GB2180251A - Thixotropic surface composition for phenol-aldehyde resin laminates - Google Patents
Thixotropic surface composition for phenol-aldehyde resin laminates Download PDFInfo
- Publication number
- GB2180251A GB2180251A GB08621355A GB8621355A GB2180251A GB 2180251 A GB2180251 A GB 2180251A GB 08621355 A GB08621355 A GB 08621355A GB 8621355 A GB8621355 A GB 8621355A GB 2180251 A GB2180251 A GB 2180251A
- Authority
- GB
- United Kingdom
- Prior art keywords
- composition
- phenol
- thixotropic
- resole
- mould
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 230000009974 thixotropic effect Effects 0.000 title claims abstract description 27
- 229920003987 resole Polymers 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000000945 filler Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000004034 viscosity adjusting agent Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- 230000002787 reinforcement Effects 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 5
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 3
- 239000003365 glass fiber Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- 238000003853 Pinholing Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- -1 sulphuric acid Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
This invention relates to a thixotropic composition and the use thereof as a surface composition for preparing shaped laminated composites. The composition contains an acid hardenable phenol-aldehyde resole, a filler and a viscosity modifier and the composition at 25 DEG C has a viscosity of 200-800 poise measured using a Brookfield RVT instrument, spindle 7 at 50 revolutions per minute. The use of the thixotropic surface composition gives laminated composites with a surface which is free of defects.
Description
SPECIFICATION
Phenol-aldehyde resin laminates
The present invention relates to a composition suitable for surface lamination of shapes from phenol-aldehyde resins, especially glass reinforced phenol-aldehyde resins.
Phenol-aldehyde resols are thermosetting resins and are conventionally prepared by reacting a molar-excess of an aldehyde, e.g. formaldehyde with phenol. Such resins are hardenable and may be used for producing shapes and moulds. The resins after shaping can be cured in the presence ofacidicoralkaline catalysts. The resins may also be reinforced prior to shaping using strands or matrices ofglassfibre and such products are the so-called glass reinforced phendlic resins.
It is known that shapes of glass reinforced phenolic resins prepared by conventional techniques, e.g. by hand lay up or spray deposition, have a tendency to exhibitthe phenomenon known as "pin-holingl on the surface. This so-called "pin-holing" is caused by the slow loss of volatile gases/vapours generated during the strong acid catalysed thermosetting of the resin at elevated temperature.
The object of the present invention is to devise a suitable surface composition compatible with such resins and capable of being treated with suitable primers and top coats after demoulding so as to provide an excellent surface finish on the moulded product. Such products are also substantially free of pin-holing.
Accordingly, the present invention is a thixotropic surface composition capable of surface lamination of shapes from phenol-aldehyde resins, said thixotropic composition comprising (a) an acid hardenable phenol-aldehyde resole, (b) a filler and (c) a viscosity modifier such that the viscosity of the composition is from 200to 800 poise measured at 250C using a Brookfield RVT instrument, spindle 7 at 50 revolutions per minute.
In this composition, the acid hardenable phenol-aldehyde resole is suitably a phenol-fo rmaldehyde resole.
The phenol-aldehyde resole in thethixotropic composition suitably has a viscosity of 200-300 centistokesat 25 C, a specific gravity of 1.22-1.23, a solids content of 65-70%, a pH of 7.3 to 7.8 and a free formaldehyde content of not more than 2.5% by weight. The resole is suitably prepared by reacting a molar excess of an aldehyde e.g. formaldehyde, with phenol in the presence of an alkaline catalyst. The resole is suitably prepared by reacting the components at a temperature from 60to 100"C. Examples of alkaline catalysts that may be used to prepare the resole include an alkali oran alkaline earth metal hydroxide e.g.sodium hydroxide or calcium hydroxide respectively.
The resole is suitably mixed with one or more fillers selected from glass beads, alumina, titanium dioxide, china clay, siliceous earths, diatomaceous earths and mixtures thereof and the like. The fillers suitably have a particle size from 10 nanometers to 75 microns, preferably from 7 to 60 microns.
The amount of filler present in the resole composition is suitably from 5to 50 wt%, preferably from 10to45 wt% based on the resole.
The thixotropic resole composition is used in the form of a paste. The paste can be formed by adding to the resole-filler mixture a viscosity modifier. An example ofthetype of viscosity modifier that may be used is
BYK-W980which is a proprietary product sold by BYK-Chemie GmbH and is a salt of polyamino amidesand an acid ester dissolved in 2-butoxy ethanol.
The amount of viscosity modifier used is suitably from 0.2-2%, preferably from 0.5-1.5% by weight ofthe total thixotropic composition. The viscosity of the thixotropic surface composition at 25"C measured by the
Brookfield RVT instrument above is preferably from 300-500 poise, spindle 7, at 50 revolutions per minute.
The thixotropic surface composition is kept free ofthe acid hardener during storage.
The acid hardener used is suitably selected from mineral acids and organic acids, e.g. sulphuric acid, an alkyl- oraryl-sulphonicacid our a compound capable of giving rise to an acid under hydrolysis conditions e.g.
an acyl halide.
In use, the mould is prepared to a prearranged pattern of the shaped laminated composite. The surface of the mould is first treated with conventional sealer and mould release agents. Thereafterthethixotropic surface composition is mixed with a hardener, suitably 5-15% by weight thereof and applied as a thin coat to the mould surface.
Thereafter it is preferable to allowthethixotropic surface composition in the mould to partially curefora short period, e.g. 5-60 minutes at a temperature below 75"C, preferably ambientto 60"C before building thereon layers of conventional fibre reinforced, phenol-formaldehyde resin which forms the main body of the shaped laminated composite combined with an acid hardener. The fibre reinforced phenol-aldehyde resin forming the main body ofthe shaped laminated composite is suitably derived from a phenol-aldehyde resole which may be the same or different from the resole used in the thixotropic surface composition.It is preferable that the resole used in the main body of the composite has the following characteristics: a viscosity from 100-2,500 centistokes, preferably from 500-1,600 centistokes at 25'C, a specific gravity from 1.22-1.24; a pH from 7.3 to 7.8, and a maximum freeformaldehyde content of up to 5% byweight.
The fibre-reinforcement may be in the form of chopped strands, a mat formed from bonded, woven or compressed fibres, ora combination thereof. The fibre reinforcement in the main body resin is suitably of glass. The proportion of the fibre reinforcement to the resole resin in the main body of the shaped laminated composite is suitably from 1 :3to 3:1 by weight, preferablyfrom 1 :2to 2:1 byweight. The layers ofthe main body fibre-reinforced resin can be built upon the partially cured thixotropic Surface composition by hand lay, spray or other conventional techniques.
The whole composite shape can be cured in the mouldforup to 40 hours, preferably for 1-24 hours at elevated temperature. The curing is suitably carried out in two stages, e.g. for 1-16 hours at 40-600C before removal from the mould andfora further2-16 hours at 40-1 000C as final post curing.
Thus, according to a further embodiment, the present invention is a method of preparing in a mould of prearranged pattern a shaped laminated composite from a fibre reinforced phenol-aldehyde resin, said method comprising:
(A) applying as a thin coaton the mould surface a thixotropic surface composition comprising::
(a) an acid hardenable phenol-aldehyde resole,
(b) afiller,
(c) a viscosity modifier, and
(d) an acid catalyst
said composition having aviscosityof200-800 poise measured at25 C using a Brookfield RVT instrument,spindle7at50 rpm; (B) allowing thethixotropic composition to partially cure at ambient to elevated temperature;;
(C) applying on the partially cured surface from (B) above one or more layers of a fibre reinforced
phenol-aldehyde resin, which forms the main body of the shaped composite and which may be the
same as ordifferentfrom the phenol-aldehyde resin in the resole forming the thixotropic composition,
admixed with an acid catalyst,
(D) curing in the mould the composite resulting from steps (A) to (C) above in one or more stages at ambient
and/or elevated temperature, and
(E) recovering the shaped laminated composite from the mould.
The above embodiment can be typically performed using a thixotropic surface composition which has a filler content above 35% by weight of the total thixotropic surface composition. However, if the filler content ofthe thixotropic surface composition is lower, e.g. below 35% by weight, then it is preferable to place on the thin coating ofthe surface composition already applied on the mould a fibrous reinforcement priorto building thereon layers ofthe main body resin. By "fibrous reinforcement" is meant here and throughoutthe specification a wettable tissue-like reinforcement which may be formed from strands of a woven or compressed fibrous material e.g. glass fibres.
Where an intervening layer of a fibrous reinforcement is placed on the thin coat of the thixotropicsurface composition in the mould,the fibrous reinforcement is preferably impregnated thoroughly with the surface composition.This may be achieved by brushing or by using a roller.
The shaped, laminated product resulting from the above does not experience any change in the chemical or
mechanical resistance properties of the main body glass fibre reinforced phenolic resin composite. For
example the volume of smoke generated during combustion of such a surface coated product is not
measurably greaterthan that of the base composite formed from the main body glass fibre reinforced resin
alone. The use of the surface coating gives a product which is free of defects e.g. pin-holing, and requires no
additional processing priorto priming and top coating.The adhesion ofprimerand top coatto the surface is
also excellent.
The present invention is further illustrated with reference to the following Examples.
Example I
Athixotropic surface coating composition comprising a mixture of catalysed phenol formaldehyde resole which was filled with a mixture of various fillers (as shown below) and a viscosity modifier BYK-W980 (Registered Trade Mark) was prepared asfollows:
The phenol aldehyde resin used to form the thixotropic surface composition had the following characteristics:
Resole: Phenol-formaldehyde (Phenol to formaldehyde mole ratio 1:1.6)
Viscosity at 25"C: 200-300 centistokes 25"C Specific gravity: 1.223 pH:7.4 Free formaldehyde: 2.1% The above resole was mixed in a higher shear mixerwith the fillers and viscosity modifier in thefollowing
proportions::
Resole resin 100 parts by weight
Glass spheres of average
particle diameter 30 microns 25 parts by weight
English china clayGrade D of
average particle diameter30-45 microns 15 parts by weight
Aerosil 200 LDCVAlumina of average
primary particle diameter 12 nanometers 2.8 parts by weight
Viscosity modifier 1.0 parts by weight
The composition at 250C had a viscosity of 400 poise measured by the Brookfield RVT instrument using spindle 7 at 50 rpm.
Example 2
Amould was prepared to a prearranged pattern ofthe shaped laminated composite. The surface of mould was treated with a sealer and a release agent. The surface composition of Example 1 above with 8% weight of a Phencat 10 (Registered Trade Mark, ex-Libra Chemicals) catalyst, which is an aqueous mixture of p-tol uene su I phon ic acid and phosphoric acid, was applied as a thin coat on the mould surface. This coating was allowed to cure for 45 minutes atambienttemperature. A glass tissue was then placed on the surface composition in the mould and thoroughly impregnated by brushing the surface composition to impregnate the tissue with the thixotropic surface composition.Thereafter, the surface composition together with the impregnated glass tissue was partially cured for 5 minutes at ambient temperature before building further layers of the conventional main body fibre reinforced phenol formaldehyde resole and Phencat 10 acid catalyst (8% wt) by hand lay. The phenol-formaldehyde resin used to form the main body ofthe laminate had the following composition and characteristics:
Resin:Phenol-formaldehyde (phenol to formaldehyde mole ratio 1:1.6)
Viscosity of resin: 500-600 centistokes at 250C
Specific gravity of resin: 1.233
pH of resin: 7.6
Free formaldehyde: 2.3%wt
Glass fibre: chopped strand mat
Ratio ofglassto resin: 1:2 by weight
The whole composite was then cured on the mould for 16 hours atambienttemperature before removal and final post curing was carried out at 600C for 16 hours.
Properties derived from use of sufface paste The use of the surface composition did not result in any reduction in mechanical or chemical resistance properties of the main body phenolic resin glass fibre reinforced composite. The volume of smoke generated during combustion was no greaterthan that of the composite from the main body glass fibre reinforced resin alone. Use ofthe thixotropic surface composition gave a surface which was free of defects and required no further processing before priming and top coating. Adhesion ofthethixotropicsurface composition to the main body glass fibre reinforced composite in the laminate was excellent.
Claims (12)
1. Athixotropic surface composition capable of surface lamination ofshapesfrom phenol-aldehyde resins, said thixotropic composition comprising:
(a) an acid hardenable phenol-aldehyde resole,
(b) a filler, and
(c) a viscosity modifier such that the viscosity of the composition is from 200 to 800 poise measured at 25"C using a Brookfield RVT instrument, spindle 7 at 50 revolutions per minute.
2. Athixotropic composition according to claim 1 wherein the phenol-aldehyde resole is a phenol-formaldehyde resole having a viscosity of 200-300 centistokes at25 C, a specific gravity of 1.22-1.23, a solids content of 65-70% w/w, a pH of 7.3-7.8 and a free formaldehyde content of not more than 2.5%w/w.
3. Athixotropic composition according to claim 1 or 2 wherein the filler is selected from glass beads, alumina, titanium dioxide, china clay, siliceous earths, diatomaceous earths and mixtures thereof.
4. Athixotropic composition according to any one of the preceding claims wherein the filler is present in an amount from 5-50% w/w based on the resole.
5. A thixotropic composition according to any one of the preceding claims wherein the filler is present in an amount from 5-50% w/w based on the resole.
6. Athixotropic composition according to any one of the preceding claims wherein the viscosity modifier is a salt of a polyamide and an ester dissolved in 2-butoxyethanol.
7. Athixotropic composition according to any one of the preceding claims wherein the viscosity modifier is used in an amountfrom 0.2-2%w/wofthetotalcomposition.
8. A method of preparing in a mould of prearranged pattern a shaped laminated composite from a fibre reinforced phenol-aldehyde resin, said method comprising:
(A) applying as a thin coat on the mould surface a thixotropic surface composition comprising:
(a) an acid hardenable phenol-aldehyde resole,
(b) a filler,
(c) a viscosity modifier, and
(d) an acid catalyst
said composition having a viscosity of 200-800 poise measured at 250C using a Brookfield RVT
instrument, spindle 7 at 50 rpm,
(B) allowing the thixotropic composition to partially cure at ambient two elevated temperature;;
(C) applying on the partially cured surface from (B) above one or more layers of a fibre reinforced
phenol-aldehyde resin, which forms the main body of the shaped composite and which may be the
same as or different from the phenol-aldehyde resin in the resole forming the thixotropic composition,
admixed with an acid catalyst,
(D) curing in the mould the composite resulting from steps (A) to (C) above in one or more stages art ambient and/or elevated temperature, and
(E) recovering the shaped laminated composite from the mould.
9. A process according to claim 8 wherein the thixotropic surface composition has a filler content above 35%w/wofthetotal composition.
10. A process according to claim 8 wherein the thixotropic surface composition has a filler content below 35%w/w ofthe total composition and a fibrous reinforcement is placed on the mould after step (B) prior to step (C).
11. A process according to claim 10 wherein the fibrous reinforcement is thoroughly impregnated with the thixotropic surface composition.
12. A process according to any one of the preceding claims 8-11 wherein the shaped, laminated composite after recovery from the mould is cured for a further duration at elevated temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8621355A GB2180251B (en) | 1985-09-12 | 1986-09-04 | Thixotropic surface coating for producing phenol-aldehyde resin laminates |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB858522757A GB8522757D0 (en) | 1985-09-12 | 1985-09-12 | Phenol-aldehyde resin laminates |
| GB8621355A GB2180251B (en) | 1985-09-12 | 1986-09-04 | Thixotropic surface coating for producing phenol-aldehyde resin laminates |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8621355D0 GB8621355D0 (en) | 1986-10-15 |
| GB2180251A true GB2180251A (en) | 1987-03-25 |
| GB2180251B GB2180251B (en) | 1989-08-23 |
Family
ID=26289770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8621355A Expired GB2180251B (en) | 1985-09-12 | 1986-09-04 | Thixotropic surface coating for producing phenol-aldehyde resin laminates |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2180251B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0476829A2 (en) * | 1990-09-01 | 1992-03-25 | BP Chemicals Limited | Thixotropic compositions |
| WO2021140319A1 (en) * | 2020-01-07 | 2021-07-15 | Advanced Insulation Limited | Coating for protecting a substrate |
-
1986
- 1986-09-04 GB GB8621355A patent/GB2180251B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0476829A2 (en) * | 1990-09-01 | 1992-03-25 | BP Chemicals Limited | Thixotropic compositions |
| EP0476829A3 (en) * | 1990-09-01 | 1992-11-25 | Bp Chemicals Limited | Thixotropic compositions |
| AU641542B2 (en) * | 1990-09-01 | 1993-09-23 | Borden Chemical Gb Limited | Thixotropic compositions |
| US5334630A (en) * | 1990-09-01 | 1994-08-02 | Bp Chemicals Limited | Thixotropic compositions |
| WO2021140319A1 (en) * | 2020-01-07 | 2021-07-15 | Advanced Insulation Limited | Coating for protecting a substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2180251B (en) | 1989-08-23 |
| GB8621355D0 (en) | 1986-10-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19920904 |