GB2277742A - Anti-fouling resinous compositions for marine structure - Google Patents

Abstract

A resinous moulding composition comprising one or more of polyol compounds (A) (eg an epoxy group-containing polyol compound, an isocyanate group-containing polyol compound, a urethane link and epoxy group-containing polyol compound, an acryloyl or methacryloyl group-containing polyol compound and a urethane link and acryloyl or methacryloyl group-containing polyol compound) combined with a 3-isothiazolone derivative (B) of the formula <IMAGE> (wherein, X<1> and X<2> each are independently hydrogen halogen or C1-C4 alkyl having a linear or branched chain and Y is C1-C14 alkyl having a linear or branched chain without a substituent; C1-C9 aralkyl which may be substituted by halogen or lower alkyl, or C1-C9 aryl which may be substituted by phenoxy, hydroxy, trihalomethyl, halogen, lower alkyl or lower alkoxy group), said derivative (B) being blended in an amount of 3 - 50 parts by weight per 100 parts by weight of said polyol compound (A).

Description

Anti-Fouling Resinous Compositions For Marine Structure This invention relates to a resinous composition useful for the prevention or inhibition of fouling of marine structures such as vessel hulls, buoys, fenders marine hoses, piers, pilings and the like by organisms in sea water without adversely affecting the environment.

Such marine structures are susceptible to the deposition and proliferation on their underwater surfaces of organisms such as barnacles, oysters, blue mussels, hydrozoans, serupura, sea mosses, ascidians, fimbriate sea mosses, sea lettuces, green lavers and the like. These organisms tend to adhere to for example a marine vessel hull over a period of time to an extent to reduce normal cruising speed, resulting in increased fuel consumption, declined mechanical strength and malfunctioning of the marine structure.

It has been proposed for preventing marine organisms from depositing onto marine structures to use an organotin compound or cuprous oxide known as an antifouling compound. However, organotin compounds are liable to accumulate in and become hazardous to animal and plant and therefore their use is being restricted or banned for ecological reasons.

Various advanced methods and effective compounds have been proposed to cope with the antifouling problems as disclosed in the following categories of Patent documents.

The first category includes Japanese Laid-Open Patent Publication (Kokai) No. 84166/1987, No.

283167/1987, No. 5121/1989, No. 252677/1989, No.

266171/1989 and No. 306479/1989 which disclose respective methods for forming a surface material resistant to marine organisms.

The second category embraces Japanese Patent Publication No. 4577/1977 and No. 24551/1988, Japanese Laid-Open Patent Publication (Kokai) No. 33304/1988, No.

304069/1988, No. 229028/1989, No. 36211/1990 and No.

69576/1990 which deal with the approach of combatting the fouling of marine structures with a minimum amount of antifouling agents.

The third category is known from Japanese Patent Publication No. 6628/1988 and No. 5121/1989, Japanese Laid-Open Patent Publication (Kokai) No. 298497/1987 and No. 229081/1989 which respectively pertain to the use of cilia and the like.

The above proposed methods and materials, however, have difficulties yet to be overcome when applied to rubber or resin surfaces, or when used as rubber or resin molded products.

Japanese Patent Publication No. 4577/1977 is directed to the use of organotin compounds which are environmentally objectionable.

Japanese Patent Publication No. 50984/1986 discloses an anti fouling paint in which 3-isothiazolone derivatives are used but is silent as to the composition thereof or the usefulness for a rubber, resin or resilient molded product. The disclosed antifouling paint remains effective only for seven months.

Japanese Laid-Open Patent Publication (Kokai) No.

222063/1985 discloses the use of 3-isothiazolone derivates for rubber but fails to teach their anti fouling performance.

Japanese Laid-Open Patent Publication (Kokai) No.

300806/1992 discloses an antifouling resin composition containing 3 to 50 parts by weight of N-(2,4,6-trichlorophenyl) maleimide per 100 parts by weight of a prepolymer having polyetherpolyol or polyesterpolyol nuclei. This composition has much to be desired as regards both resiliency and antifouling efficacy depending upon the type of marine structures for which it is used.

With the foregoing difficulties of the prior art in view, the present invention seeks to provide a resinous composition for preventing or inhibiting fouling of marine structures, which composition can be cured into a flexible moulded article capable of exhibiting anti fouling performance over prolonged periods of time and without resort to organotin compounds.

The principal objective of the invention can be achieved by the provision of a resinous composition comprising one or more of polyol compounds (A) selected from the group consisting of an epoxy group-containing polyol compound, an isocyanate group-containing polyol compound, a urethane link and epoxy group-containing polyol compound, an acryloyl or methacryloyl group-containing polyol compound and a urethane link and acryloyl or methacryloyl group-containing polyol compound combined with a 3-isothiazolone derivative (B) of the formula

wherein, X1 and X2 each are independently hydrogen atom, halogen or an alkyl group having a linear or branched chain of 1 to 4 or carbon atoms, and Y is an alkyl group of 1 to 14 carbon atoms having a linear or branched chain without a substituent; an aralkyl group of 1 to 9 carbon atoms which may be substituted by halogen or lower alkyl group, or an aryl group of 1 to 9 carbon atoms which may be substituted by phenoxy, hydroxy, trihalomethyl, halogen, lower alkyl or lower alkoxy group), said derivative (B) being blended in an amount of 3-50 parts by weight per 100 parts by weight of said polyol compound (A).

The term moulded article is used to designate various forms of antifouling article ranging from a web-like, tape tubular, laminate to other polygonal materials configured to fit complimentary marine structures.

It has now been found that such moulded articles should have a thickness of at least imam, preferably 3mm or greater to retain effective antifouling behavious over extended periods of time.

The resinous composition of the invention predominantly comprises a prepolymer which can be cured into a resilient or pliable matrix and which is one or more polyl compounds (A) selected from the group consisting of a polyol compound (a], an epoxy group-containing polyol compound [b), an isocyanate group-containing polyol compound [c], a urethane link and epoxy group-containing polyol compound td], an acryloyl or methacryloyl group-containing polyol compound [e], and a urethane link and acryloyl or methacryloyl group-containing polyol compound [f].

The polyol compound [a] specifically refer to polyetherpolyol or polyesterpolyol. Polyetherpolyol is a product derivable from addition polymerization of one or more of alkylenes such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran with a compound containing at least two active hydrogen atoms such as a polyhydric alcohol, an alkanolamine and a polyhydric phenol.

Polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, glycerin, hexanetriol, trimethylol propane, neopentyl glycol, 1,6-hexanediol, 1,3, 6-hexanetriol and pentaerythritol.

Alkanolamines include ethanolamine and propanolamine.

Polyhydric phenols include resorcin and bisphenol.

Polyethylene glycol, polypropylene glycol, polyetramethylene glycol and polybutylene glycol are preferred, of which polytetramethylene glycol is particularly preferred.

Polyesterpolyols include a condensate of polyhydric alcohol and polybasic carboxylic acid, a condensate of hydroxycarboxylic acid and polyhydric alcohol and lactone polymers.

The polybasic carboxylic acids include adipic acid, sebacic acid, glutaric acid, azelaic acid, fumaric acid, maleic acid, succinic acid, dodecenylsuccinic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, hexahydrophthalic acid, dimer acid, trimellilic acid, pyromellitic acid and anhydrides thereof.

The condensate of hydroxycarboxylic acid and polyhydric alcohol includes castor oil, a reaction product of castor oil and ethylene glycol, and a reaction product of castor oil and propylene glycol.

The lactone polymers include those obtained by ring opening polymerization of s-caprolactam, 6-methyl-s-caprolactam or e-methyl-s-caprolactam in the presence of an appropriate polymerization initiator.

The epoxy group-containing polyol compound [b] is a compound having an epoxy introduced into the polyol compound [a]. Specifically, it is a compound obtained by making the hydroxyl group of the polyol compound [a] into sodium alkoxide with sodium methoxide or sodium hydride and reacting with epichlorohydrin, or alternatively obtained by reacting the hydroxyl group of the polyol compound [a] with an anhydride such as maleic anhydride, phthalic anhydride, trimellitic acid anhydride or tetrahydrophthalic anhydride, followed by further reaction with an epoxy resin.

The isocyanate group-containing polyol compound [c] is a compound having an isocyanate group introduced into the polyol compound [a]. Specifically, it is a compound obtained by addition reaction of a polyisocyanate compound with the hydroxyl group of the polyol compound [a]. The polyisocyanate compound used in such addition reaction includes 2,4-tolylenediisocyanate, 2, 6-tolylenediisocyanate, phenylenediisocyanate, xylenediisocyanate, diphenylmethane-4,4'-diisocyanate, naphthylne-l, 5-diisocyanate, and a compound hydrogenated thereto, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, l-methyl-2,4-diisocyanate cychohexane, 1-methyl-2,6-diisocyanate cyclohexane, dicyclohexylmethane diisocyanate, triphenylmethane triisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate.

The reaction conditions are not particularly restricted, but the ratio of a starting polyol compound to a polyisocyanate compound is such that the resulting hydroxyl group of the polyol compound is not more than 1 per 1 isocyanate group of the polyisocyanate compound, preferably 0.95 to 0.75 hydroxyl group. The reaction may be conducted under ordinary conditions; i.e., at a temperature of about 500 to 1000C under atomospheric pressure.

The urethane link and epoxy group-containing polyol compound (d] is a compound obtained by having urethane link or epoxy group introduced into the polyol compound (a]. Specifically, it is a compound obtained by addition reaction of the hydroxyl group of a compound containing hydroxyl and epoxy groups with the isocyanate group of the isocyanate group-containing polyol compound [c]. The compound containing hydroxyl and epoxy groups includes glicidol and glycerindiglycidyl ether. The reaction conditions are not particularly restricted, but may sutably be at a temperature of 800 to 100C for 4 to 10 hours.

The acryloyl or methacryloyl group-containing polyol compound [e] is a compound obtained by having an acryloyl or methacryloyl group introduced into the polyol compound [a]. Specifically, it is a compound obtained by ester forming reaction of the hydroxyl group of the polyol compound [a] with the carboxyl group of a compound such as acrylic acid, methacrylic acid, 2-acryloyl or methacryloyl oxyethylsuccinic acid, 2-acryloyl methacryloyl oxyethylphthalic acid or 2-acryloyl or methacryloyl oxyethylhexahydrophthalic acid. This eater forming reaction may be typically effected at 800 to 1200C for 10 to 20 hours.

The urethane link and acryloyl or methacryloyl group-containing polyol compound [f] is a compound obtained by having a urethane link and acryloyl or methacryloyl group introduced into the polyol compound [a]. Specifically, it is a compound obtained by addition reaction of the isocyanate group of the isocyanate group-containing polyol compound [c] with the hydroxyl group of a compound containing a hydroxyl group and acryloyl or methacryloyl group thereby forming a urethane link.

The compound containing hydroxyl group and acryloyl or methacryloyl group includes 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate, 2-hydroxy-3-phenoxypropyl acrylate or methacrylate, and 2-hydroxybutyl acrylate or methacrylate. The addition reaction may be suitably effected at 800 to 1000C for 8 to 16 hours.

The polyol compounds (A) under consideration have a polyether or polyester skeleton in their molecule.

Therefore, by curing such a resinous composition with 3-isothiazolone derivative (B) referred to hereafter, the latter component can be retained and released effectively over prolonged time to demonstrate optimum antifouling behaviour.

The antifouling component (B) in the resinous composition of the invention is represented by the formula

(wherein , X1 and X2 each are independently hydrogen atom, halogen or an alkyl group having a linear or branched chain of 1 to 4 carbon atoms, and Y is an alkyl group of 1 to 14 carbon atoms having a linear or branched chain without a substituent; an aralkyl group of 1 to 9 carbon atoms which may be substituted by halogen or lower alkyl group, or an aryl group of 1 to 9 carbon atoms which may be substituted by phenoxy, hydroxy, trihalomethyl, halogen, lower alkyl or lower alkoxy group), said derivative (B) being blended in an amount of 3-50 parts by weight per 100 parts by weight of said polyol compound (A).) The 3-isothiazolone derivative (B) is highly effective for preventing deposition and growth of marine organisms on marine structures without toxic or otherwise deleterious effects upon human body or other living things, thus with no fear of enviromental pollution.

Specific examples of X1 in the formula preferably include hydrogen, chloro, bromo, iodo, methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group.

Specific examples of X2 include hydrogen, chloro, bromo, iodo, methyl group, ethyl group, propyl group, isopropyl group, buthyl group, t-butyl group, chloromethyl group, chloropropyl group, bromomethyl group, bromoethyl group and bromopropyl group.

Specific examples of Y include methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, decyl group, pentadecyl group, octadecyl group, cyclopropyl group, cyclohexyl group, benzyl group, 3,4-dichlorobenzyl group, 4-methoxybenzyl group, 4-chlorobenzyl group, 3,4-dichlorophenyl group, hydroxymethyl group, chloromethyl group, chloropropyl group, diethylaminoethyl group, cyanoethyl group, carbomethoxyethyl group, ethoxyethyl group, 2 -methoxy- 1 -bromomethyl group, 3,3,5-trimethylcyclohexyl group, phenoxyethyl group, P-chloroanilinomethyl group, phenylcarbamoxymethyl group aryl group, propinyl group, vinyl group, carboxyethyl group, l-isothyazonylethyl group and 1,2,2-trichlorovinyl group.

Preferred examples Xl and X2 are chloro and that of Y is 1 to 9 non-substituted aralkyl group or aryl group, particularly CgH17.

Exemplary of such 3-isothiazolone derivative is a 4,5-dichloro-2-n-octylisothiazoline-3-on as typically represented by LD50 of the 4,5-dichloro-2-n-octylisothiazoline-3-on which is 1700 mg/kg (male rat) and 2800 mg/kg (female rat).

Further details on the 3-isothiazolone derivative (B) are recited in Japanese Patent Publication No.

50984/1986.

In the inventive composition, the 3-isothiazolone derivative (B) is added in an amount of 3 to 50 parts by weight, preferably 10 to 30 parts by weight per 100 parts by weight of the polyol compound (A). When the content of (B) is less than 3 parts by weight, the antifouling effect would become substatially nil, and if it exceeds 50 parts by weight, the intended cured product would be less flexible.

A plurality of and different combinations of compounds (A) and (B) may be used in the formulation of the inventive composition.

There may be used a curing agent (including hardenning catalysts, photopolymerization initiators and the like) to promote curing of the resinous composition.

Such curing agent may be dependent on the type of a reactive functional group in the polyol compound (A).

Specifically, it is preferably selected from the aforementioned polyisocyanate compounds when the polyol compound [a] is chosen for (A). When the polyol (A) is the epoxy group-containing polyol compound [b] having an epoxy group or the urethane link and epoxy group containing polyol compound td], the curing agent is suitably selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, bis(hexamethylene)triamine, polymethylenediamine, isophoronediamine and other aliphatic amines, diaminodiphenylmethane, diaminodiphenylsulfone, methylenebisorthochloroaniline and other aromatic amines, secondary or tertiary amine and anhydrides referred to above on the epoxy group-containing polyol compound [b].

With the isocyanate group-containing polyol compound [c] selected for (A), the curing agent may be selected from the polyhydric alcohols and the amines recited hereinabove.

When (A) is the acryloyl or methacryloyol group-containing polyol compound [e] whose reactive functional group is acryloyl or methacryloyl group or the urethane link and acryloyl or methacryloyl group-containing polyol compound [f], the curing catalyst such as benzoyl peroxide, methylacetoacetate peroxide, methylethylketone peroxide, acetylacetone peroxide and other peroxides, and a photopolymetization initiator such as 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone and 2-methyl-1-(4-methylthio)phenyl)-2-morpholinopropanone-l may be suitably used.

The amounts of the curing agent, curing catalyst and photopolymerization initiator to be added to the resinous composition of the invention are subject to an extent such that is free from adversely affecting the properties of the 3-isothiazolone derivative (B). They may be added selectively or jointly.

Other additives such as a filler, plasticizer or antioxidant may also be used.

The inventive composition may be of one-pack type or two-pack type and the curing conditions therefor such as by heating or irradiation are dependent upon the particular combination of the polyol compound (A) and the curing compounds.

It is believed that the effective and prolonged antifouling behaviour of the inventive resinous composition is attributable to the derivative (B) being anchored in a matrix (high-molucular gel mesh) resulting from the curing treatment of the compound (A) as well as to its strong affinity with the polyether or polyester skeleton of the latter, whereby an optimum amount of (B) can be released showly over a period of approximately two consecutive years to prevent or inhibit the tendency of objectionable organisms to deposit and proliferate on marine structures.

A moulded article such as for example in the form of a sheet resulting from the curing of the inventive resinous composition may be applied partially or wholly to a given marine struture as by means of an adhesive compound, or alternatively moulded directly over the structure, or any known manner suitable for the particular configuration of the structure. The moulded anti fouling material according to the invention should be at least 1 mm, preferably greater than 3 mm thick depending upon the characteristics and function of the marine structure to which it is applied.

The invention will be further described in connection with the examples given below.

Polyetherpolyols and polyesterpolyols numbered (1) through (9) below were used for compound (A).

4,5-dichloro-2-n-octylisothiazoline-3-on was used as derivative (B). Table A shows the formulations of respective resinous compositions. Table B shows the test results.

(Polyetherpolyol and Polyesterpolyol) (1) Terminal epoxy group polyetherpolyol: Two mols of hexahydrophthalic anhyderide were reacted with one mol of polypropylene glycol &num;1000 (Mw=1000 made by Asahi Glass Co.) Then, 2.5 mols of epoxy resin (Type 828 made by Sumitomo Chemical Co.) were reacted therewith to synthesise an epoxy group-containing polyetherpolyol.

Epoxy equivalent of this compound was about 1000.

(2) Urethane link and epoxy group-containing polyetherpolyol: Two mols of isophoronediisocyanate were reacted with one mol of polytetramethylene glycol X2000 (Mw=2000 made by Mitsubishi Chemical Industries), followed by addition of 2.1 mols glycidol (made by Daiseru Kagaku) to synthesise a urethane link and epoxy group-containing polyetherpolyol. Epoxy equivalent of this compound was 1350.

(3) Terminal isocyanate group polyetherpolyol: A commercially available prepolymer, polyester-based Hypren L-100 (made by Mitsui Toatsu Chemicals) was used. Isocyanate % in this compound was 4.2%.

(4) Terminal acryloyl group polyetherpolyol: one mol of polyethlene glycol &num;1000 (made by Kanto Kagaku) was reacted with 2.1 mol of acrylic acid.

(5) Urethane link and acryloyl group-containing polyetherpolyol: One mol of polytetramethylene glycol &num;850 (Mw=850 made by Mitsubishi Chemical Industries) was reacted with 2.05 mol of 4,4' -diphenylmethanediisocyanate, followed by reaction with 2.1 mol of 2-hydroxyethylacrylate to synthesise a urethane link and acryloyl group-containing polyetherpolyol.

(6) Terminal epoxy group polyesterpolyol: A commercially available prepolymer, Purakusel G-402( made by Daiseru Ragaku Kogyo) was used. Epoxy equivalent of this compound was 1350.

(7) Terminal isocianate group polyesterpolyol: A commercially available prepolymer, Purakusel EP-1500 (made by Daiseru Kagaku Kogyo) was used. Isocianate % in this compound was 4.25%.

(8) Urethane link and acryloyl group-containing polyesterpolyol: Two mols of 4,4'-diphenylmethanediisocyanate were reacted with one mol of polycaprolactondiol known as Purakusel T-2205 (made by Daiseru Kagaku Kogyo), followed by reaction with 2.1 mols of 2-hydroxyethylacrylate thereby synthesising a urethane link and acryloyol group-containing polyesterpolyol.

(9) Urethane link and epoxy group-containing siliconediol (Cotrols): Two mols of isophoronediisocyanate were reacted with one mol of siliconediol (X-22-160A made by Shin-Etsu Chemical), followed by addition of 2.1 mol of glycidol (made by Daiseru Kagaku) to synthesise a urethane link and epoxy group-containing siliconediol. Epoxy equivalent of this compound was 1200.

(Performance Evaluation Test) 1) Normal State Physical Properties Test Each of the listed compositions was kneaded or mixed and formed into a sheet 150 x 150 x 3 mm, which was cured under the conditions shown in Table A. The cured products were subjected to a tensile test using No. 2 dumbbell test piece according to JIS K 6301 for tensile stress (M25) and elongation (E).

2) Seawater Immension Test Each of the compositions was kneaded or mixed and formed into a sheet and cured under the conditions shown in Table A to form a test piece measuring 300 x 300 x 5mm. These test pieces were immersed to a depth of about one meter from the surface of the seawater at the Bay of Suruga, about 10 m from the guay off Uchiura-nagahama, Numazu-shi, Shizuoka, Japan. They were pulled up at selected time intervals to evaluate the deposits of marine organisms according to the criteria given below. This test was started in 1991.

(Deposit of Organisms) A: No deposits were observed.

B: Traces were found but with no further growth.

C: Deposits to about 1/3 of the entire area were observed.

D: Deposits to about 1/2 of the entire area were observed.

E: Deposits over the entire area were observed. Table A

Examples 1 2 3 4 5 6 (1) Terminal epoxy group 100 polyetherpolyol (2) Urethane link and epoxy group- 100 100 containing polyetherpolyol Compound A (3) Hypren L-100 100 (4) Polyethylene glycol *1000 100 diacrylate (5) Polytetramethylene glycol &num;;850 urethaneacrylate 100 4,5-dichloro-2-n- 20 20 20 20 20 3 Compound B octylisothiazoline-3-on N-(2,4,6-trichlorophenyl)maleimide Isophoronediamine 4.0 Curing Agent Diaminodiphenylmethane 3.8 3.8 Methylenebisorthochloroaniline 12 Polymerization Initiator Irgacure 184 3 Curing Catalyst Methylethylketoneperoxide 3 Curing Conditions 100 C, 120 C, 100 C, * 100 C, 120 C 1 hr. 12 hrs. 6 hrs. 8 hrs. 12 min.

* Ultraviolet rays were irradiated with an 80-W high-pressure mercury lamp from a distance of 30 cm for 10 minutes.

Table A - continued - [1]

Examples Controls 7 8 9 10 2 3 (1) Terminal epoxy group polyetherpolyol (2) Urethane link and epoxy group- 100 100 100 100 100 containing polyetherpolyol Compound A (3) Hypren L-100 100 (4) Polyethylene glycol &num;1000 diacrylate (5) Polytetramethylene glycol &num;;850 urethaneacrylate 4,5-dichloro-2-n- 30 50 20 1 100 Compound B octylisothiazoline-3-on N-(2,4,6-trichlorophenyl)maleimide Isophoronediamine Curing Agent Diaminodiphenylmethane 3.8 3.8 3.8 3.8 3.8 Methylenebisorthochloroaniline 12 Polymerization Initiator Irgacure 184 Curing Catalyst Methylethylketoneperoxide Curing Conditions 120 C, 120 C, 40 C, 120 C, 120 C, 120 C 12 hrs, 12 hrs. 48 hrs. 12 hrs. 12 hrs. 12 hrs.

Table A - continued - [2]

Examples 10 11 12 13 14 (6) Terminal epoxy group 100 polyesterpolyol (7) Terminal isocyanate group 100 100 100 polyesterpolyol Compound A (8) Urethane link and acryloyl group-containing 100 polyesterpolyol (9) Urerthane link and epoxy groupcontaining siliconediol 4,5-dichloro-2-n- 20 20 20 3 30 Compound B octylisothiazoline-3-on N-(2,4,6-trichlorophenyl)maleimide 1,3-bisaminomethylcyclohexane 3.0 Curing Agent Methylenebisorthochloroaniline 12 12 12 Polymerization Initiator Irgacure 651 3 Curing Conditions 100 C, 100 C, * 100 C, 100 C, 1 hr. 6 hrs. 6 hrs. 6 hrs.

* Ultraviolet rays were irradiated with an 80-W high-pressure mercury lamp from a distance of 30 com for 10 minutes.

Table A - continued - [3]

Controls Example 15 4 5 6 7 (6) Terminal epoxy group 100 polyesterpolyol (7) Terminal isocyanate group 100 100 100 polyesterpolyol Compound A (8) Urethane link and acryloyl group-containing polyesterpolyol (9) Urethane link and epoxy groupcontaining siliconediol 100 4,5-dichloro-2-n- 50 20 1 85 Compound B octylisothiazoline-3-on N-(2,4,6-trichlorophenyl)maleimide 20 1,3-bisaminomethylcyclohexane 3.0 3.0 Curing Agent Methylenebisorthochloroaniline 12 12 12 Polymerization Initiator Irgacure 651 Curing Conditions 100 C, 100 C, 100 C, 100 C, 100 C, 6 hrs. 1 hr. 1 hr. 6 hrs. 6 hrs.

Table B

Examples Controls 1 2 3 4 5 6 7 8 9 1 2 3 Normal State Test Tensile Strength 40 26 42 30 35 30 26 31 43 25 -* 25 (kg/mm2) Elongation (%) 350 460 320 360 350 450 450 420 450 460 -* 460 Immersion Test after 3 months A A A A A A A A A A -* C after 6 months A A A A A A A A A B -* D after 1 year A A A A A A A A A D -* E after 2 years A A A A A A A A A E -* E * The composition sample was not cured.

Table B - continued -

Examples Controls 10 11 12 13 14 15 4 5 6 7 Normal State Test Tensile Strength 35 30 35 25 25 25 33 90 30 -* (kg/mm2) Elongation (%) 400 400 350 450 450 470 370 100 450 -* Immersion Test after 3 months A A A A A A A A A -* after 6 months A A A A A A B A B -* after 1 year A A A A A A B C D -* after 2 years A A A A A A B D E -* * The composition sample was not cured.

Claims (6)

1. A resinous composition comprising one or more of polyol compounds (A) selected from the group consisting of an epoxy group-containing polyol compound, an isocyanate group-containing polyol compound, a urethane link and epoxy group-containing polyol compound, an acryloyl or methacryloyl group-containing polyol compound and a urethane link and acryloyl or methacryloyl group-containing polyol compound combined with a 3-isothiazolone derivative (B) of the formula

(wherein , X1 and X2 each are independently hydrogen atom, halogen or an alkyl group having a linear or branched chain of 1 to 4 carbon atoms, and Y is an alkyl group of 1 to 14 carbon atoms having a linear or branched chain without a substituent; an aralkyl group of 1 to 9 carbon atoms which may be substituted by halogen or lower alkyl group, or an aryl group of 1 to 9 carbon atoms which may be substituted by phenoxy, hydroxy, trihalomethyl, halogen, lower alkyl or lower alkoxy group), said derivative (B) being blended in an amount of 3-50 parts by weight per 100 parts by weight of said polyol compound (A).

2. A resinous composition as defined in claim 1 which further incorporates a curing agent.

3. A moulded article resulting from the curing of the resinous composition of claim 1 or 2 and having a minimum thickness of imam.

4. A moulded article of claim 3 having a minimum thickness of 3 mm.

5. A resinous composition substantially as hereinbefore described.

6. A moulded article substantially as hereinbefore described.