EP0136344A1 - Resine du type phenolique contenant de la formamide pour un laminage a basse pression - Google Patents

Resine du type phenolique contenant de la formamide pour un laminage a basse pression

Info

Publication number
EP0136344A1
EP0136344A1 EP84901247A EP84901247A EP0136344A1 EP 0136344 A1 EP0136344 A1 EP 0136344A1 EP 84901247 A EP84901247 A EP 84901247A EP 84901247 A EP84901247 A EP 84901247A EP 0136344 A1 EP0136344 A1 EP 0136344A1
Authority
EP
European Patent Office
Prior art keywords
resin
formamide
laminating
alkaline
laminating resin
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.)
Withdrawn
Application number
EP84901247A
Other languages
German (de)
English (en)
Inventor
Leopold F. Bornstein
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.)
Georgia Pacific LLC
Original Assignee
Georgia Pacific LLC
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 Georgia Pacific LLC filed Critical Georgia Pacific LLC
Publication of EP0136344A1 publication Critical patent/EP0136344A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • D21H17/48—Condensation polymers of aldehydes or ketones with phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles

Definitions

  • This invention relates to a new resole-type phenolic laminating resin having excellent penetration and rapid cure suitable for making high-grade decorative laminates at high speed and low pressure.
  • Conventional decorative laminates are typically produced in a batch wise procedure by curing a plurali ty of t her m os et ti n g resin-impregnated fibrous substrate layers in a press at high pressures (e.g., 800-1500 psi) and elevated temperatures (e.g., 250-350 ⁇ F).
  • high pressures e.g., 800-1500 psi
  • elevated temperatures e.g. 250-350 ⁇ F
  • the laminates generally consist of three elements: a core section consisting of several sheets of an inexpensive substrate, e.g., kraft paper, satu ⁇ rated or impregnated with a resole-type phenolic resin, a j print sheet of alpha cellulose saturated with an expensive amino resin, e.g., a melamine resin and a translucent overlay of rayon or alpha cellulose, also saturated with an expensive amino resin.
  • an inexpensive substrate e.g., kraft paper, satu ⁇ rated or impregnated with a resole-type phenolic resin
  • a j print sheet of alpha cellulose saturated with an expensive amino resin e.g., a melamine resin
  • a translucent overlay of rayon or alpha cellulose also saturated with an expensive amino resin.
  • the paper substrate When preparing the laminate, the paper substrate is first passed through a dip tank filled with resin. Resin penetration of the substrate is substantially accomplished during immersion in the tank. Excess resin is generally removed from the substrate by opposed scraper bars or blades as the substrate leaves the dip tank. Residual
  • the drying zone generally comprises a long oven where the resin solvent is evaporated and the resin is substantially advanced to an infusible stage (B-Stage).
  • B-Stage infusible stage
  • the advanced resin removed from the drying oven is then cut to size, stacked and consolidated in the hot, high pressure press.
  • the laminate is cured in the press for about 15 to ' 60 minutes.
  • a laminating resin composition comprising a resole-type phenolic resin in an organic solvent having about 2 to about 15%, by weight of a material selected from the group consisting of formamide, N-methyl formamide, N,N-dim ethyl formamide, N-ethyl formamide, N,N-diethyl formamide, N,N-diphenyl formamide and N-methyl formanilide, and a catalytic amount of an inorganic alkaline material.
  • the present invention also relates to a process for producing a phenolic laminate comprising the steps of saturating a plurality of continuous, fibrous substrate sheets with a fast-curing phenolic lami ⁇ nating resin, said resin comprising a resole-type phenolic resin in an organic solvent, about 2 to about 15% by weight of a material selected from the group consisting of formamide, N-methyl formamide, N,N-dimethyl formamide, N-ethyl formamide, N,N-diethyl formamide, N,N-diphenyl formamide and N-methyl formanilide, and a catalytic amount of an inorganic alkaline material; drying the resin-saturated continuous sheets so as to remove the organic solvent; consolidating the dried, resin-saturated continuous sheets at a pressure of between about 140 to 400 psi and at a temperature sufficient to cure the resin.
  • the present invention specifically relates to a fast curing phenolic laminating resin, modified with a material selected from the group consisting of formamide N-methyl formamide, N,N-dimethyl - 4 -
  • Phenolic resins useful for preparing laminating resins of the present invention are produced in accordance with reaction conditions normally observed for manufacturing phenolic resoles, i.e., by reacting a molar excess of an aldehyde with a phenolic- component in the presence of alkaline catalytic material under moderately elevated reaction temperature conditions. The reaction is typically conducted under reflux at atmospheric pressure.
  • aldehyde components such as formaldehyde, acetaldehyde, propionaldehyde, furfural or the like can be used.
  • Formaldehyde is generally preferred because of its low cost and high reactivity.
  • the formaldehyde is generally added as 50% aqueous solution (formalin), although anhydrous para-formaldehyde can also be used.
  • suitable phenolic components include phenol, substituted phenols, e-g.- cresol, and phenol homologs, which are generally employed for forming phenolic resole resin. Phenol is generally preferred.
  • about 1.5 to 3.0 mols of formalde ⁇ hyde are used for each mol of phenol.
  • the formal ⁇ dehyde to phenol molar ratio is about 2.0.
  • an alkaline catalyst In order to produce a resin with desired properties an inorganic alkaline material is typically employed as the catalyst.
  • an alkali metal hydroxide or an alkali metal salt of a weak acid is used as the alkaline material.
  • Suitable alkaline materials include sodium and potassium hydroxide and potassium and lithium carbonate. Potassium carbonate is particularly preferred because it yields a resin having . a reactivity at least equal to and gen ⁇ erally higher than a resin prepared using sodium hydroxide as the cat ⁇ alyst, and it does not undesirably increase the molecular weight of the resin to a point which interferes with penetration.
  • a resin catalyzed with potassium carbonate unexpectedly can be employed without the
  • the phenol- formaldehyde reaction is preferably advanced under carefully controlled conditions. After blending the phenol and formal ⁇ dehyde components, a first quantity of alkaline catalyst material is added to the reaction mixture. The mixture is then subjected to mild heating, e.g., up to atmospheric reflux, for a short time, e.g., about 15 minutes. The mixture is then partially cooled, additional alkaline material is added and the reaction mixture is again subjected to mild heating. This procedure is preferably repeated one more time before the resin is vacuum dehydrated with mild heating to reduce its water content. Preferably, a weak organic acid, e.g., lactic, citric, boric, propionic, butyric, etc. is added to neutralize the reaction mixture before the vacuum distillation step so as to inhibit excessive resin advancement during this stage. Thereafter, the resin is cooled to ambient conditions.
  • mild heating e.g., up to atmospheric reflux
  • the laminating resin of the present invention is then prepared by adding a material selected from the group consisting of formamide, N-methyl formamide, N,N-dimethyl formamide, N-ethyl formamide, N,N-diethyl formamide, N,N-diphenyl for ma mide and N-m ethyl formanilide, an organic solvent and additional alkaline material to the resin.
  • a material selected from the group consisting of formamide, N-methyl formamide, N,N-dimethyl formamide, N-ethyl formamide, N,N-diethyl formamide, N,N-diphenyl for ma mide and N-m ethyl formanilide, an organic solvent and additional alkaline material to the resin.
  • the formamide or disclosed formamide equivalent, solvent and alkaline material can be added to the resin at any time prior to the step of .saturating the fibrous substrate sheets.
  • the resin's penetration must to some extent be undesirably compromised.
  • a fast curing laminating resin suitable for use in the continuous, low pressure laminating process outlined above could be prepared having a high penetration as well as a suitably high flash point.
  • the present invention is based in part on the discovery that by using formamide or disclosed formamide equivalent in formulating the laminating resin, the amount of organic solvent otherwise required to appropriately enhance the penetration of a fast curing resin is advan ⁇ tageously reduced. Consequently, the laminating resin has a lower organic to aqueous solvent ratio and accordingly a higher flash point.
  • Peterson et al U.S. 2,981,652 discloses an aqueous phenolic adhe ⁇ sive, i.e., a phenolic condensation product or resin dissolved in a highly alkaline aqueous alkali - metal hydroxide solution, which employs formamide as a setting accelerator. Since the formamide is used as a setting accelerator by means of the reaction with excess caustic, it is not blended with the alkaline phenolic solution until the point of use.
  • the adhesive described by Peterson is obviously not suitable as a lami ⁇ nating resin because of high molecular weight and insufficient satu ⁇ ration essential for high speed operation.
  • a sufficient amount of organic solvent is also added to the phenolic resin so as to provide the laminating resin with a viscosity between about 80-150 cps.
  • Suitable solvents include alcohols, e.g., methanol, ethanol, and isopropyl alcohol, and ketones, e.g., acetone and methyl ethyl ketone. Methanol is the preferred solvent.
  • Additional alkaline material is also added to the resin at this time.
  • the resin is stable for about 2 to 4 weeks at room temperature.
  • laminating resin modifiers may optionally be added to the laminating resin composition for further enhancing specific properties of the laminating resin.
  • urea is generally added to reduce the free formaldehyde content to below about 2%.
  • a small amount of a polyamide resin and/or a polyol, e.g., a polyglycol or a polyglycerine, may also be added to aid penetration and enhance resin flow at low consolidation pressures.
  • a suitable lubricant, such as oleic acid may also be added to ease the release of the fully cured laminate from the rolls.
  • the additional curing agent can be used in amounts of from about 2 to 10% by weight depending on the type of cure desired.
  • the present invention also comprises a continuous, low pressure laminating process for producing decorative laminates employing the fast-curing laminating resin of this invention.
  • a plu ⁇ rality of continuous, fibrous substrate sheets are saturated with the fast curing phenolic laminating resin described above.
  • the fibrous substrate may be paper, e.g., heavy kraft paper, textiles, asbestos, glass fibers and the like.
  • the substrate can typically be saturated in as little as 10- seconds.
  • the saturated resin is then dried to evaporate the solvent and advance the resin. At temperatures between about 350° and 450 °F drying takes between about 5 and 15 seconds. Nor ⁇ mally, the resin content of the dried resin-saturated sheets will be on the order of 20 to 40% by weight.
  • the continuous sheets are then consolidated, e.g., between the nips of opposing, serially positioned rollers, at a pressure of between 140 to 400 psi, e.g., 200 psi and at a temperature sufficient to cure the resin. Press temperatures are generally between about 350 ° to 450 °F. At these conditions, the consolidated laminate is fully cured in about 10 to 30 seconds. The fully cured laminate may be cut to size immediately after curing or stored in roll form for later use.
  • the invention has been described primarily for use in pre ⁇ paring decorative laminates, the invention is broadly suited to the manufacture of other laminates which employ phenolic resins, e.g., lam ⁇ inates for electrical applications.
  • the laminating resin of this invention is particularly suitable for use -in connection with the continuous low pressure laminating process, it can also be used to pre ⁇ pare high pressure laminates using the conventional batch process.
  • a suitable phenolic resole resin for preparing the laminating resin of the present invention was produced by blending 42.82 parts by
  • the phenol-formaldehyde condensation reaction was controllably advanced by adding the alkaline material in a stepwise manner. Initially, 0.08 parts by weight of a 50% aqueous sodium hydroxide solution was added and the mixture was heated to about 96-100 °C and held for about 15 minutes. The mixture was then cooled to about 90 °C; 0.11 parts of the aqueous sodium hydroxide solution was added, and the mixture was again heated to about 96-100 °C and held for an additional 15 minutes. This procedure was repeated once more as 0.38 parts of the aqueous sodium hydroxide solution was added to the reaction mixture.
  • the reaction mixture was thereafter cooled to about 80 °C and held at this temperature until the resin reached a viscosity in the range of 150-200 cps (at 25 °C) Lactic acid, about 0.73 parts by weight, was then added to neutralize the reaction mixture and the resin was vacuum dehydrated. After the water content of the resin had been reduced to the desired extent, the resin was cooled to ambient conditions.
  • Example 1 The Example 1 process for preparing a phenolic resole resin was repeated with the following formulation:
  • reaction viscosity end point can go to 350-400 cps at 25 ⁇ C.
  • Tests were conducted which compared the penetration character ⁇ istics of a laminating resin containing formamide with the same resin containing some of the other disclosed formamide equivalents. Assigning the laminating resin containing formamide a relative pene ⁇ tration value of 1, the other laminating resins tested containing the noted formamide equivalent had the following relative penetration values N-m ethyl formanilide (1.30); N-methyl formamide (0.82); N,N-diphenyl formamide (2.40) and N,N-di ⁇ ethyl formamide (0.38).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

Résine phénolique de laminage à polymérisation rapide comprenant une résine de résol dans un solvant organique, 2 à 15 % environ d'un matériau sélectionné dans le groupe se composant de formamide, N-méthyl formamide, N,N-diméthyl formamide, N-éthyl formamide, N,N-diéthyl formamide, N,N-diphényl formamide et N-méthyl formanilide, ainsi qu'une quantité catalytique d'un matériau alcalin inorganique. La résine de laminage présente des caractéristiques de pénétration suffisamment élevées et de polymérisation rapide, permettant de l'utiliser dans un procédé de laminage en continu à basse pression.
EP84901247A 1983-02-22 1984-02-17 Resine du type phenolique contenant de la formamide pour un laminage a basse pression Withdrawn EP0136344A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US46854783A 1983-02-22 1983-02-22
US468547 1983-02-22
US57818184A 1984-02-14 1984-02-14
US578181 1984-02-14

Publications (1)

Publication Number Publication Date
EP0136344A1 true EP0136344A1 (fr) 1985-04-10

Family

ID=27042441

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84901247A Withdrawn EP0136344A1 (fr) 1983-02-22 1984-02-17 Resine du type phenolique contenant de la formamide pour un laminage a basse pression

Country Status (2)

Country Link
EP (1) EP0136344A1 (fr)
WO (1) WO1984003293A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4611020A (en) * 1985-01-11 1986-09-09 Georgia-Pacific Resins, Inc. Melamine-modified phenolic type resin for continuous lamination
IT1293483B1 (it) * 1997-06-06 1999-03-01 Orv Spa Uso di resine fenoliche, in particolare resolo, come impregnanti di insiemi di fibre di materie termoplastiche

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1469823A1 (de) * 1959-10-28 1969-08-07 Borden Co Bei niedriger Temperatur haertendes Harzbindegemisch
DE1234513B (de) * 1962-10-26 1967-02-16 Scheufelen Papierfab Erhoehung der Harzaufnahmegeschwindigkeit und des Harzaufnahmevermoegens bei der Beharzung von Laminatpapieren
FR2009474A1 (en) * 1968-05-28 1970-02-06 Basf Ag Curing phenol formaldehyde condensates
US3707692A (en) * 1969-03-10 1972-12-26 Mc Graw Edison Co Method of treating cellulosic material to improve the usefulness thereof as an insulator in electrical apparatus
JPS55123644A (en) * 1979-03-19 1980-09-24 Mitsui Toatsu Chem Inc Fast-curing phenolic resin composition
JPH07316352A (ja) * 1994-05-23 1995-12-05 Sumitomo Chem Co Ltd 射出成形用エチレン系樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8403293A1 *

Also Published As

Publication number Publication date
WO1984003293A1 (fr) 1984-08-30

Similar Documents

Publication Publication Date Title
US4264671A (en) Phenol formaldehyde resoles and laminates
US4831106A (en) Low-Formaldehyde binders
US5646219A (en) Method of preparing binder system and product thereof
US4185017A (en) N-substituted ε-caprolactams
US2385372A (en) Production of resin
US2639258A (en) Production of articles from synthetic resinous materials
USRE23347E (en) Art of making phenol-aldehyde re
US3940352A (en) Process for preparation of lignin resin
US2457493A (en) Art of making phenol-aldehyde reaction products and the product thereof
US4611020A (en) Melamine-modified phenolic type resin for continuous lamination
US5756599A (en) Binder resin, binder system, cellulosic composite articles, and method of making the same
EP3887474B1 (fr) Procédé de préparation d'une solution de lignine dans un milieu aqueux
EP0136344A1 (fr) Resine du type phenolique contenant de la formamide pour un laminage a basse pression
US2941918A (en) Novel polymeric products and process
US5763559A (en) Phenol-formaldehyde resins modified with guanidine salts
US4661412A (en) Melamine-modified phenolic type resin for continuous lamination
US4235989A (en) Production of thermosetting phenol-formaldehyde resins
US3677979A (en) Sulfonated phenol-aldehyde resins
US3897589A (en) Fast curing, water-resistant laminate made with accelerated melamine-aldehyde resin and accelerated phenol-aldehyde resin and method of making it
US2563614A (en) Phenolic resin and method of making
US3993851A (en) Novolak-type resins and varnishes
CN1287981C (zh) 使用干性油改性酚醛树脂组合物的酚醛树脂层压板
US4011280A (en) Process for the production of binders for weather-proof wood materials and product
US2538883A (en) Phenol-modified acetone resins
WO1998050467A1 (fr) Composition de resine et panneau realise avec cette resine

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB LI NL SE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19850123

RIN1 Information on inventor provided before grant (corrected)

Inventor name: BORNSTEIN, LEOPOLD, F.