GB2172894A - Melamine/formaldehyde and urea/formaldehyde resinous materials - Google Patents

Melamine/formaldehyde and urea/formaldehyde resinous materials Download PDF

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Publication number
GB2172894A
GB2172894A GB08508351A GB8508351A GB2172894A GB 2172894 A GB2172894 A GB 2172894A GB 08508351 A GB08508351 A GB 08508351A GB 8508351 A GB8508351 A GB 8508351A GB 2172894 A GB2172894 A GB 2172894A
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GB
United Kingdom
Prior art keywords
formaldehyde
urea
melamine
resinous material
salt
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.)
Granted
Application number
GB08508351A
Other versions
GB2172894B (en
GB8508351D0 (en
Inventor
Jack Needham Muirhead
John Arthur Elvidge
James Henry Semark
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MUIRHEAD DATA COMMUNICATIONS L
Original Assignee
MUIRHEAD DATA COMMUNICATIONS L
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by MUIRHEAD DATA COMMUNICATIONS L filed Critical MUIRHEAD DATA COMMUNICATIONS L
Priority to GB8508351A priority Critical patent/GB2172894B/en
Publication of GB8508351D0 publication Critical patent/GB8508351D0/en
Publication of GB2172894A publication Critical patent/GB2172894A/en
Application granted granted Critical
Publication of GB2172894B publication Critical patent/GB2172894B/en
Expired legal-status Critical Current

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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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/20—Duplicating or marking methods; Sheet materials for use therein using electric current
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/043—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24
    • C08G12/046—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24 one being urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/09—Sulfur-containing compounds
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)

Abstract

A resinous material comprising a cured melamine/formaldehyde or urea/formaldehyde resin contains sulphamic acid or a salt thereof to reduce emission of formaldehyde from the material. The material may contain a filler, such as a cellulosic filler of natural origin and, in accordance with one preferred embodiment, takes the form of an electrolytic recording paper comprising a higher wet-strength base paper, reinforced with a melamine/formaldehyde or urea/formaldehyde resin, and impregnated with an aqueous solution of an organic compound capable of forming a mark on the paper upon electrolysis together with a water-soluble electrolyte.

Description

SPECIFICATION Melamine/formaldehyde and urea/formaldehyde resinous materials This invention is concerned with improvements in and relating to melamine/formaldehyde and urea/ formaldehyde resinous materials and to composite materials comprising such resinous materials together with a filler.
Important examples of such composite materials are those in which the filler is a cellulosic material of natural origin, such as high wet-strength paper, chipboard blockboard and plywood.
Melamine/formaldehyde and urea/formaldehyde resins serve as satisfactory binders for such composite materials but suffer from one inherent disadvantage; they tend to liberate free formaldehyde.. Formaldehyde is classified as a material which is dangerous to health. Accordingly, persons working in environments where such composite materials are manufactured, stored or used may be exposed to undesirably high levels of formaldehyde in their working environments. It would, accordingly, be desirable to reduce, or indeed substantially eliminate, the amount of formaldehyde released from a composite material containing a melamine/formaldehyde or urea/formaldehyde resinous binder.
It has now been found, in accordance with the present invention, that emission of formaldehyde from a material containing a cured melamine/formaldehyde or urea/formaldehyde resinous material may be reduced by the incorporation in the material of sulphamic acid or a salt thereof, such as an alkali metal salt or a salt with a nitrogenous base, especially ammonium sulphamate.
According to the invention, therefore, there is provided a resinous material comprising a cured melamine/formaldehyde or urea/formaldehyde resin together with sulphamic acid or a salt thereof.
Generally, the resinous material will also contain filler, commonly a cellulosic filler as discussed above.
Melamine/formaldehyde and urea/formaldehyde resins are well known and are described, for example, in "The Chemistry of Organic Film Formers", D.H. Solomon, Robert E. Krieger Publishing Company, 2nd Edition, 1977, at pages 233-252. In essence, such resins are prepared by the reaction of melamine or urea with formaldehyde to form an insoluble cross-linked product, generally under the action of heat and in the presence of an acidic material as catalyst. The resins may be prepared simply melamine/formaldehyde or urea/formaldehyde resinous binder.
It has now been found, in accordance with the present invention, that emission of formaldehyde from a material containing a cured melamine/formaldehyde or urea/formaldehyde resinous material may be reduced by the incorporation in the material of sulphamic acid or a salt thereof, such as an alkali metal salt or a salt with a nitrogenous base, especially ammonium sulphamate.
According to the invention, therefore, there is provided a resinous material comprising a cured melamine/formaldehyde or urea/formaldehyde resin together with sulphamic acid or a salt thereof.
Generally, the resinous material will also contain a filler, commonly a cellulosic filler as discussed above.
Melamine/formaldehyde and urea/formaldehyde resins are well known and are described, for example, In "The Chemistry of Organic Film Formers", D.H. Solomon, Robert E. Krieger Publishing Company, 2nd Edition, 1977, at pages 233-252. In essence, such resins are prepared by the reaction of melamine or urea with formaldehyde to form an insoluble cross-linked product, generally under the action of heat and in the presence of an acidic material as catalyst. The resins may be prepared simply by reaction of melamine or urea with formaldehyde to produce the desired end product but, commonly, the melamine or urea are first reacted with formaldehyde to form a soluble intermediate resinous product (which may be etherified with an aliphatic alcohol such as butanol), the intermediate subsequently being cured to yield the final cross-linked product.
In accordance with the invention, the cured melamine/formaldehyde or urea/formaldehyde resinous material contains sulphamic acid (H2N.SO3H) or a salt thereof, e.g. an alkali metal salt or a salt with a nitrogenous base, especially the ammonium salt. These salts are readily water-soluble and may be conveniently incorporated into reinforced cellulosic materials to prevent the emission of free formaldehyde.
The weight ratio of sulphamic acid or sulphamate salt to resin is is suitably from O.15: 2. 5:1, preferably from 1:1 to 1:1. In general, the more highly cured the final end product, the less suiphamic acid or salt required to reduce formaldehyde emission and vice versa. The preferred sulphamate salt is ammonium sulphamate which has proved to be particularly useful for reducing formaldehyde emission.
Examples Commercially available base paper containing about 3% by weight of a cured melamine/formaldehyde resin as wet-strength improving agent was impregnated, to a pick-up of about 50% by weight based on the dry weight of the paper, of an aqueous solution (a) or (b) having the formulation given below containing:: Solution (a) Grams Polyethylene glycol 10.0 Tetra-sodium pyrophosphate 5.0 Protocatechuic acid 18.0 Thiourea 3.0 Sodium chloride 75.0 Sodium nitrate 20.0 Sodium chlorate 25.0 Ammonium sulphamate 20.0 Deionised water to 1 litre Solution (b) Grams Succinic acid 20.0 Citric acid 1.96 Sodium hydroxide 4.9 Sodium nitrate 50.0 N-allyl-N'-2-hydroxyethylthiourea 3.75 Catechol 50.0 Sodium chlorate 100.0 Ammonium sulphamate 20.0 Deionised water to 1 litre The resulting papers were then used as recording papers in an electrolytic recording apparatus (K 649 and 949 marketed by Muirhead PLC). During the course of operation, the air one cm from the paper at the point where the copy emerged from the machine was sampled and its formaldehyde content determined.
By way of comparison, the procedure was repeated omitting ammonium sulphamate from the impregnating solutions. The results are shown in the following Table.
TABLE Free Formaldehyde content of air (ppm) Copier No. Ammonium Ammonium (No. of copies) sulphamate sulphamate present absent K 949 (4) < 0.5 4 K 949 (9) < 0.5 4 K 949 (14) < 0.5 4 K 649 (4) < 0.5 3 K 649 (9) < 0.5 3

Claims (7)

1. A resinous material comprising a cured melamine/formaldehyde or urea/formaldehyde resin together with sulphamic acid or a salt thereof.
2. A resinous material as claimed in claim 1 in which the sulphamate salt is ammonium sulphamate.
3. A resinous material as claimed in claim 1 or claim 2 in which the weight ratio of sulphamic acid or sulphamate salt to melamine/formaldehyde or urea/formaldehyde resin is from 0.15:1 to 2.5:1.
4. A resinous material as claimed in any one of the preceding claims also containing a filler.
5. A resinous material as claimed in claim 4 in which the filler is a cellulosic filler of natural origin.
6. A resinous material as claimed in claim 5 in which the resinous material takes the form of an electrolytic recording paper comprising a high wet-strength paper reinforced with a melamine/formaldehyde or urea/formaldehyde resin, and impregnated with an aqueous solution comprising an organic compound capable of giving a mark upon the paper upon electrolysis, and a water-soluble eiectrolyte.
7. A resinous material as claimed in claim 1 substantially as hereinbefore described with reference to the Examples.
GB8508351A 1985-03-29 1985-03-29 Melamine/formaldehyde and urea/formaldehyde resinous materials Expired GB2172894B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB8508351A GB2172894B (en) 1985-03-29 1985-03-29 Melamine/formaldehyde and urea/formaldehyde resinous materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8508351A GB2172894B (en) 1985-03-29 1985-03-29 Melamine/formaldehyde and urea/formaldehyde resinous materials

Publications (3)

Publication Number Publication Date
GB8508351D0 GB8508351D0 (en) 1985-05-09
GB2172894A true GB2172894A (en) 1986-10-01
GB2172894B GB2172894B (en) 1989-05-10

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Family Applications (1)

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GB8508351A Expired GB2172894B (en) 1985-03-29 1985-03-29 Melamine/formaldehyde and urea/formaldehyde resinous materials

Country Status (1)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3815204A1 (en) * 1988-05-04 1989-11-16 Gruber & Weber Gmbh Co Kg PROCESS FOR PRODUCING COMPOSITE MATERIALS WITH REDUCED FORMALDEHYDE EMISSION

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB890515A (en) * 1958-06-02 1962-02-28 West Point Mfg Co Preventing odours in filamentary or sheet material treated with thermosetting aldehyde resins
GB1027725A (en) * 1962-08-30 1966-04-27 Ici Australia Ltd Improved thermosetting moulding powders
GB1232031A (en) * 1967-10-05 1971-05-19
GB1239143A (en) * 1968-03-21 1971-07-14
GB1296246A (en) * 1969-09-12 1972-11-15
GB1321680A (en) * 1970-09-21 1973-06-27 Cabot Corp Process for the continuous manufacture of crosslinked amino-resin polymer
GB1358605A (en) * 1970-07-30 1974-07-03 Cabot Corp Urea-formaldehyde resins
GB1360339A (en) * 1971-08-25 1974-07-17 Cassella Farbwerke Mainkur Ag Highly condensated aminoplast resins of unlimited dilutability in water and a process for preparing them
GB1366256A (en) * 1971-10-07 1974-09-11 Cassella Farbwerke Mainkur Ag Aminoplast resin and coated or laminated article of manufacture
GB1390370A (en) * 1971-08-05 1975-04-09 British Industrial Plastics Process for manufacturing aminoplast precondensates
GB1410722A (en) * 1972-01-21 1975-10-22 Cassella Farbwerke Mainkur Ag Process for the preparation of alkylene-bis-amides
GB1524590A (en) * 1975-12-23 1978-09-13 Cassella Farbwerke Mainkur Ag Aminoplast and use thereof
GB1536229A (en) * 1975-04-05 1978-12-20 Cassella Farbwerke Mainkur Ag Condensation products useful in the production of paper and board
GB2009752A (en) * 1977-12-09 1979-06-20 British Industrial Plastics Foam
EP0019040A1 (en) * 1979-03-31 1980-11-26 Hüls Troisdorf Aktiengesellschaft Process for curing urea resin moulding compositions, and urea resin moulding compositions
GB1603088A (en) * 1977-06-11 1981-11-18 British Industrial Plastics Resin manufacture
GB2102829A (en) * 1981-07-27 1983-02-09 Georgia Kaolin Co Opacifying pigments for paper

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB890515A (en) * 1958-06-02 1962-02-28 West Point Mfg Co Preventing odours in filamentary or sheet material treated with thermosetting aldehyde resins
GB1027725A (en) * 1962-08-30 1966-04-27 Ici Australia Ltd Improved thermosetting moulding powders
GB1232031A (en) * 1967-10-05 1971-05-19
GB1239143A (en) * 1968-03-21 1971-07-14
GB1296246A (en) * 1969-09-12 1972-11-15
GB1358605A (en) * 1970-07-30 1974-07-03 Cabot Corp Urea-formaldehyde resins
GB1321680A (en) * 1970-09-21 1973-06-27 Cabot Corp Process for the continuous manufacture of crosslinked amino-resin polymer
GB1390370A (en) * 1971-08-05 1975-04-09 British Industrial Plastics Process for manufacturing aminoplast precondensates
GB1360339A (en) * 1971-08-25 1974-07-17 Cassella Farbwerke Mainkur Ag Highly condensated aminoplast resins of unlimited dilutability in water and a process for preparing them
GB1366256A (en) * 1971-10-07 1974-09-11 Cassella Farbwerke Mainkur Ag Aminoplast resin and coated or laminated article of manufacture
GB1410722A (en) * 1972-01-21 1975-10-22 Cassella Farbwerke Mainkur Ag Process for the preparation of alkylene-bis-amides
GB1536229A (en) * 1975-04-05 1978-12-20 Cassella Farbwerke Mainkur Ag Condensation products useful in the production of paper and board
GB1524590A (en) * 1975-12-23 1978-09-13 Cassella Farbwerke Mainkur Ag Aminoplast and use thereof
GB1603088A (en) * 1977-06-11 1981-11-18 British Industrial Plastics Resin manufacture
GB2009752A (en) * 1977-12-09 1979-06-20 British Industrial Plastics Foam
EP0019040A1 (en) * 1979-03-31 1980-11-26 Hüls Troisdorf Aktiengesellschaft Process for curing urea resin moulding compositions, and urea resin moulding compositions
GB2102829A (en) * 1981-07-27 1983-02-09 Georgia Kaolin Co Opacifying pigments for paper

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3815204A1 (en) * 1988-05-04 1989-11-16 Gruber & Weber Gmbh Co Kg PROCESS FOR PRODUCING COMPOSITE MATERIALS WITH REDUCED FORMALDEHYDE EMISSION

Also Published As

Publication number Publication date
GB2172894B (en) 1989-05-10
GB8508351D0 (en) 1985-05-09

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19950329