EP0014026B1 - Teilweise gehärtete Aminoaldehydharzfasern enthaltendes Papier und Verfahren zu dessen Herstellung - Google Patents
Teilweise gehärtete Aminoaldehydharzfasern enthaltendes Papier und Verfahren zu dessen Herstellung Download PDFInfo
- Publication number
- EP0014026B1 EP0014026B1 EP80300016A EP80300016A EP0014026B1 EP 0014026 B1 EP0014026 B1 EP 0014026B1 EP 80300016 A EP80300016 A EP 80300016A EP 80300016 A EP80300016 A EP 80300016A EP 0014026 B1 EP0014026 B1 EP 0014026B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibres
- amino
- paper
- aldehyde resin
- aldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H5/00—Special paper or cardboard not otherwise provided for
- D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
- D21H5/20—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of organic non-cellulosic fibres too short for spinning, with or without cellulose fibres
Definitions
- This invention relates to paper in which at least a proportion of the fibrous component consists of fibres formed from an amino/aldehyde resin.
- the properties of the paper may be improved if certain amino/aldehyde resin fibres are employed.
- the tensile and burst strengths may be improved.
- paper is made from amino/aldehyde resin fibres that have been cured to 50-90% by heating at above 80°C prior to paper formation.
- Such paper has different properties from that described in aforementioned FR-A-2365001.
- the fibrous content consists of amino/aldehyde resin fibres that are free of carbohydrate and bound inorganic oxyacid radicals and that have been cured, prior to incorporation into the paper, to a degree of cure of between 30 and 90% by heating at above 80°C.
- Such partially cured amino/aldehyde resin fibres have a controlled solubility in water: the degree of water solubility is such that the fibres are stable enough to be dispersed in water and incorporated into paper with unacceptable weight loss, and have adequate strength and resistance to damage by the paper making process but have the ability to bond with themselves and with cellulose fibres in paper structures.
- the degree of cure is assessed by determining the proportion of fibre dissolved in water under specified conditions.
- the test procedure is as follows: A sample (approx 5 g) of the fibre that has previously been dried at 100°C is accurately weighed and then digested with 200 ml of water for 2 hours at 50°C. The undissolved fibre remaining is recovered by filtration and dried at 100°C in air for 2 hours and then reweighed. The (%) degree of cure is defined as
- Amino/aldehyde resin fibres that are free of bound inorganic oxyacid radicals and that have been described, for example in aforesaid DE-A-2810299 and EP-A-9322, for use in paper compositions, have generally been cured using a catalyst such as ammonium sulphate for 3 or more hours at 120°C. Such fibres have a degree of cure of 90-92% or more.
- the fibres of use in the present invention have a degree of cure in the range 50 to 90%, preferably 60 to 85%.
- the amino/aidehyde resins are made, as is well known in the art, by reacting a polyfunctional amine, such as urea or melamine, with an aldehyde, particularly formaldehyde.
- a polyfunctional amine such as urea or melamine
- aldehyde particularly formaldehyde
- the reaction is generally performed in aqueous solution using a molar excess of the aldehyde.
- the aldehyde/urea molar ratio is preferably in excess of 1.2:1 and is preferably in the range 1.5:1 to 2.5:1.
- Preferred amino resins are made by reacting urea, optionally phenol and/or melamine in an amount of up to 1 mol of phenol and/or melamine per mol of urea, with formaldehyde, the amount of formaldehyde being such that the molar ratio of formaldehyde to urea (plus any phenol and/or melamine) is in the range 1.5:1 to 2:1.
- the reaction between the amine and aldehyde should be conducted in the absence of any significant amount of inorganic oxyacid radicals that can become bound into the resin.
- the total amount of any sulphite, phosphite, phosphate, or borate should be less than 0.5 mols per 100 mols of aldehyde.
- a curing catalyst is added and the resin is spun into fibres.
- the nature and amount of catalyst, together with the spinning and any post spinning heat treatment conditions, will determine the degree of cure for any given resin.
- weak catalysts include di(ammonium) hydrogen phosphate and ammonium formate: moderate catalysts include formic acid, ammonium sulphate, ammonium chloride and dihydrogen ammonium phosphate; while strong catalysts include phosphoric, sulphuric sulphamic and hydrochloric acids.
- the amount of catalyst employed with generally be within the range 0.05 to I % by weight of the resin solids.
- the time necessary to effect the required degree of curing will naturally depend on the nature and quantity of catalyst employed, but for any given catalyst and concentration will depend on the curing temperature: at low temperatures longer times are required than at high temperatures.
- the curing will generally be effected at temperatures of 80 to 200°C: at temperatures below 100°C a time of several hours may be necessary while at above 180°C the curing time will generally be less than 5 minutes.
- the curing conditions necessary to obtain the desired degree of cure can be determined by simple experimentation. In determining the curing time it should be appreciated that some curing may take place during the spinning process used to convert the resin to the fibrous form.
- the resin may be converted into fibres by conventional spinning of a viscous resin syrup into hot air (“dry spinning") or into an acid bath (“wet spinning”).
- the fibres can be formed by passing a fine stream or series of drops into a flowing resin-gelling liquid or by gas fibrillation (in particular air fibrillation) by means of a co-current or transverse gas stream. This process is described in the aforesaid DE-A-2754525.
- the resin may be spun by tack spinning, by pulling the resin between two surfaces to which it adheres and subsequently severing the fibres from the surfaces.
- the resin may be moved into contact with a pair of belt surfaces so as to deposit it thereon, whereafter the surfaces of the belt are moved apart to form fibres and stretch them, and the fibres are detached and collected.
- Another, and preferred, method of forming the fibres is by centrifugal spinning, for example by the process described in DE-A-2810535.
- a spinning aid such as a water soluble high molecular weight polymer, eg polyvinyl alcohol or polyethylene oxide, is added to the resin prior to spinning.
- Fillers, pigments, optical brighteners and other additives may be added to the fibres provided they do not interfere with the attainment of the desired level of cure.
- the fibres are preferably unbranched and may be either straight or crimped.
- the fibres may be of circular or irregular cross section.
- Advantageously fibres of elliptical cross section are employed as these facilitate lay down of the paper sheet. The aforesaid centrifugal spinning process can give such fibres.
- the fibres should have a mean diameter of 1 pm to 30 pm (for irregular fibres, average diameters are taken). More particularly the average is between 2 and 20 p, particularly between 5 and 15 ⁇ m. There may be present, advantageously, a range of fibre diameters from 1 pm to 30 pm to enable the formation of paper of uniform density.
- the fibres used in the present invention characteristically have an average length of at least 1 mm.
- Long fibres (more than 2 mm) can be incorporated into papers without causing problems of premature flocculation in the paper making process and hence uneven formation of the sheet. It may therefore be desirable to use fibres that are as long as the papermaking process can accommodate.
- the practical upper limit to the length may therefore be, for this reason, in the range 5 to 10 mm.
- a minor degree of branching of the fibres may be present (due to fusion during production of the fibres) but preferably the fibres are essentially unbranched.
- Crimped fibres tend to be bulky, and characteristically their bulk density is low.
- the fibres produced by the spinning process may be reduced in length to that required for papermaking. This can be achieved by cutting, passing through rollers or milling, or by wet disintegration as is well known in the paper industry.
- the fibres should be cured to the desired degree of cure prior to any such disintegration process.
- the amino aldehyde resin fibres preferably have an average strength of at least 50 MNm- 2 when measured on a tensile test.
- Paper may be made from the amino/aldehyde resin fibres alone, or in admixture with other fibrous material, such as other synthetic resin fibres, or, preferably, with cellulose pulp.
- the paper should contain at least 1% by weight of the partially cured amino/aldehyde resin fibres and preferably contains at least 5% by weight of such fibres.
- Amino/aldehyde resin fibres having a higher degree of cure may be incorporated, if desired, in addition to the partially cured fibres.
- the fibrous component of the paper comprises 5-95% by weight of the partially cured amino/aldehyde resin fibres in admixture with cellulose pulp.
- the cellulose pulp may be a mechanical pulp or a chemical pulp. As is well known in the art the properties of the paper will depend on the nature of the pulp and its degree of beating.
- the invention is illustrated by the following Example.
- a commercially available aqueous urea/formaldehyde resin having a U:F molar ratio of 1:2 of solids content 67% by weight was diluted with water to a viscosity of 30 poise (3 Pa's).
- 10% by weight, based on the weight of resin solids of an aqueous solution containing 1.6% by weight poly(ethylene oxide) and 6.7% by weight ammonium sulphate was mixed continuously with the resin solution as it was fed to a spinning cup of a centrifugal spinning apparatus.
- the resin was spun by the process described in aforesaid DE-A-2810535 using a spinning cup of 12.7 cm. diameter having 24 rectangular holes and rotating at 10000 rpm.
- Air at 165°C was blown into the spinning chamber to transport the fibres from the spinning cup and to effect some curing.
- the resin was spun at a rate of 170 g min-'.
- the fibres were continuously removed from the spinning apparatus and cured by heating in air at 200°C for 30 minutes.
- the resultant fibres which had an average diameter of 12 pm, had a degree of curing of 98.4%.
- the fibers were distintegrated in a standard laboratory pulp disintegrator in water (consistency 0.3% by weight) to a length of about 2 mm.
- Paper handsheets were made on standard pulp evaluation equipment from a mixture of equal weights of the UF fibres and a beaten birch sulphate pulp.
- the Burst Index (burst pressure in kNm- 2 divided by the substance in gm- 2 ) was determined.
Landscapes
- Paper (AREA)
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7901930 | 1979-01-19 | ||
GB7901930 | 1979-01-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0014026A1 EP0014026A1 (de) | 1980-08-06 |
EP0014026B1 true EP0014026B1 (de) | 1983-02-09 |
Family
ID=10502606
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80300016A Expired EP0014026B1 (de) | 1979-01-19 | 1980-01-03 | Teilweise gehärtete Aminoaldehydharzfasern enthaltendes Papier und Verfahren zu dessen Herstellung |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0014026B1 (de) |
AU (1) | AU5456780A (de) |
CA (1) | CA1140707A (de) |
DE (1) | DE3061824D1 (de) |
NZ (1) | NZ192586A (de) |
ZA (1) | ZA80108B (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3161960D1 (en) * | 1980-07-29 | 1984-02-23 | Ici Plc | Method of making a laminated sheet material |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2365001A1 (fr) * | 1976-09-21 | 1978-04-14 | Sunden Olof | Structure de papier semi-synthetique a base d'uree |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB572962A (en) * | 1942-05-25 | 1945-10-31 | Sylvania Ind Corp | Paper products and methods of making the same |
US3821074A (en) * | 1972-12-07 | 1974-06-28 | Carborundum Co | Paper from pitch based organic fibers |
GB1573114A (en) * | 1976-12-08 | 1980-08-13 | Ici Ltd | Paper |
-
1980
- 1980-01-03 DE DE8080300016T patent/DE3061824D1/de not_active Expired
- 1980-01-03 EP EP80300016A patent/EP0014026B1/de not_active Expired
- 1980-01-08 ZA ZA00800108A patent/ZA80108B/xx unknown
- 1980-01-11 AU AU54567/80A patent/AU5456780A/en not_active Abandoned
- 1980-01-11 NZ NZ192586A patent/NZ192586A/xx unknown
- 1980-01-18 CA CA000343931A patent/CA1140707A/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2365001A1 (fr) * | 1976-09-21 | 1978-04-14 | Sunden Olof | Structure de papier semi-synthetique a base d'uree |
Also Published As
Publication number | Publication date |
---|---|
DE3061824D1 (en) | 1983-03-17 |
AU5456780A (en) | 1980-07-24 |
CA1140707A (en) | 1983-02-08 |
ZA80108B (en) | 1980-12-31 |
EP0014026A1 (de) | 1980-08-06 |
NZ192586A (en) | 1983-02-15 |
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