluble cationic prepolymer, which is the addition product of 5 - 100 mol% of a cationic monomer and 95-0 mol% of an ethylenically unsaturated nonionic monomer with amide functionality, in aqueous solution and in the presence of a water-soluble initiator for free radical polymerization. The prepolymer portion of the graft polymer particle is present on the surface of the particles. The latex has a content of 15 - 60% solids.
The invention also relates to a process for preparing this latex by graft polymerization in aqueous medium and in the presence of a water-soluble free radical initiator of an ethylenically unsaturated monomer and a water-soluble cationic prepolymer, and to use the resulting latex in the preparation of paper as an opacifier.
7910339-6
The present invention relates to novel organic pigments intended specifically for use as fillers in paper.
Paper often includes mineral fillers, e.g. clay, calcium carbonate or titanium dioxide. A mineral filler acts to increase the opacity of the paper and prevent it from being visible; low opacity means that the text from the underlying page shines through in e.g. books, magazines and newspapers. Although mineral fillers do this task very well with relatively low costs, they also have disadvantages. They greatly reduce the strength of the paper. This may cause problems in later use, but of greater importance is that low paper strength may make it necessary to operate the paper machine at a lower speed. Another disadvantage is that the mineral fillers have relatively high densities (2.5 - 4.0) and thus increase the weight of the paper. This is becoming an increasing problem due to the rising costs of sending printed matter, e.g. magazines, with the post lead to the demand for lightweight paper. Thus, in the paper industry, there is a need for a low density agent for paper, which means that the paper is opaque and does not adversely affect the strength of the paper.
It is known to use latex particles as light fillers for paper. Polystyrene latexes are commercially available for this application. Like mineral fillers, these polystyrene latexes consist of anionic particles, which require cationic retention aids for good retention on anionic pulp fibers. In addition, polystyrene latex fillers reduce the strength of paper containing them, although this reduction is lower than for mineral fillers.
Small particles of urea-formaldehyde resin have been used as fillers in paper. These particles are said to be of minor weight and, when used as a filler in paper, lead to better opacity, lightness, evenness and bulk of the paper; however, they have a negative effect on the paper strength, although this effect is stated to be less than that of mineral fillers.
7910339-6
U.S. Patent No. 3,824,144 discloses microcapsules having a solid polymeric casing and a solid non-sticky polymer core grafted onto the polymeric casing. The microcapsules may be applied to cellulosic substrates or incorporated into such substrates and then melted to obtain cellulosic substrates with a polymeric film bonded therewith having greater strength. From this patent, column 3, lines 29 - 40, it can be seen that polymer-containing microcapsules can be prepared with an average particle diameter of between about 0.5 and about 1.0 µm. The patent document also shows that the particles are capable of producing high opacity in the coatings of different substrates. It is also stated that microcapsules can be mixed with cellulose fibers and formed into a web of these fibers, and that the polymer capsules act as non-abrasive, opacity-inducing agents and impart high opacity to the formed cellulose substrate.
It is an object of the present invention to provide organic pigments which can be used as fillers for low weight paper and which produce opacity, lightness and evenness without adversely affecting the strength of the paper. Another object of the present invention is to provide organic pigments which are retained in the papermaking, i.e., the organic pigments are well retained by the pulp fibers without the use of conventional retention aids.
The present invention relates to a latex of water-insoluble graft polymer particles suitable for use as organic pigments, particularly as filler in paper, which particles consist of a free radical catalyzed graft polymerization product of (1) at least one ethylenically unsaturated monomer and (2) a water-soluble cationic polymer. an RSV (reduced specific viscosity) of 0.1 to 2.5 (1M NaCl, 1%, 25 ° C), the prepolymer portion of the graft polymer particle being present on the surface of the particles. Characteristic of the latex is that the monomer (1) is a momomer of the formula
7910339-6
<img file="SE435845B_D0001.tif" />
wherein R is hydrogen or methyl, Y is methyl or chlorine, and n is 0, 1, 2 or 3 and the prepolymer (2) is the addition polymerization product of (i) 5 to 100 mole percent of at least one cationic monomer selected in the by (I)
<img file="SE435845B_D0002.tif" />
CEL = CCOOC "HN
2 4
<img file="SE435845B_D0003.tif" />
wherein hydrogen or methyl represents R<sub>2</sub> represents alkyl with
Represents hydrogen, alkyl of 1-4 carbon atoms,
OH
I -CH<sub>2</sub>CHCH<sub>2</sub>Y, wherein Y represents hydroxyl or halogen, or
O / | -CH<sub>2</sub>CHCH<sub>2</sub> , and X is an anion, (II) HC
<img file="SE435845B_D0004.tif" />
<img file="SE435845B_D0005.tif" />
<img file="SE435845B_D0006.tif" />
X wherein R<sub>2</sub>, R ^ <sup>oc</sup>hrs
7910339-6
X has the meaning given by formula (I), (III)
<img file="SE435845B_D0007.tif" />
wherein R<sub>2</sub>, R 2 and X have the meaning given under formula (I), (IV)
<img file="SE435845B_D0008.tif" />
wherein R 2 and X are as defined in formula (I),
<img file="SE435845B_D0009.tif" />
(V) ch<sub>2</sub>Cconh = (CH<sub>2</sub>
<img file="SE435845B_D0010.tif" />
wherein R ^, R.<sub>2</sub>, R 2 and X have the meaning given by formula (I), and n is an integer of 1,2 or 3 and
RR
I (VI) CH<sub>9</sub>= CCOOCH<sub>9</sub>CHCH<sub>9</sub>NO
212 v 2
OH <sup>X</sup> Rj wherein R ^, R.<sub>2</sub>, R 2 and X are as defined in formula (I), consisting of the group and (ii) 95 to 0 mole percent of at least one ethylenically unsaturated nonionic monomer having amide functionality,
7910339-6 wherein the amount of prepolymer (2) used in the preparation of the graft polymer particles is 1 to 25 parts by weight per 100 parts by weight of monomer used (1). Substantially the entire cationic prepolymer portion of the graft copolymer particles resides on the surface of the obtained particles.
When these graft polymer particles are suspended in water in the presence of cellulose pulp fibers, they are attracted to the anionic sites on the surface of the fibers and adhere to the pulp fibers. During preparation of paper by dewatering a slurry of pulp fibers, the cationic particles remain on the pulp fibers and thus remain substantially in the paper.
Graft polymer particles prepared using water-soluble prepolymers containing optimum cationic functionality are retained during the production of paper, i.e. when these particles are slurried together with pulp fibers prior to sheet making, the particles are strongly adhered to the anionic pulp fibers and a very small amount of wetting goes away. papermaking. Thus, no retention aid is required to retain the particles on the pulp fibers. However, known retention aids can be used in papermaking if desired. In addition, paper containing such graft polymer particles has strength properties which are usually equal to or in better blend than paper of the same weight, which does not contain filler. Paper containing mineral pigments, e.g. clay or titanium dioxide, has significantly lower strength properties than equivalent paper without filler.
The monomers used to prepare these particles are those which graft polymerize on the cationic water-soluble prepolymers to form a water-insoluble graft polymer. It is the insolubility of the graft polymer that gives rise to the formation of individual, substantially spherical, water suspended particles. The initial function of the water-soluble cationic prepolymer is to stabilize the suspension and prevent coagulation of the individual particles. After the first graft copolymerization, some homopolymerization of the monomer may occur within the particles. Substantially stable latex of graft copolymer particles is prepared according to the present invention without the need for the presence of another stabilizer. There are two main requirements on the graft polymer particles. They must (1) be water insoluble and (2) have a sufficiently high melting or softening point so that they do not deform to any significant degree under conditions of heat and / or pressure, under which conditions they are subjected to use. Use as a filler for paper requires that the particles remain discrete and substantially spherical during web formation, drying and calendering. Preferably, the graft copolymer has a transition temperature
<img file="SE435845B_D0011.tif" />
<img file="SE435845B_D0012.tif" />
the order (glass transition temperature, T) of about 9 examples of graft polymer prepared
<img file="SE435845B_D0013.tif" />
the mers have a glass transition temperature, T, greater than 75 ° C.
All monomers which graft polymerize with the water-soluble cationic prepolymers, which are described below, to obtain graft polymer particles meeting the above requirements, can be used in the present invention. Suitable monomers are monoethylenically unsaturated monomers of the formula __C = CH<sub>2</sub>
<img file="SE435845B_D0014.tif" />
wherein R is hydrogen or methyl, Y is methyl or chlorine and n is 0, 1, 2 or 3. Examples of such monomers are styrene, α-methylstyrene, monochlorostyrene, dichlorostyrene,
7910359-6 trichlorostyrene, monoethylstyrene, dimethylstyrene and trimethylstyrene.
Mixtures of two or more monoethylenically unsaturated monomers can be used in the practice of the present invention, provided that the graft copolymer particles obtained are water insoluble and have a T of about 75 ° C or greater. Also polyethylenically unsaturated monomers such as divinylbenzene can be used in admixture with monoethylenically unsaturated monomers to obtain cross-linked graft copolymer particles.
The water-soluble cationic prepolymers can be many different kinds of polymers. The main criterion is that they provide optimal cationic charge for good retention of the graft copolymer particles produced in paper. For example, in a latex prepared using about 10 percent prepolymer, based on the weight of the monomer used, the opacity is highest when the molar portion of the cationic monomer portion in the water-soluble prepolymer is in the range of about 5 to 50 mole percent, the optimum range being about 10 to about 30 mole percent. These ranges, of course, depend on the content of water-soluble cationic prepolymer used to prepare the latex. For example, when about 5 percent water-soluble prepolymer, based on monomer, is used, the range is from about 10 to about 100 mole percent cationic monomer, with the optimum range being about 20 to about 60 mole percent. Similar corrections can be made when other levels of water-soluble polymer are used and are within the skill of the art.
The cationic water-soluble prepolymers which are particularly suitable for use in the present invention are addition-type polymers prepared from ethylenically unsaturated cationic monomers of formula (I), (II), (III), (IV), (V) and ( WE).
7910339-6 (I)
<img file="SE435845B_D0015.tif" />
<img file="SE435845B_D0016.tif" />
CH<sub>2</sub>= CCOOC<sub>2</sub>hrs<sub>u</sub>N
<img file="SE435845B_D0017.tif" />
In formula (I), hydrogen or methyl; R<sub>2</sub> represents hydrogen or alkyl of 1-4 carbon atoms, for example methyl, ethyl, propyl or butyl; Rg carbon atoms,
OH
IN
-CH<sub>2</sub>-CfICH<sub>2</sub>Y is hydrogen, alkyl of 1-4 wherein Y is hydroxyl or halogen, eg chlorine and bromine, 0/1
-CH<sub>2</sub>.CHCH<sub>2</sub> and (CH<sub>2</sub>CH<sub>2</sub>O)<sub>n</sub>H, wherein n is an integer 1 or greater, preferably 1-20; and X represents an anion, for example Cl, Br, CHgOSOg and CHgCOO. Monomers of formula (I) are quaternary ammonium salts and acid salts of amino acrylates such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminolethyl methacrylate and diethylaminoethyl methacrylate. Specific monomers of quaternary salts of formula (I) are methacpyloyloxyethyl trimethyl ammonium methyl sulfate and methacryloyloxyethyl trimethyl ammonium chloride. Specific monomers of
<td colspan="2">Acid salts of formula (I) are methacryloyloxyethyl dimethyl ammonium chloride and methacryloyloxyethyl dimethyl ammonium acetate.</td>
<td>CH " Ii <sup>1</sup></td><td>F<sup>2</sup></td>
<td>(II) I -C</td><td>Γ<sup>1</sup></td>
<td>CH "</td><td>CH + X</td>
V / <sup>2</sup>
N
<img file="SE435845B_D0018.tif" />
In formula (II), hydrogen or alkyl having 1-4 carbon atoms represents. R<sub>2</sub> represents hydrogen, alkyl or substituted alkyl.
Typical alkyl groups which can stand for R<sub>2</sub>, contains 1-18
7V10335 access
The cd is preferably in 1-6 carbon atoms and includes methyl, ethyl, propyl, isopropyl, t-butyl, hexyl, octyl, decyl, dodecyl, tetradecyl and octadecyl. R<sub>2</sub> may also be a substituted alkyl group, with suitable substituents being any substituent which does not interfere with polymerization via a vinyl double bond. Typical substituents are carboxylate, cyano, ether, amino (primary, secondary or tertiary), amide, hydrazide and hydroxyl. R<sub>g</sub> and X has the meaning given under formula (I). Monomers of formula (II) are quaternary ammonium salts and acid salts of diallylamine of formula
CH
- II
R-C
<img file="SE435845B_D0019.tif" />
C1E <sub>/ C</sub>hrs<sub>2</sub> \ / <sup>S</sup>N wherein and R<sub>2</sub> has the meaning given above. Specific examples of monomers of quaternary ammonium salts of formula (II) are dimethylallylammonium chloride and dimethylldiallylammonium bromide. Specific examples of acid salts of formula (II) are methyldiallylammonium acetate, diallylammonium chloride, N-methyldiallylammonium bromide, 2,2'-dimethyl-N-methyldiallylammonium chloride, N-etyldiallylammonium bromide, N-isopropyldiallylammonium , N-ok tadecyldi ullylamine ammonium chloride, Nacetami dodi in allylamammonium chloride, N-cyanomethyldiallylammonium chloride, Ν-β-propionamidodiallylanimonium bromide, N-acetyl ester-substituted diallylammonium chloride, with N-ethylmethyl ether substituted diallylammonium bromide, N-β-ethylaminediallylammonium chloride, N-hydroxyethyldiallylammonium bromide, and with N-acetohydrazide-substituted diallylammonium chloride
7910339-6 (III)
<img file="SE435845B_D0020.tif" />
In formula (III), R 2, R 8 R 9 and X have that of formula (I). stated meaning. Specific examples of monomers of formula (III) are vinyl benzyl trimethylammonium chloride and vinyl benzyltr iniety lammo n iumbr om i d.
(IV)
<img file="SE435845B_D0021.tif" />
In formula (IV), R 1, R 9 and X have the meaning given under formula (I). Specific examples of monomers of formula (IV) are 2-vinylpyridinium chloride and 2-vinylpyridinium bromide.
<sup>R</sup>1 in<sup>1</sup> + (V) CH = CC0NH (CH2) N
2 n
<img file="SE435845B_D0022.tif" />
In formula (V), Rp Rg, Rg and X have the meaning given under formula (I) and n represents an integer 1, 2 or 3. A specific example of a monomer of formula (V) is methacrylamidopropyl dimethylammonium chloride.
(WE)
Rf Rg
IN<sup>1</sup> + / <sup>z</sup>
CH "= CCOOCH_CnCH" N - R_
4« \ <sup>R</sup>3
X
791Ö339-6
In formula (V), R has<sub>2</sub>, Rg and X<sup>-</sup> the meaning given by formula (I). A specific example of a monomer of formula (VI) is 3-methacryloyloxy-2-hydroxypropyl dimethylammonium chloride.
As can be seen from the foregoing, there is an optimal level of cationic charge on the polymer particle, which charge is required for good retention in the paper. The optimum charge can be obtained with a cationic homopolymer by varying the amount of homopolymer used to prepare the graft polymer latex. However, it is preferred to adjust the cationic charge using a copolymer of at least one cationic monomer and at least one nonionic unsaturated monomer capable of addition type polymerization. Examples of nonionic monomers are monoethylenically unsaturated amide monomers, e.g. acrylamide, methacrylamide, N-acetamidoacrylamide, N-acetamidomethacrylamide, N-methylolacrylamide, diacetonacrylamide, diacetone methacrylamide, N, Ndimethylacrylamide and N-methylacrylamide. Other suitable nonionic monomers are vinyl acetate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and N-vinyl pyrrolidone. The copolymer of vinyl acetate is later hydrolyzed to exchange substantially all acetate groups against hydroxyl groups.
The water-soluble cationic prepolymers used in the present invention can be (A) homopolymers of cationic monomers of formula (I) - (VI), (B) the copolymer of at least two monomers of the formula (I) (VI) and (C) the copolymer of at least one of the monomers of formula (I) - (VI) and at least one other ethylenically unsaturated monomer, preferably a nonionic monomer. Thus, the preferred water-soluble cationic prepolymers consist essentially of about 5 mole percent to 100 mole percent of at least one monomer of formula (I) - (VI) and about 95 mole percent to 0 mole percent of at least one other ethylenically unsaturated nonionic monomer.
7910339-6
Very satisfactory water-soluble cationic prepolymers for use in preparing the present graft copolymer particles are (1) prepolymers made from about 70 mole percent to 98 mole percent, preferably about 5 82 mole percent to about 90 mole percent, acrylamide. and about mole percent to about 2 mole percent, preferably about mole percent to about 10 mole percent dimethyldiallylammonium chloride; (2) prepolymers made from about 67 mole percent to about 98 mole percent, preferably about 67 mole percent 10 to about 89 mole percent, acrylamide and about 33 mole percent to about 2 mole percent, preferably about 33 mole percent to about 11 mole percent, methyldiallylammonium chloride; (3) prepolymers made from about 70 mole percent to about 98 mole percent, preferably about 82 mole percent to about 91 mole percent, acrylamide and about 30 mole percent to about 2 mole percent, preferably about 18 mole percent to about 9 mole percent methyldialylammonium acetate; and (4) prepolymers made from about 70 mole percent to about 95 mole percent, preferably about 70 mole percent to about 88 mole percent, acrylamide and about 30 mole percent to about 5 mole percent, preferably about 30 mole percent to about 12 mole percent, methacryloyloxyethyl trimethyl ammonium sulfate.
The water-soluble cationic prepolymers are prepared simply and quickly by simultaneously adding the desired monomers, in the desired amounts, and a water-soluble free-radical polymerization initiator, each in aqueous solution, to a reaction vessel containing water, which is kept at a temperature of about 80 ° C to about 90 ° C. Suitable free radical polymerization initiators are those used in the preparation of the present graft copolymer particles and are described in part: the following. The amount of initiator used is that sufficient to form water-soluble cationic prepolymers with an RSV of about 0.1 to about 2.5, preferably about 0.1 to about 1.0, measured as a 1% solution in 1 M NaCl at 25 ° C.
In some cases, reactive functionality is desirable, i.e. having reactive groups on the surface of graft copolymer.
7910339-6 i?
merpartiklarna. The reactive groups generally increase the bonding properties of the graft copolymer particles. Preferred reactive groups are those which react with cellulose.
Reactive groups may be introduced into the cationic monomers prior to preparation of the prepolymer or they may be introduced into the prepolymer after it has been prepared or they may be introduced onto the graft copolymer particles after they have been prepared.
Cellulose reactive groups can be introduced by reaction of an epihalohydrin, e.g., epichlorohydrin, and polymers containing secondary amine functionality and / or tertiary amine functionality. Reactive groups obtained with epihalohydrin may be an epoxide, the halohydrin of the epoxide or an azetinium group.
Reactive groups can be introduced using an aldehyde, for example, formaldehyde, glyoxal and glutaraldehyde, with polymers containing amide functionality, e.g. for example in prepolymers made from diallylamine salts. When using dialdehydes, for example glyoxal, the reactive group will be an aldehyde. When using formaldehyde, the reactive group will be the N-methylol group.
The amount of functionality providing agent used to obtain reactive groups on the graft copolymer particles of the present invention is about 0.25 mole to about 3 mole, preferably 1 mole to about 2 mole, for each mole of amide or amine functionality.
The reaction is carried out at a temperature of about 20 ° C. In 1.1, about 60 ° C is stirred. The pH of about 8 µl 10, except when formaldehyde is used as a means of forming functionality, when the reaction is carried out at a pH of about 2 to 3.
The reactive groups can improve the paper holding phase by reacting the graft copolymer particles with the cellulose fibers. Conventional fillers generally decrease
7910339-6 paper strength by interfering with the bonding between cellulose fibers. Using graft copolymer particles containing groups that react with cellulose, it is possible to obtain higher paper strength by bonding between fibers via the reactive functional groups on the particles.
The amount of prepolymer used in preparing the present graft copolymers can vary from about 1 part by weight to about 25 parts by weight for every 100 parts by weight of monomer used. The preferred range is 2 - 10 parts prepolymer for every 100 parts monomer.
Graft copolymerization is carried out by adding monomer to an aqueous solution of water-soluble cationic prepolymer in the presence of a free radical polymerization initiator. The water-soluble prepolymer may be present in the reaction vessel at the beginning of the preparation or may feel the whole amount or parts thereof being added simultaneously with the monomer. The initiator is usually added continuously together with the monomer. The total reaction time can vary from about 1 hour to about 24 hours, with the preferred time being about 2-6 hours. Latex prepared according to the present invention has a solids content of about 15% to about 60%. Preferably, the amount of water used in preparing the latex is such that one obtains latex with a solids content of about 25% to about 55%. In some cases, it is possible to dry the latex into a fine powder. In these cases, the powder can again be dispersed in water and then added to the pulp slurry prior to forming the paper. Drying of the latex to a fine powder is usually not possible when the graft copolymer particles are ultrasonic with reactive groups.
The final product is a stable suspension of substantially spherical graft copolymer particles in water. According to the present invention, graft copolymer particles can be produced having a particle size of about 0.1 µ to about 2 µ.
7910339-6
ICE
A large number of chemical polymerization initiators can be used to prepare. the present latex, wherein peroxide compounds are particularly useful. Preferably, the initiator is water-soluble.
Suitable water-soluble initiators include those activated with heat, e.g., sodium persulfate and ammonium persulfate. Polymerization carried out with these initiators is usually carried out at temperatures of 70 - 95 ° C. Other water-soluble initiators which are suitable include so-called redox initiator systems, for example, ammonium persulfate sodium hydrogen sulfite iron (II) ions and t-butyl hydroperoxide sodium formaldehyde sulfoxylate. Redoxinators are activated at relatively low temperatures, and polymerization using these systems can be carried out at temperatures of about 20 ° C to 80 ° C. The amount of initiator used can be readily determined by one skilled in the art. Typically, about 0.1 parts by weight to about 5 parts by weight of initiator per 100 parts by weight of monomer is used. The following examples illustrate the invention.
Example 1
A water jacket equipped with a thermometer, a stirrer, a condenser and three separating funnels was filled with 87.0 g of distilled water. In the funnels, (1) 71.25 g of acrylamide (1.0 mole) was charged into 166.0 g of distilled water, (2) 3.7 g of dimethyldialylammonium chloride (DMDAAC, 0.023 mole) in 8.75 g of distilled water and (3) 1.88 g of ammonium persulfate (0.008 mol) in 35.6 g of distilled water. The contents of the vessel were heated to 85 - 89 ° C, and the contents of the three separating funnels were added dropwise over a period of 3 hours. After heating for a further 15 minutes, cool the solution to room temperature (23 ° C). The product solution contained 21.9% solids and had an RSV, reduced specific viscosity, of 0.32 (1% solution in NaCl at 25 ° C).
A water jacket fitted with a thermometer, a stirrer, a condenser and three separating funnels was filled with 493.0 g of distilled water and 54.4 g
7910339-6 of a solution containing 10% solids of the indicated copolymer (5.44 g dry copolymer). The separating funnels were filled with: (1) 164.0 g of the solution containing 10% solids of the indicated polymer (16.4 g dry copolymer), (2) 218.0 g styrene and (3) 6.0 g ammonium persulfate in 24 , 2 g distilled water. The contents of the vessel were stirred and heated to 88 ° C. The contents of the three separating funnels were added over a period of 3 hours while the vessel temperature was maintained at 88 - 93 ° C. After heating for another 15 minutes, the product was cooled to room temperature. The product was a latex containing 25.2% solids. About half of the latex was dialyzed using a membrane (48 angstroms) of regenerated cellulose to remove unreacted water-soluble prepolymer.
240.0 g of the dialyzed latex (50.0 g of dry polymer, 0.056 mol of acrylamide) was placed in a reaction vessel and the pH was changed from 4.2 to 9.1 with 0.9 ml of 1 M sodium hydroxide solution. Glyoxal (16.2 g of a 40% aqueous solution, 0.112 mol) was added and the pH was changed from 6.5 to 9.0 with 0.8 ml of 1 M sodium hydroxide solution. The wafer (56-ml) was added to lower the solids content. The mixture was heated for 4 hours at 50 ° C, and the pH was then lowered to 2.0 with 0.5 ml of concentrated hydrochloric acid. The final product contained 18.2 »solids.
Examples 2-5
Four additional latexes were prepared by the procedure described in Example 1, except that the ratio of acrylamide to DMDAAC was varied in the manner shown in Table 1.
Example G
The compositions of Examples 1-5 were evaluated as filler for paper. Hand sheets are set on a Noble & Wood machine. The pulp consisted of a 50:50 mixture of pulp of bleached low-bleached softwood, which pulp was ground to a Canadian Standard Freeness of 300 ml. The paper is prepared at a pH of 4.5 (sulfuric acid, no alum). The latex ut7910339-6
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7910339-6 was evaluated at addition levels of 4% and 8% (based on dry material). The control experiments were carried out with paper without filler and paper containing 10% and 20% kaolin clay. The clay was retained using 1% alum and 0.05% of a high molecular weight cationic polyacrylamide retention agent. The results of the experiments on paper are summarized in Table 2.
Examples 7-10
Four latexes were prepared by the procedure described in Example 1 using 10% of various copolymers of acrylamide and DMDAAC. The latex was not reacted with glyoxal. The conditions for latex synthesis are given in Table 3.
Example 11
The graft copolymers of Examples 7-10 were evaluated as fillers in paper in the manner set forth in Example 6. The results are summarized in Table 4.
Examples 12-16
Several latexes were prepared by the example described except that the water-soluble prepolymer used to prepare the graft copolymers were copolymers of acrylamide and methacryloyloxyethyl trimethyl ammonium methyl sulfate (MTMMS). The reaction conditions are summarized in Table 5. The latex was not reacted with glyoxal.
Example 17
The graft copolymer particles of Examples 12 - 16 were evaluated as fillers in paper in the manner described in Example 6. A commercially available polystyrene latex was used as an additional control experiment. The particles in the polystyrene latex exhibited negative charges, and because of this, the retention agent shown was used.
Example 18
The clay and a commercially available polystyrene latex were evaluated as filler in paper in the manner described in Example 6. The two fillers were evaluated both with and without a cationic polyacrylamide retention agent. The test results are summarized in Table 7.
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<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>S</td>
<td>CM</td><td></td><td></td><td></td><td></td><td></td><td></td><td>•HRS</td><td>S</td>
<td></td><td> 00</td><td></td><td></td><td></td><td></td><td></td><td>A</td><td>yl</td>
<td colspan="2">- = Γ Ο</td><td></td><td>Ο</td><td>O</td><td>O</td><td>O</td><td>O</td><td></td>
<td>π</td><td>CM</td><td>Μ)</td><td>Λ</td><td>Λ</td><td>A</td><td> . .«*</td><td>AS</td><td>• rl</td>
<td></td><td>ω</td><td>ο</td><td>CO</td><td>CD</td><td>CD</td><td>CO</td><td>o</td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>O</td><td>stay</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>P</td><td>C</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Λί</td><td>•HRS</td>
<td> 1</td><td></td><td></td><td></td><td></td><td></td><td></td><td>• μ</td><td>C</td>
<td></td><td>C</td><td>ζ- »</td><td> 00</td><td> 00</td><td>CO</td><td> 00</td><td>ε</td><td>ω</td>
<td>-μ</td><td> 0)</td><td>W</td><td>yl</td><td>yl</td><td>we</td><td>we</td><td>C</td><td>YES</td>
<td>ω</td><td>f</td><td>χ-ζ</td><td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>ο</td><td>rH</td>
<td colspan="2">rH</td><td> 00</td><td> 00</td><td>co</td><td> 00</td><td>•HRS</td><td colspan="2">ω</td><td>Ρ</td>
<td>P</td><td></td><td>we</td><td>we</td><td>we</td><td>we</td><td>ω</td><td> 2</td><td></td><td>: ιΒ</td>
<td> 0)</td><td></td><td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>co</td><td>• η</td><td></td><td>β</td>
<td>S</td><td></td><td></td><td></td><td></td><td></td><td>• rl</td><td>R-4</td><td></td><td></td>
<td></td><td></td><td> 00</td><td></td><td>d-</td><td> 00</td><td>β</td><td></td><td></td><td>ζ- \</td>
<td></td><td> ></td><td>CM</td><td>CM</td><td>CM</td><td>rd</td><td>ω</td><td>Ό</td><td></td><td>-Ρ</td>
<td></td><td>ω</td><td>O</td><td>Γ "</td><td>n</td><td>n</td><td>α</td><td>φ</td><td></td><td> 0)</td>
<td></td><td></td><td>O</td><td>O</td><td>O</td><td>O</td><td>rd</td><td rowspan="2">β</td><td></td><td>Η</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td>μ</td><td></td><td>• Η</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td>• μ</td><td>Ό</td><td></td><td> 01</td>
<td></td><td> •</td><td>CD</td><td>-T</td><td>CO</td><td>CO</td><td></td><td>rd</td><td></td><td> 0</td>
<td>dP</td><td>CD</td><td>«V</td><td></td><td> «»</td><td>Λ</td><td>Ό</td><td>• μ</td><td></td><td>Λ</td>
<td></td><td>A</td><td>yl</td><td>we</td><td>r</td><td>we</td><td>Φ</td><td>4J</td><td></td><td> 01</td>
<td></td><td>EH</td><td>CM</td><td>CM</td><td>CM</td><td>CM</td><td> 6</td><td>rd</td><td></td><td>• Η</td>
<td> ..</td><td></td><td></td><td></td><td></td><td></td><td></td><td>X</td><td></td><td> ></td>
<td>Ό</td><td></td><td></td><td></td><td></td><td></td><td>• μ</td><td>ω</td><td>ω</td><td></td>
<td>• rl</td><td></td><td></td><td></td><td></td><td></td><td>• μ</td><td>Λ</td><td>β</td><td></td>
<td>S</td><td> 0</td><td></td><td>X</td><td>O</td><td>c</td><td>CD</td><td>O</td><td>rH</td><td>rH</td><td>ω</td><td>Λ</td>
<td> >,</td><td>s:</td><td> <</td><td>Q</td><td>cn</td><td> 00</td><td>γ-</td><td>Γ-</td><td>al</td><td>al</td><td></td><td>ω</td>
<td>γΗ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 0</td><td>O</td><td>μ "</td><td></td>
<td> 0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>P</td><td>P</td><td>ω</td><td>Ό</td>
<td>α</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>U1</td><td> 01</td><td>id</td><td>rd</td>
<td>μ</td><td>CM</td><td></td><td></td><td></td><td></td><td></td><td></td><td>rH</td><td>rH</td><td></td><td>μ</td>
<td> :0</td><td>/ "Χ</td><td></td><td></td><td></td><td></td><td></td><td></td><td> 0)</td><td>ω</td><td></td><td>φ</td>
<td></td><td></td><td colspan="2">CO Z ~ v</td><td>CO</td><td> 00</td><td>οο</td><td>ΟΟ</td><td></td><td></td><td>• R</td><td>ο</td>
<td></td><td>K</td><td>O</td><td>stay</td><td> 00</td><td>CO</td><td>CO</td><td> 00</td><td>•HRS</td><td>•HRS</td><td>rH</td><td> 3</td>
<td>ΟΟ</td><td></td><td colspan="2">CM 'o'</td><td>λ</td><td>n</td><td>fV</td><td>«χ</td><td>P</td><td>• P</td><td>rd</td><td>Ό</td>
<td>• Η</td><td>x_z</td><td>C / 3</td><td></td><td>v4</td><td>we</td><td>we</td><td>we</td><td>P</td><td>al</td><td>• μ</td><td>Φ</td>
<td>rH</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>iO</td><td><ΰ</td><td> 0</td><td>μ</td>
<td>ω</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>A</td><td>A</td><td>Eh</td><td>χ_ζ</td>
<td> :0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>rH</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>z ~ x</td><td> •</td><td></td>
<td>C</td><td></td><td>ω</td><td></td><td></td><td></td><td></td><td></td><td>H</td><td>CM</td><td>ω</td><td> ></td>
<td>Φ</td><td></td><td><ς</td><td></td><td></td><td></td><td></td><td></td><td></td><td>x_z</td><td> •</td><td>ω</td>
<td>-μ</td><td></td><td></td><td>z »</td><td>O</td><td>Γ **</td><td>we</td><td>LQ</td><td></td><td></td><td>EH</td><td>Μ</td>
<td>μ</td><td></td><td>Q</td><td>bB</td><td>n</td><td> «*</td><td>r »</td><td>c</td><td></td><td></td><td></td><td></td>
<td>rd</td><td></td><td>X</td><td></td><td>U0</td><td> 00</td><td> 00</td><td>C</td><td></td><td></td><td></td><td></td>
<td> ></td><td></td><td>island</td><td></td><td>r4</td><td>we</td><td>CM</td><td>CO</td><td></td><td></td><td></td><td></td>
7910339-6
Toro? pull the Muilen blast
Fillers Retention agent Surface weight Opacity% strengths. strength (¾) (kg / m 2) (kp / cm) (kp / cm)
<td>V1 CN</td><td>CD CO</td><td>CD Γ-</td><td>CM H</td><td>00 σ></td><td>. Rd</td><td>Ε— CO</td><td>CM <_j CO</td><td>Γ— cn</td><td>CO cn</td>
<td>CM</td><td>Ή</td><td>Η</td><td>CM</td><td></td><td>CM</td><td>rd</td><td>CM rd</td><td></td><td>yl</td>
<td>c-4</td><td>CO</td><td>CO</td><td>CM</td><td>rd</td><td>vH</td>
<td>cn</td><td>CO</td><td>Γ-</td><td>O</td><td>CO</td><td> 03</td>
<td>n</td><td>n</td><td>η</td><td>Λ</td><td> *></td><td>O</td>
<td>CM</td><td>CM</td><td>CM</td><td>co</td><td>CM</td><td>CM</td>
<td>CM</td><td>rd</td><td>O</td><td>CM</td><td>in *</td><td>Γ-</td>
<td>n</td><td>Γ "</td><td>n</td><td>n</td><td>n</td><td>n</td>
<td>to</td><td>σ></td><td>hrs</td><td>O</td><td>zt-</td><td>1-χ</td>
<td>Γ-</td><td>Γ-</td><td> .00</td><td>CO</td><td> 03</td><td>CO</td>
Φ P
<td>CM</td><td>CO</td><td>CM</td><td>C</td><td>O</td><td></td>
<td>Γ-</td><td>Γ-</td><td>ID</td><td>Γ-</td><td>Γ-</td><td>S</td>
<td>η</td><td>η</td><td>r></td><td>n</td><td>η</td><td>ω</td>
<td>CM</td><td>CM</td><td>CN</td><td>CM</td><td>CM</td><td>P</td>
Φ P Ή
O nJ ft o
Φ
<td>O</td><td>CD</td><td>CO</td><td>CO</td><td>cn</td><td>P</td>
<td>n</td><td>n</td><td>n</td><td>n</td><td>n</td><td>d</td>
<td>CD</td><td>rd</td><td>CD</td><td>cn</td><td>CM</td><td></td>
<td>CO</td><td>CO</td><td>co</td><td>r</td><td>CO</td><td>X</td>
m cm zt
IN
TJ
<td>CO</td><td>CD</td><td>CM</td><td>O)</td><td>cn</td><td>co</td><td>rT</td><td>Ή</td><td>O)</td><td>rd</td><td>CO</td><td>nJ</td>
<td>n</td><td>n</td><td>e></td><td>n</td><td>n</td><td>n</td><td>n</td><td>n</td><td>n</td><td>n</td><td>Λ</td><td>Ό</td>
<td>CD</td><td>cn</td><td>CN</td><td>t</td><td>cn</td><td>E-</td><td>CD</td><td>CO</td><td>CD</td><td>Γ-</td><td>CO</td><td>C</td>
<td>CD</td><td>CD</td><td>t</td><td>CO</td><td>co</td><td>CD</td><td>CD</td><td>CD</td><td>CD</td><td>CD</td><td>CD</td><td>Φ P</td>
ω
<td colspan="12">TJ</td><td>P</td>
<td></td><td></td><td>• rl</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>hO</td>
<td></td><td></td><td> £</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>• rl</td>
<td></td><td></td><td>nJ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>rd</td>
<td></td><td></td><td>rd</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> £</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Φ</td>
<td></td><td></td><td>k</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td rowspan="2">P</td>
<td></td><td></td><td>Ai</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td>ω</td><td>nJ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>P</td>
<td></td><td> 2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td>rd</td><td> 1—1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>S</td>
<td></td><td>ft</td><td rowspan="2">0 a</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>P</td>
<td></td><td>Zs</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Φ</td>
<td></td><td>o'P</td><td>x</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> +></td>
<td></td><td></td><td>ω</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>'rd</td>
<td> 1</td><td>Ή</td><td>• rd</td><td>o \ °</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td>IN</td><td>IN</td><td> 1</td><td> 1</td><td>O</td>
<td></td><td></td><td> £</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>nJ</td>
<td></td><td></td><td> 0</td><td>ID</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ft</td>
<td></td><td> £</td><td>• n</td><td>O</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>O</td>
<td></td><td></td><td>P</td><td>n</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>z></td>
<td></td><td>rd</td><td>nJ</td><td>O</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>P</td>
<td></td><td> <</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>xz</td>
<td></td><td>z ~ x</td><td>z ~ x</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td>O</td><td>O</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>z ~ x</td><td></td><td></td>
<td></td><td>Ή</td><td>CN</td><td></td><td>zs</td><td></td><td>z <</td><td>z ~ p</td><td>Z "s</td><td>zs</td><td>at</td><td> 00</td><td></td>
<td></td><td></td><td>s_z</td><td></td><td>at</td><td>co</td><td>at</td><td>co</td><td>at</td><td>co</td><td>x_z</td><td>x »z</td><td></td>
<td></td><td></td><td></td><td></td><td>X_f</td><td></td><td>O</td><td></td><td>O</td><td>\ Z</td><td></td><td></td><td></td>
<td></td><td>KJ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>O</td><td></td><td></td>
<td></td><td>P</td><td></td><td></td><td>C</td><td></td><td>co</td><td></td><td>CD</td><td></td><td>rd</td><td></td><td></td>
<td></td><td>Φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td>i-1</td><td></td><td></td><td>rd</td><td></td><td> 1—1</td><td></td><td>rd</td><td></td><td>rl</td><td></td><td></td>
<td></td><td>c</td><td></td><td></td><td>ω</td><td></td><td> 0)</td><td></td><td>Φ</td><td></td><td>Φ</td><td></td><td></td>
<td>P</td><td>• rd</td><td></td><td></td><td>ft</td><td></td><td>ft</td><td></td><td>ft</td><td></td><td>ft</td><td></td><td></td>
<td> 0)</td><td>i-1</td><td></td><td></td><td>β</td><td></td><td>β</td><td></td><td> £</td><td></td><td>β</td><td></td><td></td>
<td>stay</td><td> 0</td><td></td><td></td><td>QJ</td><td></td><td> (1)</td><td></td><td>Φ</td><td></td><td>Φ</td><td></td><td></td>
<td>β</td><td>OH</td><td></td><td></td><td>X</td><td></td><td>X</td><td></td><td>X</td><td></td><td>X</td><td></td><td></td>
<td>hrs</td><td> >4</td><td></td><td></td><td>W</td><td></td><td>w</td><td></td><td>w</td><td></td><td>ω</td><td></td><td></td>
7910339-6
<img file="SE435845B_D0041.tif" />
<td>ο</td><td> <0</td><td>CD</td><td>CD</td><td>· Γ *</td><td>O</td>
<td>Λ</td><td>ft</td><td>ft</td><td>η</td><td>ft</td><td></td>
<td>(D</td><td>IO</td><td>IO</td><td>IO</td><td></td><td></td>
<td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>rd</td>
<td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>CN</td>
<td>O</td><td>CD</td><td>O</td><td>CD</td><td>O</td>
<td></td><td></td><td> :3-</td><td>zf</td><td>JD</td>
<td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>CN</td>
<td></td><td></td><td> [></td><td>CO</td><td> 00</td>
<td>CD</td><td>LD</td><td>CO</td><td>J-</td><td>CD</td>
<td>r4</td><td>Ή</td><td>Ή</td><td>rH</td><td>rH</td>
<td></td><td>ft</td><td>rt</td><td> *»</td><td>ft</td>
<td>O</td><td>O</td><td>O</td><td>O</td><td>O</td>
<td>CD</td><td>CD</td><td>CO</td><td>O</td><td> £**»</td>
<td>ft</td><td>ft</td><td></td><td>ft</td><td>ft</td>
<td>rH</td><td>rd</td><td>rH</td><td>rd</td><td>rd</td>
<td>CM</td><td>CM</td><td>CM</td><td>CN</td><td>CN</td>
<td>O</td><td>CO</td><td> 00</td><td>rH</td><td>LO</td><td colspan="2">Λ</td><td colspan="2">ω · Η</td>
<td>Γ-</td><td>R</td><td> 00</td><td>CD</td><td>CD</td><td>λ:</td><td>Ρ</td><td>Λ</td><td>Ο</td>
<td></td><td></td><td></td><td></td><td></td><td>ω</td><td>Ρ- <</td><td> □</td><td>sew</td>
<td></td><td></td><td></td><td></td><td></td><td>rd</td><td></td><td>ω</td><td>Λ</td>
<td></td><td></td><td></td><td></td><td></td><td> &</td><td>ft</td><td></td><td>U)</td>
<td>tn</td><td>ID</td><td>LD</td><td>LO</td><td>ID</td><td> 0</td><td>ο</td><td> 4-></td><td></td>
<td>α</td><td>ft</td><td>ft</td><td>ft</td><td>ft</td><td>• Ρ</td><td>ο</td><td>ω</td><td>τ)</td>
<td>CM</td><td>CN</td><td>CN</td><td>CN</td><td>CN</td><td>ω</td><td>CN</td><td>, Φ</td><td>Φ</td>
<td>CN</td><td>CM</td><td>CN</td><td>CN</td><td>CN</td><td>rd</td><td></td><td>Uh</td><td>Η</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td>ft</td><td></td><td>Φ</td>
<td></td><td></td><td></td><td></td><td></td><td> •</td><td></td><td>• Ρ</td><td>ο</td>
<td></td><td></td><td></td><td></td><td></td><td>Μ</td><td> (0</td><td>rd</td><td> □</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td>Φ</td><td>your</td><td>TJ</td>
<td></td><td></td><td></td><td></td><td></td><td>Jj</td><td>W</td><td> 4-></td><td>ω</td>
<td>O</td><td>O</td><td>O</td><td> 00</td><td>O</td><td>(π</td><td>♦ rd</td><td>Ο</td><td>Μ</td>
<td>ft</td><td>ft</td><td>ft</td><td>ft</td><td>ft</td><td>α.</td><td>Q</td><td>Η</td><td></td>
<td>CD</td><td>O</td><td>CD</td><td>rf</td><td>LD</td><td></td><td></td><td></td><td></td>
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7910339-6 i
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7910339-6
Example 19
Dimethylaminoethyl methacrylate (157 g) was added dropwise to 98 g of 37% hydrochloric acid. Cooling was required to keep the temperature below 30 ° C. Water (381 ml) and isopropanol (12.2 ml) were added to give a 30% solution. The solution was heated to 50 ° C and purged with nitrogen for 30 minutes, followed by heating to 75 ° C and the addition of 3.6 ml of 0.1 M FeSO 3 H 2 O and then 10.9 ml of t-butyl hydroperoxide (90%). When the addition of the catalyst was complete, the solution was stirred for 30 minutes and cooled to room temperature. The viscous solution was diluted to a content of 15.85% solids. RSV = 0.53 (1 M NaCl, 1%, 25 ° C).
A two-liter, 2-liter vessel equipped with a thermometer, stirrer, condenser and three separating funnels was filled with 269 ml of distilled water. To the separating funnels were added: (1) 183 g of a 12.3% aqueous solution of the poly (methacryloyloxyethyl dimethyl ammonium chloride) produced, (2) 225 g of styrene and (3) 6 g of ammonium persulfate in 25 ml of distilled water. The contents of the vessel were stirred and heated to 80 ° C under nitrogen. The contents of the separatory funnels were added dropwise over a period of two hours while maintaining the vessel temperature at 88 - 95.5 ° C. After heating for another 15 minutes, the product was cooled to room temperature. The final product was styrene-free and had a total solids content of 36.4%.
Example 20
Poly (methacryloyloxyethyl dimethyl diammonium chloride) was prepared as in Example 19 except that the solution was diluted to a solids content of 30% instead of 15.85%. 1G1.5 g of this 30% solution was placed in a reaction vessel with 359 g of distilled water. The pH of the solution was changed from 1.9 to 1.0 with 3.6 ml of concentrated HCl. Epichlorohydrin (34.7 g) was added to the reaction vessel to give 15% solids. The mixture was stirred underneath
6.5 hours, increasing the pH to 7.6. The pH was then adjusted to 0.5 with 13.7 ml of concentrated HCl. Total
7910339-6 solids content = 12.3%.
A water-filled 2-liter vessel, equipped with a thermometer, stirrer, condenser and three separating funnels, was filled with 269 ml of distilled water. To the separating funnels was added (1) 183 g of a 12.3% aqueous solution of the water-soluble epichlorohydrin modified prepolymer as above, (2) 225 g styrene and (3) 6 g ammonium persulfate in 25 ml distilled water. The contents of the vessel were stirred and heated to 89 ° C under nitrogen. The contents of the separating funnels were added dropwise over a period of 2 hours while maintaining the temperature of the vessel at 89 97 ° C. After heating for another 15 minutes, the product was cooled to room temperature. The final product was styrene-free and had a total solids content of 36.8%.
Example 21
To a reaction vessel was added 4130 g of distilled water and 145.5 g of a 51.95% aqueous solution of poly (methyldiallyl ammonium chloride). The contents of the vessel were heated to 87 ° C under nitrogen. 228 g of poly (methyldiallylammonium chloride) in 1597 g of distilled water, 3040 g of styrene and 83.7 g of ammonium persulfate in 338 g of distilled water were added simultaneously dropwise over a period of 2 hours. The temperature was maintained at 87-100 ° C. The contents of the vessel were stirred an additional 15 minutes, cooled to room temperature and filtered through a 100 mesh screen. The resulting latex had a total solids content of 37.2%, and the particle size was 0.5 µm, as measured by Loebel (see Table 5). 806.5 g of the latex (300 g of solid) was placed in a reaction flask, and the pH was changed from 1.6 to 1.1 with 8.8 ml of concentrated hydrochloric acid. Epichlorohydrin (34.2 g) was added, then stirred at room temperature. During the course of the reaction the pH rose to 7.3, after which the pH was adjusted to 1.55 with concentrated hydrochloric acid. The resulting latex had a solids content of 37 °.
Example 22
To a reaction vessel was added 200 g of distilled water, 0.24 g of acetic acid, 3.64 g of sodium acetate and 1 g of isopropanol. This was heated to 60 ° C under nitrogen and kept at this temperature for 15 minutes. Methylolacrylamide (40 g in 160 g distilled water), methyl diallyl ammonium chloride (13.3 g in 53.1 g distilled water) and ammonium persulfate (0.8 g in 20 g distilled water) were added simultaneously and dropwise over a period of about 1.8 hours, followed. of stirring for one hour. The viscous copolymer solution was cooled to room temperature and the pH changed from 5.0 to
7.2 with 1.4 ml of 5M NaOH. The total solids content of the reaction mass was 12.8%. The latex synthesis consisted of adding 493 g of distilled water, 54.4 g of a 10 Vig aqueous solution of the copolymer, and heating it to 89 ° C under nitrogen. 164 g of a 10% aqueous solution of the copolymer, styrene (218 g) and ammonium persulfate (6 g in 24.2 g distilled water) were added simultaneously over a period of 2 hours. The temperature was adjusted between 89 and 9'6 ° C. After stirring for 15 minutes, the latex was cooled to room temperature and filtered through a 100 mesh screen. The filtered latex had a solids content of 26%.
Example 23
To a reaction vessel was added 200 g of distilled water, 0.24 g of acetic acid, 3.6 4 g of sodium acetate and 1.5 g of isopropanol. This was heated to 60 - 62 ° C under nitrogen, and kept at this temperature for 15 minutes. Methyl oil acrylamide (40 g in 160 g distilled water), dimethyldiallyl ammonium chloride (13.3 g in 53.1 g distilled water) and ammonium persulfate (0.8 g in 20 g distilled water) were added simultaneously and dropwise over a period of two Glues, then stirred. for an hour. The copolymer solution, which had a solids content of 12.3%, was cooled to Lill room temperature, and the pH was adjusted to 7.3 to 0.5 ml. <sup>r</sup>> M NaOII. To eLL reaction vessels was added 439 g of distilled water, 54.4 g of 10% aqueous solution of the copolymer indicated. The contents of the reaction vessel were heated to 88-90 ° C under nitrogen. 164 g of a 10% aqueous solution of the specified copolymer, 218 g of styrene and 6 g of ammonium persulfate
7910339-6 in 24.2 ml of distilled water was added simultaneously, dropwise over a period of about 2 hours, to the reaction vessel. After the addition was complete, the contents of the vessel were stirred for 15 minutes and cooled to room temperature. The resulting latex had a solids content of 25.4%.
Example 24
To a reaction vessel was added 170 ml of distilled water, which was heated to 85 ° C under nitrogen injection. After blowing for 15 minutes, acrylamide (110.3 g in 257.3 ml distilled water), methyldiallyl ammonium acetate (133.2 g of a 29.8% aqueous solution) and ammonium persulfate (7.5 g in 71.3 ml distilled water) were added. simultaneously and dropwise over a period of 1.75 hours, then stirred for 15 minutes and cooled Total solids = 20.4%, RSV = 0.35 (1 M NaCl, 1%, 25 ° C).
The latex synthesis consisted of adding 798 ml of distilled water to the reaction vessel and 1308 g of a 10% aqueous solution of the copolymer produced. This was heated to 93 ° C under nitrogen. Styrene (1308 g), t-butyl, hydroperoxide (14.6 g in 127.6 g distilled water) and sodium formaldehyde sulfoxylate (14.4 g in 127.8 ml distilled water) were added simultaneously and dropwise over a period of 3 hours, after which followed stirring for 15 minutes and cooling to room temperature. The latex was filtered through a 100 mesh screen. Total solids content = 39.7%. Particle size = 0.65 µm - measured according to Loebel - see Table 5.
Example 25
Glyoxal modification of the latex of Example 24 was carried out as follows: 214 g of the latex was placed in a reaction vessel. The pH was changed from 4.9 to 8.5 with
1.4 ml of 5M NaOH. Glyoxal (9.3 µl 13.9 g distilled water) was added to give a pH of 6. This was changed to
8.5 with 1.3 ml of 5M NaOH. The latex-glyoxal mixture was stirred and the pH of the mixture was maintained at 8.5 by periodic additions of a total of 0.2 ml of 5M NaOH. After about 30 minutes the viscosity increased from 31 - 61 cP. The reaction was terminated by the addition of 0.4 ml of concentrated Total content
7910339-6 solid 39.2%.
Example 26
The latex of Examples 24 and 25 was evaluated as paper filler according to the method described in Example 6. The results are presented in Table 8.
Table 8
<td>filling</td><td></td><td>grammage</td><td>Dry draft</td><td>Mullen</td><td>Opacity</td>
<td>average</td><td></td><td>(kg / 1000 m<sup>2</sup>)</td><td>strength</td><td>blast</td><td> %</td>
<td> (¾)</td><td></td><td></td><td></td><td>strength</td><td></td>
<td></td><td></td><td></td><td></td><td>(Kg / cm<sup>2</sup>)</td><td></td>
<td>Nothing</td><td></td><td> 65,8</td><td> 3,16</td><td> 2,17</td><td> 79,4</td>
<td>Example 24</td><td> (4)</td><td> 67,1</td><td> 3,11</td><td> 2,29</td><td> 86,2</td>
<td> 24</td><td> (8)</td><td> 68,9</td><td> 2,68</td><td> 1,93</td><td> 89,2</td>
<td> 25</td><td> (4)</td><td> 67,6</td><td> 3,49</td><td> 2,53</td><td> 86,3</td>
<td> 25</td><td> (8)</td><td> 68,9</td><td> 3,15</td><td> 2,17</td><td> 89,3</td>
<td>Kaolin clay '<sup>1</sup></td><td> · (10)</td><td> 72,0</td><td> 2,72</td><td> 1,55</td><td> 86,2</td>
<td></td><td> (20)</td><td> 77 ,5</td><td> 2 ,25</td><td> 1,26</td><td> 89,4</td>
* 0.05% of cationic polyacrylamide based on the paper weight was used as retention agent for the kaolin clay.
(1)
Opacity measured according to Tappi Standard T-425 (Diano Opacity Meter)
Example 27
A water jacket fitted with a thermometer, a stirrer, a condenser and four separating funnels was filled with 30.0 g of distilled water, 0.6 g of acetic acid and 0.85 g of sodium acetate. In the separating funnels were placed: (1) 60.0 g of styrene, (2) 6.0 g of chitosan, 6.0 g of acetic acid and 114.0 g of distilled water, (3) 0.65. .g of a 20% aqueous solution of t-butyl hydroperoxide and 25.0 g of distilled water, and (4) 0.65 g of sodium formaldehyde sulfoxylate and 25.0 g of distilled water. The contents of the vessel were stirred and heated to 88 ° C. The contents of the four funnels were added dropwise over a period of 4 hours while maintaining the vessel at a temperature of 60 ° C. After heating for another 30 minutes, the product was cooled to room temperature. Not all styrene reacted and did not react styrene
7910339-6 was removed with a rotary evaporator. The product was a latex with a solids content of 28.8 percent. The pax wicks of this latex were evaluated as filler for paper by the method described in Example 6. The results are presented in Table 9.
Table 9
<td rowspan="2">Fillers. (%).</td><td colspan="2" rowspan="2">grammage (kp / 1000 m<sup>2</sup>)</td><td colspan="2">(1) Opacity Dry draft</td><td rowspan="2">Mull explosive strength (kp / cm<sup>2</sup>)</td>
<td> (¾).</td><td>strength</td>
<td>Nothing</td><td></td><td> 66,11</td><td> 80,0-</td><td> 3,36</td><td> 2,24</td>
<td>Example 27</td><td> (4)</td><td> 66,5</td><td> 84,1</td><td> 3,31</td><td> 2 ,03</td>
<td>Kaolin clay</td><td> (10)</td><td> 72,7</td><td> 85,7</td><td> 2,72</td><td> 1,62</td>
<td></td><td> (20)</td><td> 75,4</td><td> 87,5</td><td> 2,38</td><td> 1,31</td>
<td>Commercial</td><td></td><td></td><td></td><td></td><td></td>
<td>Polystyrene*</td><td> (4)</td><td> 66,8</td><td> 83,5</td><td> 3,16</td><td> 1,99</td>
<td></td><td> (8)</td><td> 67,1</td><td> 86,1</td><td> 2,91</td><td> 1,85</td>
* 0.05% of commercial polyacrylamide, based on the weight of paper, was used as retention agent for the filler (1)
Opacity measured according to Tappi Standard T-425 (Hunter Opacity Meter)
The outstanding advantages of the present pigments are best shown by the data in Tables 1 and 2. The organic pigments were added in amounts of 4% and 8% and compared to kaolin clay added in amounts of 10% and 20% (equivalent to 4% by volume and 8% by volume of the present organic pigments). Alum and a high molecular weight cationic polyacrylamide were used as a retention agent for kaolinic acid. No retention agent is used with the present organic pigments. The filler containing the opacity of the paper is a measure of the retention of the filler in the paper.
Dry tensile strength and Mullen burst strength data in Table 2 show the strength properties obtained with the present organic pigments. It can be seen that kaolin clay reduces the strength properties relative to paper
7910339-6 without filler by about 20 - 30%. The present organic pigments, on the other hand, give the highest opacity values (compositions according to Examples 3 and 4) and also give better strength by about 5 - 15% compared to paper without filler. In relation to clay, with the present organic pigments, an opacity which is equivalent to that of the clay is obtained and 20 - 50% higher strength properties.
A further advantage of the present filler is shown in Table 2. The clay-filled paper is substantially heavier than the container, while paper containing the present filler is only slightly heavier than the weight of the control.
The data in Tables 3 and 4 summarize the evaluation of a similar series of organic pigments which have been stabilized using acrylamide dimethyldiallylammonium chloride copolymers as the water-soluble cationic prepolymer but which have not reacted with glyoxal. Because the particles lack reactive functionality, the strength properties were poorer in this experiment than in the past.
The data in Tables 5 and 6 summarize a similar experiment in which the organic pigments were prepared using various copolymers of acrylamide and methacryloyloxyethyl trimethylammonium methyl sulfate as the water-soluble cationic prepolymer. Because the particles lacked reactive functionality, the strength properties were slightly inferior to those of the control but always significantly better than those of paper with clay as filler. For further comparison, a commercially available polystyrene latex was evaluated in this experiment. The particles in this latex have anionic charges, so alum and a polymeric retention model are used. The data show that all the polystyrene particles produced paper with slightly higher opacity than the present organic pigments (but also greater surface weight). The polystyrene particles degraded the paper strength, although not as much as the clay.
The data in Table 7 shows that conventional fillers, such as clay and polystyrene, require retention agents for
7910339-6 optimal design. Without retention means. the opacity is very low in both cases. As shown in Tables 2, 4 and 6, the present organic pigments provide good opacity without the use of retention agents.
Example 28
A water jacket fitted with a thermometer, a stirrer, a condenser and a separating funnel is filled with 89 grams of distilled water and 436 grams of a 10% aqueous solution of poly (ethyldiallylammonium chloride). The resulting solution was heated to 87-88 ° C by circulating heated water through the jacket of the reaction vessel. Styrene (425.2 grams) and divinylbenzene (10.9 grams) were mixed and placed in the separator funnel. 13.3 g of a 90% aqueous solution of t-butyl hydroperoxide and 108 grams of distilled water were placed in a burette; and 13.6 grams of sodium hydrogen sulfite, dissolved in 124.5 grams of distilled water, were placed in a second burette. The mixture of styrene and divinylbenzene; t-butylhydroperoxidlösningen; and the sodium hydrogen sulfite solution was added dropwise, simultaneously, over a period of 2 hours to the reaction vessel. After stirring for 20 minutes, a slight odor was noticed by the styrene. Additional tbutyl hydroperoxide solution (3.4 grams of t-butyl hydroperoxide dissolved in 27 grams of distilled water) and additional sodium hydrogen sulfite solution (3.4 grams of sodium hydrogen sulfite dissolved in 31 grams of distilled water) were added to the reaction mass, and the reaction mixture was stirred for an additional 20 minutes. The resulting latex was cooled to room temperature and filtered through a 100 mesh screen. Total solids content = 27.7%. Particle size = 0.8 µm - measured in a Coulter counter.
As can be seen from the foregoing, polyethylenically unsaturated monomers, such as divinylbenzene, can be used in admixture with monoethylenically unsaturated monomers to obtain cross-linked graft copolymer particles. Examples of suitable polyethylenically unsaturated monomers used which may be used for this purpose are diallyl phthalate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol di7910339
3 methacrylate, trivinylbenzene, divinylnaphthalene, dially imaleate, diallyl fumarate, trimethylolpropane trimethacrylate and pentaurytritol tetracrylate. The preferred polyethylenically unsaturated monomers, also referred to as cross-linking monomers, are divinylbenzene, diallyl phthalate, ethylene glycol dimethacrylate and 1,3-butylene glycol dimethacrylate.
Although the present organic pigments have particular utility as a filler in paper, they can also be used in paper coatings together with a suitable binder. In addition, they can be used in colors, inks and the like. They can also be applied as a coating? together with a suitable binder on glass surfaces, metal surfaces, wooden surfaces, plaster surfaces and the like.
Example 29
One vessel fitted with a water jacket and equipped with a thermometer, a stirrer, a condenser and three separating funnels was filled with 75.0 g of distilled water. To the separating funnel were added: separating funnel (1) 35.0 g of acrylamide (0.49 mol) in 70.0 g of distilled water, separating funnel (2) 15.0 g of vinyl benzyl trimethylammonium chloride (0.07 mol) in 60.0 g of distilled water and separating funnel (3) 1.25 g of ammonium persulfate in 50.0 g of distilled water. The contents of the vessel were heated to 80 ° C, and the contents of the separatory funnels were added dropwise over a period of 2.5 hours while maintaining the temperature at 80 - 85 ° C. After heating for an additional 30 minutes, the solution was cooled to room temperature (about 23 ° C). The product solution contained 22.0% solids and had an RSV, reduced specific viscosity, of 0.27 (1% solution in IM NaCl, 25 ° C).
A vessel equipped with the water jacket and equipped with a thermometer, a stirrer, a condenser and three separating funnels was filled with 503.8 g of distilled water and 26.2 g of the above copolymer solution (5.8 g of dry copolymer). To the funnels were added the following: separating funnel (1) 78.6 g of the above copolymer solution (17.3 g of dry copolymer) and 120.0 g of distilled water, separating funnel (2) 230.0 g of styrene, and separating funnel (3) , 1 g of ammonium persulfate i
7910339-6
120.0 g of distilled water. The contents of the vessel were stirred and heated to 79 ° C. The contents of the three separating funnels were added dropwise over a period of 4 hours while maintaining the vessel temperature at 79 - 88 ° C. After heating for a further 15 minutes, the product was cooled to room temperature, and the pH was changed from 1.9 to 7.5 with 25% sodium hydroxide solution. The product was filtered through a 100 mesh screen. The product was a white latex containing 25.1% solids and having an average particle size of 0.62 µm (according to AB Loebel, Official Digest, 200, February 1959).
Example 30
200 g of distilled water was filled into a vessel fitted with a water jacket and equipped with a thermometer, a stirrer, a condenser and two separating funnels. Into the separating funnel were added: separating funnel (1) 77.0 g of acrylamide (1.08 mol), 17.1 g of 4-vinylpyridine (0.16 mol) and 16.0 g of concentrated hydrochloric acid solution (0.19 mol) in 200 g distilled water, and separating funnel (2) 2.5 g of ammonium persulfate in 100 g of distilled water. The contents of the vessel were heated to 80 ° C and the contents of the separatory funnels were added dropwise over a period of 2 hours and 25 minutes while maintaining the temperature at 80 - 85 ° C. After heating for another 30 minutes, the solution was filled to room temperature (about 23 ° C). The product solution contained 21.6% solids and had an RSV, reduced specific viscosity, of 0.34 (1% solution IM NaCl, 25 ° C).
A water jacket equipped with a thermometer, a stirrer, a condenser and three separator funnels was filled with 503.4 g of distilled water and 26.6 g of the above copolymer solution (5.7 g of dry copolymer). Filled in the separating funnel: separating funnel (1)
79.8 g of the above polymer solution (17.2 g dry copolymer) and 120 g distilled water, separating funnel (2) 230 g styrene, and separating funnel (3) 5.1 g ammonium persulfate in 120.0 g distilled water. The contents of the vessel were stirred and heated to 78 ° C. The contents of the separating funnels
79'10339-6 was added dropwise at the same time. The contents of the separating funnels (i) and (2) were added over a period of 4 hours. The contents of the separating funnel (3) were added over a period of 4 hours and 15 minutes. The temperature of the vessel was kept at 78 84 ° C for the time being, for the addition. The product is cooled to room temperature and its pH changed from 2.0 to 4.6 with 10% sodium hydroxide solution. The product was filtered through a 100 mesh screen. The product was a wide latex containing 25.8% total solids and with an average particle size of 0.45 µm (according to Loebel, Official Digest, 200, February, 1959).
Example 31
A water jacket fitted with a thermometer, a stirrer, a condenser and two separating funnels were filled with 200 g of distilled water. To the separating funnels were added the following: separating funnel (1) 69.0 g of acrylamide (0.97 mol) and 31.0 g of methacrylamidopropyltrimethylammonium chloride (0.14 mol) in 200 g of distilled water and separating funnel (2) 2.5 g of ammonium persulfate in 100 g Distilled water. The contents of the vessel were heated to 77 ° C, and the contents of the separatory funnels were added dropwise over a period of 2.5 hours while maintaining the temperature at 77 - 85 ° C. After heating for an additional 15 minutes, the solution was cooled to room temperature (about 23 ° C). The product solution contained 22.7% solids and had a RSV, reduced specific viscosity, of 0.52 (1% solution in 1 M NaCl, 25 ° C).
In a water jacket equipped and ined with a thermometer, a stirrer, a condenser and three separating funnels, 504.7 g of distilled water and 25.3 g of the above polymer solution (5.7 g dry copolymer) were filled. The separating funnel was filled: separating funnel (1) 76.1 g of the specified copolymer solution (17.3 g dry copolymer) and 120.0 g distilled water, separating funnel (2) 230.0 g styrene and separating funnel (3) 5.1 g ammonium persulfate in 120 g of distilled water. The contents of the vessel were stirred and heated to 79 ° C. The contents of the three separating funnels were added dropwise and simultaneously. Content of
7910339-6 separating funnel (1) and (2) were added over a period of four hours. The contents of the separating funnel (3) were added over a period of 4 hours and 15 minutes. The temperature of the vessel was maintained at 79 - 87 ° C during the additions. The product was cooled)
room temperature, and the pH was changed from 2.1 to 8.0 with 25% sodium hydroxide solution. The product was filtered through a 100 mesh screen. The product was a latex containing .2 5.5% total solids content and has an average particle size of 0.47 µm (according to Loebel, Official Digest, 200, February 10, 1959).
Example 32
In a water jacket equipped with a thermometer, a stirrer, a condenser and two separating funnels, 200 g of distilled water was filled. The separating funnels were filled: separating funnel (1) 67 g of acrylamide (0.94 mol) and 33 g of 3-methacryloyloxy-2-hydroxypropyl trimethylammonium chloride (0.14 mol) in 200 g of distilled water, and separating funnel (2) 2.5 g of ammonium persulfate in 100 g of distilled water. The contents of the vessel were heated to 80 ° C and the contents of the funnels were added dropwise over a period of hours and 25 minutes while maintaining the temperature at 80 - 84 ° C. After heating for an additional 15 minutes, the solution was cooled to room temperature (about 23 ° C). The product solution contained 21.3% solids and had an RSV, reduced specific viscosity, of 0.46 (1% solution IM NaCl, 25 ° C).
In a water jacket equipped with a thermometer, a stirrer, a condenser and three separating funnels, 503 g of distilled water and 27 g of the above copolymer solution (5.8 g dry copolymer) were filled. 1 separator funnel was filled: separator funnel (1) 81 g of the above copolymer solution (17.3 g dry copolymer) and 120 g distilled water, separator funnel (2) 230 g styrene, and separator funnel (3) 5.1 g ammonium persulfate in 120 g Distilled water. The contents of the vessel were stirred and heated to 77 ° C. The contents of the separating funnels were added dropwise at the same time. The contents of the separating funnels (1>
7910339-6 and (2) were added over a period of 4 hours. The contents of the separatory funnel (3) were added over a period of 4 hours 5 minutes. The vessel temperature was maintained at 77 - 88 ° C throughout the addition. The product was cooled to room temperature and the pH was changed from 1.9 to 6.5 with 25 Vig sodium hydroxide solution. The product was filtered through a 100 mesh screen. The product was a white latex containing
25.5 ό total solids with an average particle size of 0.8 µm (according to Loebel, Official 'Digest, 200, February, 1959).
Example 33
The compositions of Examples 29 - 32 were evaluated as filler for paper. Hand sheets were made on a device by Noble & Wood. The pulp consisted of a 50:50 blend of bleached hardwood and bleached softwood pulp which had been ground to a Canadian Standard Freeness of 500. The paper was made at a pH of 4.5 (sulfuric acid, no alum). The latex was evaluated at addition levels of 4 a and 8% (on a dry basis). The check was paper without filler. The experimental results for the papers are summarized in Table 20 10.
The present new organic pigments can be used alone or in combination with other organic pigments and / or inorganic pigments as fillers and coatings for paper.
7910339-6
Table 10, „·. , ,,
Dry drag-Mullen-<sup>kd</sup>' ' (1) (2)
Surface layer Opacity Lightness strength explosive strength
Filler (%) (kp / 1000 nT) (¾) (kp / cm) (kp / cm 2) <y
<td>CD</td><td>un</td><td>to</td><td>CM</td><td>CD</td><td></td><td>CO</td><td>ft</td><td>P Φ</td><td>Pi 0)</td>
<td>CM</td><td>ft</td><td>CO</td><td>CO</td><td>ft</td><td>co</td><td>ft</td><td>CM</td><td> £</td><td>Ρ</td>
<td>ft</td><td> 4%</td><td> «1</td><td>O</td><td>ft</td><td>ft</td><td>Λ</td><td> ·></td><td>CD</td><td> 0)</td>
<td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>P</td><td>S</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> ¢)</td><td>ω</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>P</td><td>Ρ</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>rd</td><td>Φ</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 0</td><td>χ:</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>(ΰ</td><td>ω</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ft</td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ο</td><td>• ΓΟ</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
O
<td colspan="9"></td><td>Pi</td><td colspan="4"> 0</td>
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<td>ο</td><td>ft</td><td></td><td>ft</td><td>ft</td><td>ft</td><td>«X</td><td>ft</td><td>ft</td><td>O</td><td></td><td>• r4</td><td></td><td></td>
<td>CO</td><td>co</td><td>co</td><td>CO</td><td>CO</td><td>co</td><td>CO</td><td>CO</td><td>co</td><td></td><td></td><td>Q</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>X></td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>m</td><td></td><td></td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CM</td><td></td><td>CM</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ID</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 1</td><td></td><td>JD</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>E<sup>hrs</sup></td><td></td><td></td><td></td><td></td>
<td>CM</td><td>co</td><td>CD</td><td>CD</td><td>LO</td><td> 00</td><td>ft</td><td>co</td><td>CD</td><td></td><td></td><td></td><td></td><td></td>
<td>r »</td><td>Λ</td><td>ft</td><td>ft</td><td>ft</td><td>ft</td><td>ft</td><td>ft</td><td>ft</td><td>£ in</td><td></td><td>TJ</td><td></td><td></td>
<td>Ο</td><td>τ<sup>-</sup>1</td><td>CM</td><td>co</td><td>un</td><td>CM</td><td>CO</td><td>CD</td><td>CO</td><td>ftf</td><td></td><td>Pi</td><td></td><td></td>
<td>co</td><td>CO</td><td>co</td><td>co</td><td> 00</td><td> 00</td><td>co</td><td>Γ-</td><td> 00</td><td>Ό</td><td></td><td>rtf</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Pi</td><td></td><td>Ό</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>rtf</td><td></td><td>C</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>P</td><td></td><td>rtf</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ω</td><td></td><td>P</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ω</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ft</td><td></td><td></td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ft</td><td></td><td>•HRS</td><td></td><td></td>
<td>XT</td><td>Jd *</td><td>O</td><td>CM</td><td>O</td><td>co</td><td>rh</td><td>ΟΟ</td><td> 00</td><td>ft</td><td></td><td>ft</td><td></td><td></td>
<td>ft</td><td> <·.</td><td>ft</td><td>ft</td><td>ft</td><td>ft</td><td>ft</td><td>ft</td><td>ft</td><td>rtf</td><td></td><td>ft</td><td></td><td></td>
<td>co</td><td>CO</td><td>co</td><td>CD</td><td>co</td><td>CO -</td><td>Ή</td><td>LO</td><td>O</td><td>ft</td><td>λ:</td><td>rtf</td><td>rX</td><td>, X</td>
<td>Γ-</td><td>Γ-</td><td>co</td><td>Γ-</td><td>co</td><td>Γ-</td><td> 00</td><td>c</td><td>co</td><td></td><td>:O</td><td>ft</td><td> :0</td><td> :0</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>P</td><td>ID</td><td></td><td>CD</td><td>ω</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>bD</td><td>P <</td><td>P</td><td>P <</td><td>Pi</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ft</td><td> :0</td><td>stay</td><td> :0</td><td> :0</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>t-1</td><td>P</td><td>ft</td><td>ft</td><td>ft</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>C</td><td></td><td>rd</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ω</td><td>j ·</td><td>Pi</td><td>R</td><td>co</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 0)</td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>p</td><td> ></td><td></td><td> ></td><td> ></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>P</td><td>rtf</td><td>P</td><td>rtf</td><td>(tf</td>
<td>ιο</td><td>ΟΟ</td><td>co</td><td>ΙΟ</td><td>CD</td><td>ΟΟ</td><td>CD</td><td>O</td><td> 00</td><td>: rtf</td><td></td><td>P</td><td></td><td></td>
<td></td><td>Λ</td><td>n</td><td>n</td><td>n</td><td>ft</td><td>n</td><td>ft</td><td>ft</td><td>g</td><td>Q)</td><td>: rtf</td><td>Q)</td><td><D</td>
<td></td><td>LO</td><td>co</td><td> 00</td><td>CD</td><td>Γ-</td><td>Γ-</td><td></td><td>Γ-</td><td></td><td>Ό</td><td>S</td><td>Ό</td><td>T)</td>
<td>CD</td><td>co</td><td>CD</td><td>CD</td><td>CD</td><td>ΙΟ</td><td>ΙΟ</td><td>CO</td><td>ΙΟ</td><td>P</td><td>Pi</td><td></td><td>Pi</td><td>Pi</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Φ</td><td>: «Tf</td><td>P</td><td>: rtf</td><td>: rtf</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>P</td><td> ></td><td>Φ</td><td> ></td><td> ></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ft</td><td>ft</td><td>ΛΙ</td><td>ft</td><td>ft</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>υ</td><td>Q)</td><td>ω</td><td> 0)</td><td>al)</td>
<td></td><td>ζ-χ</td><td>F-X</td><td></td><td>Z 'X</td><td>z ~ x</td><td>ζ * · χ</td><td></td><td>z x</td><td>HI</td><td>T1</td><td></td><td>Tj</td><td>Tj</td>
<td></td><td>ZT</td><td>CD</td><td></td><td>CO</td><td>J-</td><td>co</td><td></td><td>co</td><td>ft</td><td>Φ</td><td>• n</td><td>a)</td><td>al)</td>
<td></td><td>κ_ζ</td><td>XZ</td><td>x_></td><td></td><td>X /</td><td>x_z</td><td>x_z</td><td></td><td>O</td><td>TL</td><td>ft</td><td>Oath</td><td>XI</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>zx</td><td></td><td>zx</td><td></td><td>p ~ x</td>
<td></td><td>cn</td><td></td><td>O</td><td></td><td>ft</td><td></td><td>CM</td><td></td><td>'ft</td><td></td><td>CM</td><td></td><td>co</td>
<td></td><td>CM</td><td></td><td>CO</td><td></td><td>CO</td><td></td><td>CO</td><td></td><td>x_z</td><td></td><td>xz</td><td></td><td>XZ</td>
<td></td><td> 1“1</td><td></td><td>ft</td><td></td><td>ft</td><td></td><td>ft</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td> 0)</td><td></td><td>G)</td><td></td><td>(D</td><td></td><td> 0)</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Ρ</td><td>ft</td><td></td><td>ft</td><td></td><td>ft</td><td></td><td> &</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>(ϋ</td><td>e</td><td></td><td>s</td><td></td><td> 6</td><td></td><td>S</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>b0</td><td>Φ</td><td></td><td>Φ</td><td></td><td>Φ</td><td></td><td>Q)</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>C</td><td>X</td><td></td><td>X</td><td></td><td>X</td><td></td><td>X</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Μ</td><td>w</td><td></td><td>W</td><td></td><td>W</td><td></td><td>M</td><td></td><td></td><td></td><td></td><td></td><td></td>
7910339-6
Contents48
44 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44
28 members in 5 offices
Priority claims7
| Document | Office | Kind | Date |
|---|---|---|---|
| 80333077 | United States of America | A | |
| 80333077 | United States of America | A | |
| 90960678 | United States of America | A | |
| 90960678 | United States of America | A | |
| 7910339 | – | – | – |
| US19770803330 | – | – | – |
| US19780909606 | – | – | – |
Members28
| Document | Office | Kind | |
|---|---|---|---|
| US4235982A | United States of America | A | |
| ATA403278A | Austria | A | |
| SE7910339L | Sweden | L | |
| SE8100725L | Sweden | L | |
| US4281082A | United States of America | A | |
| US4282060A | United States of America | A | |
| GB1595145A | United Kingdom | A | |
| US4293666A | United States of America | A | |
| US4293667A | United States of America | A | |
| US4311809A | United States of America | A | |
| AT365615B | Austria | B | |
| US4343729A | United States of America | A | |
| US4348257A | United States of America | A | |
| US4349641A | United States of America | A | |
| US4353818A | United States of America | A | |
| CA1134091A | Canada | A | |
| US4369292A | United States of America | A | |
| US4403062A | United States of America | A | |
| US4403063A | United States of America | A | |
| US4404310A | United States of America | A | |
| US4414353A | United States of America | A | |
| US4426483A | United States of America | A | |
| US4434267A | United States of America | A | |
| US4456724A | United States of America | A | |
| US4469555A | United States of America | A | |
| SE435845BThis record | Sweden | B | |
| US4483959A | United States of America | A | |
| SE440660B | Sweden | B |
2 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
| Patent has lapsedLapsedNUG | NUG | |
| Patent in forceNAL | NAL |
Numbers
- Publication, DOCDB
- 435845
- Publication, EPODOC
- SE435845
- Application
- 7910339
- Application, DOCDB
- 7910339
- Application, EPODOC
- SE19790010339
Titles2
- Swedish
- LATEX AV VATTENOLOSLIGA YMPPOLYMERPARTIKLAR, FORFARANDE FOR DESS FRAMSTELLNING SAMT ANVENDNING DERAV SOM FYLLMEDEL I PAPPER
- English
- LATEX OF WATER-INSULATIVE GUMPOLYMER PARTICLES, PROCEDURE FOR ITS PREPARATION AND USE OF IT AS FILLING PAPER
Classification
- CPC, 4
- D21H17/455
- C08F265/10
- C08F271/00
- D21H21/285
- IPC, 4
- C08F265 10
- C08F271 00
- D21H17 45
- D21H21 28