CA1327921C - Method for the protection against water of a laminated resin wall, and a protected laminated resin wall thus obtained - Google Patents

Method for the protection against water of a laminated resin wall, and a protected laminated resin wall thus obtained

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Publication number
CA1327921C
CA1327921C CA000609008A CA609008A CA1327921C CA 1327921 C CA1327921 C CA 1327921C CA 000609008 A CA000609008 A CA 000609008A CA 609008 A CA609008 A CA 609008A CA 1327921 C CA1327921 C CA 1327921C
Authority
CA
Canada
Prior art keywords
layer
resin
barrier
gel coat
mole
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 - Fee Related
Application number
CA000609008A
Other languages
French (fr)
Inventor
Vincent Guilbaud
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.)
Chantiers Beneteau SA
Original Assignee
Chantiers Beneteau SA
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 Chantiers Beneteau SA filed Critical Chantiers Beneteau SA
Application granted granted Critical
Publication of CA1327921C publication Critical patent/CA1327921C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06Unsaturated polyesters having carbon-to-carbon unsaturation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/907Resistant against plant or animal attack
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495Thickness [relative or absolute]
    • Y10T428/24967Absolute thicknesses specified
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31786Of polyester [e.g., alkyd, etc.]

Abstract

A B S T R A C T

The invention relates to a laminate based structure, such as a boat hull or a swimming pool, in which the laminate is coated with a barrier-layer or skin coat, in turn coated with a gel layer or gel coat, in which said barrier-layer or skin coat is made of a bisphenol based resin.

Description

~ 327~21 Field of the Invention The present invention relates to laminated resin walls partaking to a structure which is in contact with water for prolongated periods, such as boat hulls, swimming pool walls, basins and containers, etc.

Backqround of the Invention The laminated resin walls are obtained by applying on the wall of a mold having the required shape mechanically resistant fibers coated with a resin. The result would be a wall in contact with the mold having surface irregularities and the mechanically resistant wall obtained would include pores, which would favour the penetration of water within the thickness of the wall, there-by degrading the constituent resins.
In order to provide a good appearance to the surface of laminated castings, it is known to coat previously the surface of the mold with a film forming resin, technically called gel ZO coat. The film forming resins used are polyesters, epoxy resins, etc., which provide semi-permeable membranes. The result is that when they are applied on laminated resin walls remaining in contact with water, such as swimming pool walls and boat hulls, the outer layers of the gel coat allow the water to penetrate rather quickly in the laminated resin, thereby causing partial separations of the resin layer of the gel coat and the formation o~ bubbles or blisters. This phenomenon, known as "blistering", lets the water flow to the laminate which is sub-jected to hydrolysis, so that in addition to the unaesthetic appearance of the blisters, the mechanical characteristics of the laminate are reduced.
In an effort to remedy this disadvantage, it has been pro-posed to interpose between the laminate and the superficial resin layer or gel coat a layer of resin forming a barrier against the water, called "skin coat". Such a use of two superimposed layers to a laminate limits the choice of the barrier-layer ."

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resin which has to be compatible in order to avoid in particular a risk of decoherence between the successive layers, particu-larly under the effect of impacts, as is the case with an inter-mediate layer in epoxy resin.
So, it has been proposed to provide such a barrier-layer in a vinylester based resin. The use of vinylester based resins, which has been known for a long time in the polyesters industry for increasing the corrosion resistance, provides a certain in-crease of the resistance to the penetration of water, while maintainingorevenincreasingthemechanical strenghtofthe lami-nate thus coated.
However, it has appeared that the vinylester based barrier-layer exhibits a certain degree of sensitivity to water and does not delay in a satisfactory way the hydrolysis of the resin of the laminate.
Due to the known high anti-corrosion characteristics of the vinylester resins, the inventor has been led to think that the part played by the barrier-against the penetration of water was not tied to the anticorrosive properties of the resin con-stituting the layer, but resulted from a purely mechanical effect.
On such a base, the inventor has studied the behaviour as barrier-layer between the gel coat and the laminate of resins having a high steric space requirement and he has established that a high steric space requirement would highly reduce the layer permeability.

Obiects and Summarv of the Invention Consequently, the object of the invention is a protection method against water, particularly sea water, of a laminated resin substrate coated on its face in contact with the water with a layer of film forming resin called "gel coat", con-sisting in interposing between the laminated resin substrate and the gel coat layer a barrier-layer, characterized by the .

: -13279~1 fact the barrier-layer i5 constituted by a resin having in its chain cyclic nuclei and double reactive bonds imparting to it a high steric ~pace requirement.
The ordering and the choice of the layers gel coat/~kin coat must follow the following rules :
- the layer of skin coat must be less permeable to water than the layer of gel coat, - the layer of skin coat must perfectly polymerize in the thin layer state.
The aim of this structure is to reverse the direction of semi-permeability of the gel coat layer.
As a result, if one considers the structure gel coat/skin coat/laminated resin reinforced by glass, there is obtained a repartition of the impermeability with respect to the layers having a dome-shape. With gel coat alone, this impermeability - decreases from the gel ccat layer towards outward.
The typical resins usable within the scope of the inven-tion are unsaturated bisphenolic polyesters, the bisphenolic polyesters hydrogen and unsaturated (the bisphenol nucleus of which is saturated) and the unsaturated isophthalic polyesters.
The bisphenolic resins are known for their properties of protection as regards chemical aggressibns, but have never been envisaged for forming a barrier against water between a laminated resin and a gel coat layer, such a barrier effect being essen-tially physico-chemical.
As bisphenol based resin which can be used preferably for forming the barrier according to the invention, one may cite a bisphenolic polyester resin sold under the trademark "STRATYL
lllO" and having the following molar formulation :
Bisphenol A : 0,2 mole Propylene glycol : 0,8 mole Maleic anhydride : 0,6 mole Phthalic anhydride : 0,4 mole in dilution in a reactive comonomer such as a styrene.
In order to ensure an excellent cohesion between the layers, ~, .. ..
.- ~ - . : - - .

- . ~ ' , . , :,~ ,: ' 1327~1 the invention provides that the gel coat layer is applied on the wall of a mold and the bisphenol based re~in layer i8 ap-plied on the gel coat layer either immediately, i.e. humid on humid ~between 0 and 20 min), or after gelation of the resin, but prior to complete polymerization, that is between 1 hour 30 min and 4 hours after application of the resin layer forming the gel coat. By applying the barrier-layer on the gel layer which is not yet polymerized, one ensures a stable bond between the two layers.
Likewise, in order to provide a good cohesion between the barrier-layer and the laminate, the invention provides that the lamination is carried out in a very short time after the deposition of the barrier-layer and prior to the complete pol-ymerization of the barrier layer.
Advantageously, the barrier-layer and the gel coat layer have each a thickness between 0.30 and 0.45 mm. Thereby is pro-vided a good preservation of the mechanical properties of the assembly, with limited weight and costs.
It is well known that, in order to increase the resistance to blistering of a laminated resin reinforced by glass and protected by a gel coat, it is sufficient to increase the thick-ness of the deposited gel coat.
Such an increase has for its upper limit the maximum thick-ness of the gel coat which can be applicated :
- due to the mechanical properties of the gel coat, - in order to avoid the consequences of a too thick layer of gel coat ~crackling, flaws).
This upper limit is of about 0.8 mm.
Therefore, the performances of two-layers structure (gel coatjskin coat) must be compared to those of a gel coat appli-cated with the same thickness.
With the same overall thickness ~0.7 mm), the gel coat/skin coat complex ~0.35 mm of gel coat, 0.35 mm of skin coat) delays the formation of bubbles or blisters by 3 or more times than what is obtained with a 0.7 mm thickness gel coat alone.
If the same comparison ls eEfected between the comple~

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.

and the skin coat alone, the effect then obtained is the same and still in favour of the complex.
The invention relates also to a structure including lami-nated resin walls, such as boat hulls, swimming pools, etc., the walls being obtained by the hereabove method.

Detailed DescriPtion of the In~ention The practising of the invention will be described in more detail hereafter.
A barrier-layer according to the invention has been used for making the hull of a boat having a length of 13 meters, with a total outer surface of 53 m2 composed of 36 m2 of under water parts wetted by the water and 17 m2 of upper parts.
On the inner wall of the mold has been applied with a gun a propylen-diethylen-neopentyl glycol maleoisophthalate based resin, with styrene as a reactive monomer. This resin used for forming the gel coat has been applied with a thickness of 0.9 mm on the:surface corresponding to the upper parts, viz. 19 kg, and of-0.41 mm on that corresponding to the underwarter parts, viz.
18.5 kg. The gelation of this gel coat has been provided by 2% of methylethylketon peroxyde in a 50~ solution in phthalate.
Three hours after application of this gel coat layer which is then polymerized and dry, there has been applied with a gun on the surface corresponding to the underwater parts and with a thickness of 0.46 mm, 18 kg of a maleophthalate of bisphenol A hydrogen and propylene, with styrene as reactive monomer. This resin is sold under the trademark of "STRATYL 1110".
The gelation of this layer has been provided with 2% of a 50% methylethylketon peroxide solution in phthalate. A bar-rier-layer, called "skin coat" has thus been provided on the underwater parts.
After polymerization during 4 hours of this skin coat layer, there has been formed on its inner face and on the inner face of the gel coat of the surEace corresponding to the upper parts, the polyester based laminated resin wall, reinforced with glass . , ; ~ . . . .
,: ' ,`' ' ~

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132792~

fibers. The hull thus made has proved to be practically imper-meable and did not exhibit blisters after having sojourned for several months in water.

ComParison test between two skin coats, one vinylester based and the other accordinq to the present invention.

In order to assess the performance of the gel coat based on maleoisophthalate of propylen-diethylen-neopentyl glycol associated with vinylester resin or bisphenolic polyester based skin coat layer, the following tests have been carried out.

1. Sensitivity to water of the skin coat constituting resins.
This test has been carrried out on plaquettes having a diameter of 8 cm, a weight of about 25 g and a thickness of 5 mm. Two plaquettes have been made,one comprising the bisphenolic polyester resin sold under the trademark of "STRATYL
1110", the other comprising a vinylester resin sold under the trademark "ATLAC 580".
The two plaquettes have been immersed in water until stabil-isation of the weight due to the water intake.
The plaquettes have been thereafter dried and weighed so as to measure the losses through solubilization of the endogenic compounds under the effect of the hydrolysis of the product and of the exogenic compounds.
The results are shown in Table N 1.

..

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, 1327~2~

Water intake losses through solubilization ___________________________________________________________ Plaquette comprising vinylester resin ~ATLAC 580" 0.7 0.35 ___________________________________________________________ Plaquette comprising bisphenolic polyester resin ~STRATYL 1110" 0.26 0.14 ___________________________________________________________ 2. Accelerated ageing when in contact with water.
The object of this second series of tests was to compare the ageing of a laminated resin protected by an isophthalic gel coat and by an isophthalic gel coat associated with a skin coat based on "ATLAC" vinylester resin and a skin coat based on ~STRATYL" bisphenolic resin. The ageing has been assessed by the occurence of blisters on the surface, after immersion in water at 60C.
The results are shown in Table n 2 ___________________________________________________________ Skin coat Results ___________________________________________________________ No skin coat Occurence of bubbles after 230 hours _______ ___________________________________________________ ATLAC based skin coat Occurence of bubbles after 910 hours ___________________________________________________________ STRATYL based skin coat No bubbles after 1600 hours ; test stopped ___________________________________________________________ ~5 . . . . .

g The bisphenolic based skin coat according to the invention improves therefore notably the protection against the pen-tration of water and hydrolysis.

Claims (12)

1. A method for the protection against water, particularly sea water, of a laminated resin substrate, coated on its face in contact with the water with a film forming resin layer, called gel coat, in which there is interposed between the laminated resin substrate and the gel coat layer a barrier-layer constituted by a resin having in its chain cyclic nuclei and double reactive bonds imparting to it a high steric space requirement.
2. A method according to claim 1, wherein the barrier-layer is constituted by a resin of the group including the unsaturated bisphenolic polyesters, the bisphenolic polyesters hydrogen and unsaturated (of which the bisphenol nucleus is saturated) and the unsaturated isophthalic polyesters.
3. A method according to claim 2, wherein the unsaturated bisphenolic polyesters resin has the following molar formulation:
Bisphenol A : 0.2 mole Propylene glycol : 0.8 mole Maleic anhydride : 0.6 mole Phthalic anhydride : 0.4 mole
4. A method according claim 1, wherein the resin layer forming the surface gel coat is applied on the wall of a mold and the resin layer forming the barrier is applied on the surface layer prior to the polymerization of the resin constituting the gel coat.
5. A method according to claim 4, wherein the resin layer forming the barrier is applied on the gel coat layer between 0 and 20 min after formation of this latter layer.
6. A method according to claim 4, in which the interval of time between the application of the resin layer forming the gel coat and the application on the latter of the resin forming the barrier-layer is between 1 hour 30 min and 4 hours 0 min.
7. A method according to anyone of claims 4 to 6, wherein the laminated resin layer is made in a very short period of time after the deposition of the barrier-layer.
8. A method according to anyone of claims 1 to wherein the resin layer forming the surface gel coat and the resin layer forming the barrier each have a thickness of between 0.30 and 0.45 mm.
9. Structure including laminated resin walls such as boat hulls, swimming pools, etc., in contact with water, including, on the surface of the laminated resin wall in contact with the water, between said surface and the gel coat layer, a barrier-layer consituted by a polymerized resin having in its chain prior to polymerization cyclic nuclei and double reactive bonds imparting to it a high steric space requirement.
10. A structure according to claim 9, wherein said barrier-layer is constituted by a resin of the group including unsaturated bisphenolic polyesters, the bisphenolic polyesters hydrogen and unsaturated (of which the bisphenol nucleus is saturated) and the unsaturated isophthalic polyesters.
11. A structure according to claim 9, wherein the unsatu-rated bisphenolic polyester resin has the following molar formu-lation :
Bisphenol A : 0.2 mole Propylene glycol : 0.8 mole Maleic anhydride : 0.6 mole Phthalic anhydride : 0.4 mole
12. A structure according to anyone of claims 9 to 11, wherein said barrier-layer and said gel coat layer each have a thickness of 0.30 to 0.45 mm.
CA000609008A 1988-08-24 1989-08-22 Method for the protection against water of a laminated resin wall, and a protected laminated resin wall thus obtained Expired - Fee Related CA1327921C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR88.11180 1988-08-24
FR8811180A FR2635716B1 (en) 1988-08-24 1988-08-24 METHOD OF PROTECTING AGAINST WATER OF A LAMINATED RESIN WALL AND WALL OF PROTECTED LAMINATED RESIN THUS OBTAINED

Publications (1)

Publication Number Publication Date
CA1327921C true CA1327921C (en) 1994-03-22

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ID=9369494

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000609008A Expired - Fee Related CA1327921C (en) 1988-08-24 1989-08-22 Method for the protection against water of a laminated resin wall, and a protected laminated resin wall thus obtained

Country Status (12)

Country Link
US (1) US4959259A (en)
EP (1) EP0356324B1 (en)
JP (1) JPH0316679A (en)
AT (1) ATE85069T1 (en)
AU (1) AU614707B2 (en)
CA (1) CA1327921C (en)
DE (1) DE68904620T2 (en)
DK (1) DK398689A (en)
FR (1) FR2635716B1 (en)
IE (1) IE62119B1 (en)
NZ (1) NZ230324A (en)
PT (1) PT91505B (en)

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Publication number Priority date Publication date Assignee Title
AU695140B2 (en) * 1995-03-13 1998-08-06 Mp Hydro Pty Limited Moulded water containers and process for making same
ES2171048T3 (en) * 1997-10-10 2002-08-16 Cook Composites & Polymers COMPOSITIONS OF UNSATURATED POLYESTER RESINS, WATER RESISTANT.
ZA9962B (en) 1998-01-20 1999-07-06 Cook Composites & Polymers Aromatic polyol end-capped unsaturated polyetherester resins and resin compositions containing the same having improved chemical and/or water resistance.
US20040034333A1 (en) * 2002-08-19 2004-02-19 Seese Timothy M. Dialysis catheters with optimized user-friendly connections
US9029460B2 (en) * 2009-02-06 2015-05-12 Stacey James Marsh Coating compositions containing acrylic and aliphatic polyester blends
US8324316B2 (en) * 2009-02-06 2012-12-04 Eastman Chemical Company Unsaturated polyester resin compositions containing 2,2,2,4-tetramethyl-1,3-cyclobutanediol and articles made therefrom
US8163850B2 (en) * 2009-02-06 2012-04-24 Eastman Chemical Company Thermosetting polyester coating compositions containing tetramethyl cyclobutanediol
US9029461B2 (en) * 2009-02-06 2015-05-12 Eastman Chemical Company Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol
US8168721B2 (en) 2009-02-06 2012-05-01 Eastman Chemical Company Coating compositions containing tetramethyl cyclobutanediol
NZ594588A (en) * 2009-02-23 2013-03-28 Hydrawall Pty Ltd Surface composition and method of application
US9598602B2 (en) 2014-11-13 2017-03-21 Eastman Chemical Company Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds
US9650539B2 (en) 2014-10-27 2017-05-16 Eastman Chemical Company Thermosetting compositions based on unsaturated polyesters and phenolic resins
US9487619B2 (en) 2014-10-27 2016-11-08 Eastman Chemical Company Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol
US20160340471A1 (en) 2015-05-19 2016-11-24 Eastman Chemical Company Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol
US20170088665A1 (en) 2015-09-25 2017-03-30 Eastman Chemical Company POLYMERS CONTAINING CYCLOBUTANEDIOL AND 2,2 BIS(HYDROXYMETHYL) AlKYLCARBOXYLIC ACID
US9988553B2 (en) 2016-02-22 2018-06-05 Eastman Chemical Company Thermosetting coating compositions
US10011737B2 (en) 2016-03-23 2018-07-03 Eastman Chemical Company Curable polyester polyols and their use in thermosetting soft feel coating formulations

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4126719A (en) * 1977-05-03 1978-11-21 Ina Seito Co., Ltd. Reinforced plastic products with decorated surfaces
US4724173A (en) * 1986-01-29 1988-02-09 The Board Of Governors For Higher Education, State Of Rhode Island Method of preventing gel coat blistering in fiber glass reinforced polymers

Also Published As

Publication number Publication date
ATE85069T1 (en) 1993-02-15
EP0356324A3 (en) 1990-03-21
DE68904620T2 (en) 1993-05-19
DK398689A (en) 1990-02-25
DE68904620D1 (en) 1993-03-11
EP0356324B1 (en) 1993-01-27
PT91505A (en) 1990-03-08
IE892617L (en) 1990-02-24
AU614707B2 (en) 1991-09-05
IE62119B1 (en) 1994-12-14
DK398689D0 (en) 1989-08-14
JPH0316679A (en) 1991-01-24
FR2635716A1 (en) 1990-03-02
NZ230324A (en) 1991-09-25
US4959259A (en) 1990-09-25
EP0356324A2 (en) 1990-02-28
FR2635716B1 (en) 1990-11-02
AU3999689A (en) 1990-03-01
PT91505B (en) 1995-05-04

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