JPS59500620A - Stabilizer composition for antifouling paints - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Stabilizer composition for antifouling paints knapsack of invention field of invention The present invention relates to an antifouling coating composition. The present invention uses cuprous oxide and a small number of repeating units. Polymerizations derived at least in part from triorganotin salts of ethylenically unsaturated The increase in viscosity that often occurs when antifouling paints containing O for stabilizer compositions that optionally prevent gelation. Explanation of conventional techniques Organisms such as vines and algae attach to submerged parts of the ship's hull. The growth substantially increases the resistance with which the hull passes through the water. the Unfortunately, the ship's fuel efficiency and maximum speed are reduced by regularly cleaning accumulated contaminants. It is necessary to remove 1. Please keep in mind the cost of this work. I need. Prevents the attachment and growth of contaminant organisms on the hull, thereby facilitating cleaning and cleaning. A commonly used method to extend the repainting period is to use paint containing antifouling agents. This method involves applying a finishing coat to the entire part of the hull that will be immersed in water. () G-n Triorganotin compounds (like butyltin) fluoride are particularly effective antifouling agents. It has been recognized for a long time that there is. US 1 Patent No. 3. There are many details in the specification of +67.473. Disadvantages of triorganohydrogen compounds, such as high toxicity to mammals. The high extractability of the triorganotin compound from the paint film due to the sea water number is Luganotin compound It is written that it will be removed. In the method described in the above US patent specification, triorganotin derivatives of ethylenically unsaturated acids such as methacrylic acid or methacrylic acid. Other ethylenes that can be polymerized alone or copolymerized with the above triorganotin derivatives. unsulfated compounds, preferably lower alkyl esters of acrylic acid or methacrylic acid It is polymerized in the presence of tel.

U.S. Patent No. 4,191.579 uses pigments that are water-insoluble and reactive with seawater. and water-insoluble, water-retaining and non-reactive pigments in antifouling finishing paints that can be applied to ship hulls. When present in water, this pigment combination causes lead to Paints are given self-leveling properties. The zero bathing degree stated to be sufficient to release an effective concentration of the poison; On the other hand, triorganotin-containing polymers used as finishing paints and as binders and antifouling agents. Premature welding with the body is prevented. According to the description in the above US patent specification, oxidized No. 1 steel and zinc oxide Ii are preferred as seawater-reactive pigments. As little as cuprous oxide Both are polymers partially derived from triorganotin salts of ethylenically unsaturated acids. A paint containing (i) is preferred from the point of view of antifouling activity of cuprous oxide (71A), This paint cannot be stored for more than 6 months because the polymer gels quickly. . The above patent specification states that if a longer storage period is required, organotin-containing It states that the combination and oxidized No. 1 steel must be packaged as separate components. Ru. These two-component paints can mix a large amount of 2m of ingredients to a moderate degree of uniformity. The final composition is unsuitable for commercial application due to its undesirable nature. If the coating is not homogeneous, the coating applied using this composition will be Possibly in a zone with relatively low concentrations of toxic substances. It is believed that early contamination occurs.

Unopened Patent No. A, +87.211 specification uses cuprous oxide as a seawater-reactive additive. No. 4.1' containing said U.S. Patent No. 4.1'? Storage stability of the antifouling paint described in No. 1.579 Qualitatively, calcium sulfate in the anhydrous and hemihydrate O form is present in this composition. various inert and water-insoluble dehydrating agents or aliphatic isocyanates. It has been stated that this can be dramatically increased by the inclusion of organic compounds that are reactive with water. There are n. However, experimental data indicate that accelerated aging performed at a temperature of 50'C Tests tested anhydrous calcium sulfate, polymeric triorganotin toxicants, and tin oxide. The viscosity of the paint containing 1 steel increased at a faster rate than the control sample in which calcium oxide was omitted. It was observed that the increase in

Summary of the invention Interventions, specific organotypic compounds and compounds and/or these compounds U.S. Patent No. 4,191.579 Celification of paints of the type described in 3 months or more at a temperature of 50"C It was also found that this can be prevented when stored. Furthermore, the viscosity of this paint is maintains a viscosity within an acceptable range for application to ship hulls by any method; .

The present invention preferably contains polymeric triorganotin carboxylate and cuprous oxide. This antifouling paint effectively retards the gradual increase in viscosity and eventual gelation of antifouling paints. A fixed formulation composition is provided. This stabilizer composition consists of fil fal monoprecious triol. Gano f4f compound and Cb) 82nd or tertiary hydroxylamine or alkali mixture with nolamine and (2) one of the reaction products of the above fal and (bl). Detailed description of the invention According to the present invention, 1) fa) triorganotinated metal and (bl general formula and R2 are a hydrocarbyl (hydr-rocar) group, a Hydrocarbyl group, (CH2)noi, and water are selected, provided that R1 and R2 Both cannot be hydrogen, and n is 0 or an integer from 1 to 4] or 2) the above triorganotin compound. A solubilized polymeric compound consisting of one or both of the reaction products of a nitrogen compound and a nitrogen compound. Liorganotin carboxylate, cuprous oxide and/or zinc oxide containing A stabilizer composition for an antifouling paint is provided.

In the more sophisticated embodiment of the present invention, triorgano tinned metal 01-H type R2S nX　i　(assn)2y　C In the formula, R4 is a hydrocarbyl group , X is halogen, pseudohagen-4/lfi alcohol, funinol, mel Captan, carboxylic acid, or a shallow group obtained by removing the easily migrated A* element from η in the broad sense , -0R5 or -3R5 (R5 is an alkyl group having 1 to 20 carbon atoms, phenyl or benzyl group), and Y is oxygen or sulfur] R and R in the above formula for a nitrogen compound are hydrogen, an alkyl group, (C''2 ) nOH1 is a cycloalkyl group, an aryl group or an acyl group, and n 0.2.3 or 4, or one or both of R1 and R2 is (C H2) nOH, either R or R is hydrogen, and n is 2 or 3, and the weight ratio of the triorganotin compound and the nitrogen compound is 1:1 to 10. :1. R4 is lower arunel, substituted lower alkyl, phenyl having 1 to 4 carbon atoms; Triorganotannides, which are lumatasubstituted phenyl groups, are effective antifouling agents.

In this case, the nitrogen compounds N, l'J-Sial, mixed aryl Alg aryl, acyl, tahalkyl, acyl, hydro, syl, amine or General formula [HO(CH2)yu], nN? ”5-m (m is 2 or 3 and n is 2 or 3) It is a di- or trialkanolamine of It is preferable that the weight ratio of the compound I and the nitrogen compound is 3:1 to 6:1.

The triorganotin compound is bis()'J-n-butyltin) oxide, which is nitrogenated. The compound is N,N-diethylhydroxylamine and SN,N-di(lower alkyl ) Human e! Zylamine or Jetanolamine or Trietano Most preferably, it is an alkanolamine such as alkanolamine, ) The weight ratio of the organometallic compound and the nitrogen compound is When the nitrogen compound is an alkanolamine, the ratio is about 5:1, and when the nitrogen compound is an alkanolamine, the ratio is about 4:1 to 6:1◎ According to another aspect of the present invention, 7'L contains one of the above-mentioned stabilizer group 552 and cuprous oxide. Antifouling 1 containing at least one polymeric triorganotin carboxylate Fees will be provided.

In a narrower embodiment of the invention, the triorganotin carboxylate is Homopolymer of tri(lower alkyl)- and triphenyltin salts of unsaturated acids or a combination of the above salts and at least one copolymerized white ethylenically incompatible compound. It is a polymer.

For the preferred actual roll, 2 is ethylene unsaturated, and 3 is acrylic or methacrylic. Acrylic acid or methacrylic acid is the comonomer used in the preparation of the polymer. and an alcohol having 1 to 8 carbon atoms. Triorgano Gift (aSSn -) The repeating unit containing the residual group is present in the polymeric triorganotin carboxylate. 01 conjugated tri-carboxylic acid that constitutes 20 to about 3 repeating units present. The weight ratio of sylate to No. 1 steel oxide and/or zinc oxide is about 3:1 to 7:1. , R4 is butyl or phenyl ・Nitrogen compound A component of the stabilizer composition of the present invention is hydroxylamine or di- or di- or tri-hydroxylamine. Compounds that are alkalamines - general formula It is expressed as When the nitrogen compound is hydroxylamine, VC is n is 0, and R1 is hydroxylamine. 2Ir1 The same tfc has different hydrocarbyl groups, substituted hydrocarbyl groups, (CI(2)nOH, hydrogen can be substituted, but both R1 and R2 are water You can't be basic. R1 and R2 are the same and have a carbon number of 1 to 2° A branched chain alkyl group, a benzyl group, a phenyl group, or a nzoyl group. (preferably) When R1 and R2 are alkyl groups, 7i1 to 4 carbon atoms Hydro The term carbyl 5 group refers to straight chain or v'i branched chain alkyl having 1 to 201 carbon atoms. Group 5 cycloalkyl group having 5 to 8 carbon atoms, aryl, tolyl and xylyl group Alkyl-substituted groups such as alkaryl groups (referred to as alkaryl groups) and benzyl and and phenylethyl groups, aryl-substituted alkyl groups (also called aralkyl groups) α-carbyl represented by R1 and R2 in the above formula The group may have no substituents or one or more substituents. When substituents are present, these include hydrocarbyloxy, cyanide, carbogyl (RCOO-1R is a hydrocarbyl group) and nitro group, etc. or halogen, hydroxyl, mercapto (-3H), carboxyl Reactive compounds such as boxy (-COOH) and incyanato (-N=C=0) groups One substituent present may be a group in the final coating composition containing the stabilizer composition of the present invention. It is preferable that it does not react with any of the components of the product.The reason is as follows. The reaction occurs because it has a detrimental effect on the stability of the coating composition. As a commercially available human 0-V-fluamine and sonotate? iN, N-di Ethylhydroxylamine and □N,N-dimethylhydroxylammonium salt Typical human o-1i' cylamino acids that can be used in the present invention include acid salts. I can name a number of things; N-phenyl, N-pensoylhydroxylami/N-benzoylhydroxyl amine N,N-di(nzoylhydroxylamine/N-methylhydrohydroxylamine) N-butyl hydroxylamine N, N-dibutylhumanoxylamine N, N-) fluoro a methyl hydroxyl Silamine N-benzyl-N-o-)Tulhydroxylamine N-Fluoyl- N-Phenylhyt'a *Jylamine 7N, N-9 methylhydroxylamine N-ethylhyFIL O-sodylamine When the nitrogen compound is di- or trial-nolamine, n in the above formula is 1. It is an integer of ~4, and FL+ is -(CH2,)nOH) R2a -(C H2) nOH, hydrocarbyl group or hydrogen. n is 2 and at is -CH, CH20H, and R is -CH2CH20T (or 7t is hydrogen) is preferred, but this suitability is based on the efficiency of stabilization.

Examples of alkanolamines that can be used in the present invention include: Ru: dimethylethanolamine diethylethanolamine ethylethanolamine diimprovir ethanolamine Pterediethanolamine , l tilgetanolamine Methyljetanolamine etherjetanolamine Improvil ethanolamine n-butylethanolamine Dimethylisopro/4)-lamine Ncrohexyl diethanolamine phenylethanolamine N-cyanoethyl-N-human aquinethylanili/□-tolyljetanolami hmm 0-methquinphenyldinitanolamine triolka/tin compound The triorgano-ifb compound present in the stabilizer composition of the present invention has a tin and a chloride content. It contains three .-ido α-carbyl groups combined. 41 identical atoms of tin atoms 1 ri, sulfur, -logen atoms, pseudo-locations, or organic or inorganic acids. , alcohol, phenol, mercaptan, mercaft alcohol Stell, mercaptocalphone, and its esters contain easily mobile hydrogen. After removing all of the easily mobile hydrogen from any organic or cormorant-free pond compounds that remain I am deeply moved by this residue. When oxygen or sulfur is bonded to >3 atoms These nine compounds are bis(triorganoid) oxide or sulfur, respectively. A)’ is 6.

= ij The three Hyde α-carbyl groups associated with Kyoko are low carbon atoms with 1 to about 6 carbon atoms. Preferably, it is an alkyl group or a phenyl group. This aptitude is this Based on the comparatively high water resistance activity shown by the chemical compound against polluting organisms. ・This activity is effective against toxic components of antifouling and antifouling materials containing the stabilizer composition of the present invention. It complements the antifouling activity of the hexapolymeric triorganotin compound and the stannous oxide. Shibara Are the three hydrocarbyl groups attached to the child the same or different? be able to. Two or three different hydride α-carbyl groups are attached to tin toshi. Triorganotin compounds have been described in the literature. If the fourth group bonded to the tin atom is a monologan, it means that fluorine, chlorine , which can be iodine or bromine. When there is a free aD group, that is, an anionic form, it bonds with hydrogen to form θ. It is also similar to Roque/ion in that it reacts with silver to form water-insoluble salts. An inorganic group that exhibits chemical properties. Shea is the main ion of the ploid. nide, thioshi7-1-(5CN-'), cyanate (OCN-'), Examples include aroto (NC0-) and isothiocyanate (NC3).

Triorganotin halide, hydrochloride or bis(triorgano) + oxide Suitable triorganos for use in Vcf to prepare bile compounds of the present invention by reacting with Suitable carboxylic acids that can form tin compounds include acetic acid, propionic acid, and butylene. Cabconic acid, Car 1/IJ acid, Dodecanoic acid, 2-ethyl F He # So 7! ! i 1Chexoic), phycosan, benzoic acid and cyclohefsancarboxylic acid can be mentioned. Suitable inorganic acids can be -5-functional or polyfunctional, with special Contains nitric acid, phosphoric acid, sulfuric acid, and sulfuric acid.

The increase in viscosity exhibited by the antifouling paint containing the parabolic stabilizer of the present invention is The percentage reduction is shown in comparison to the non-stabilized paint ffl formulation.

The preparation of the paint was carried out in the following manner: 0.8 t of bentonite clay. (Bantoe 27+ BentOns is highly registered) 0.97jD % lnor, 33.7 r methyl isobutyl ketone and 65.2 t xylene 5.2 tons of crystal compound shell consisting of.

Near C type cylinder h (Cab-0-3il-PTC) and 1t stainless steel Mixed in a teal container for approximately 5 minutes. This container lζ250.4t organo a Acrylate copolymer solution, oxidation of 229.62 zinc and 164.29 No. 1 Copper (Gltddan) steel shot with a total diameter of approximately 1 heinte approximately 400v Mouth paint f Red David Pa1nt 5hake added with l The mixture was shaken for about 1 hour on Measure this paint with a Hsgrna gauge. It had a silkiness of 2 grInd 5 (approximately 30 i chron). . The steel shot is removed by passing the paint through a fine tea strainer. did. 4.17r bis(tri-n-butyltin)oxy, do, 0.839 (DN , N-diethylhydroxylamine and 5.01 of methylimbutylketone. After the solution was completely dispersed with the G added to the above paint under high speed stirring, the solution was stirred for another 5 minutes. Brookfield viscometer R'/F'-100 type OJ: H20 Measuring viscosity at 25°C using rprnojHI”C @Rotating Oboro 4 spindle Did O A certain polymer solution of organotin acrylate used in the above-mentioned original story was disclosed in US Patent No. 4. No. 260.535. Relationship in the above patent specification Some parts are quoted in Honakedasho.

After measuring the viscosity, the paint was kept at a temperature of 5oC, thermostatically controlled. Accelerated aging tests were performed by placing in an oven. After 12 weeks, the viscosity is g oo to 1,500 centivoids, but this increase in viscosity is less than that of commercial antifouling paints. are considered permissible. In comparison, bis(tri-n-butyl ) Same except that tinγxyr and N,N-diethylhydroxylamine are omitted. maid with the composition of 5°Oc which showed an initial viscosity of 3100 centipoise After 12 weeks, the viscosity increased to 22,000 centivoids.

The increase in viscosity observed in accelerated aging experiments conducted at a temperature increase of 1 degree and the temperature observed in the same month The relationship between the viscosity increase and the 12 sides at 500C is equivalent to 1 year at room temperature. It's in charge.

Additional examples of stabilizer compositions of the present invention are shown in Table 1. These stabilizers contain only solvents. It exhibits a remarkable viscosity stabilizing effect compared to other systems.

It is recognized that the effect of stabilizers υ with the same composition varies depending on the coating preparation method. 6.1 [As shown in the table, the first crushing process and let-down process when preparing paint The amount of polymer and stabilizer in the let-down step and the milling time The viscosity stability of the paint will be affected by the paint processing conditions. The comparison of the effects of TBTO/DgT (A stabilizer system and TBTO is clearly shown in Table MIII). G6* Cu2O joint test paint shown in Ingredients parts by weight Ding Rua/Kyo 1 combined solution (SO solid content) 276.9 Gysilene 72.1 15 Kimoto*Cu O Hong sample paint Ingredients parts by weight Organotin 1 combined solution 1 (50% solids, )) 406.5 Bentone 33 b7.5 CabQ products international search report

Claims (1)

[Claims] 1. a) l) Triorganotin Halaibi, thioalkoxide, alkoxide, hydrogen Droxide; bis(triorgano/Q) oxide and bis(triorganotin) oxide; an organosensitive compound selected from the group consisting of 2) General formula: (In the formula, & and R2 are each) ~hydrocarbyl<hydrocarb yl) group, substituted -pry carbyl locarbyl group), fc ye Both LR' and R2 cannot be hydrogen; n is an integer from 1 to 4 spanning 0 to 1 mixture consisting of; 3 and b) At least one of the reaction products of the organotin compound and the elemental compound. at least a portion of ttl is ethylenically unsaturated carbon fi at least one implanted derivative of alJO 8 derivative, and a solubilizing polymer. (2) A combination consisting of copper 1, zinc oxide or a-1 silk, and a crystalline compound of zinc oxide. Viscous stabilizer Q2 for use in compositions: Ratio of organosensitive compound and nitrogen compound Stabilizer 03 according to claim 1, having a ratio of 1:1 to 10:1, Claim 2, wherein the ratio of the tin compound to the nitrogen compound is 3=1 to 6:1. Stabilizer 04, Rl2 and R2 described in section 1 are an alkyl group, a cycloalkyl group, respectively. selected from the group consisting of aryl group, (Cm(2)nOH), hydrogen and acyl group. It will be revealed. Stabilizer 05 according to claim 1, R and R each have 1 to 20 carbon atoms. Stabilizer G6 according to claim 4, which is an alkyl group of @, and n is 0 , R1 and R2 are lower alkyl groups having 1 to 4 carbon atoms. Stabilizers listed in Section 5? , R1 and R are ethyl groups. Claim 6 Stabilizers listed in section. 8.11 is (CH2)nOH and R2 is H- or (CH2”1.OH) Yes/N is 2, stabilizer 0 according to claim 1 9. The triorganotin derivative is a triorganotin derivative in which each alkyl group contains 1 to 4 carbon atoms. These are tri(lower alkyl)tin derivatives and triphenyltin derivatives. Patent claim Scope of Item 1: Song Dynasty Stabilizer 0 10.) The IJ (lower alcohol) tin derivative is a tributyltin derivative. Special The stabilizer according to claim 9. The ethylenically unsaturated carboxylic acid is acrylic acid or methacrylic acid. patent Stabilizer according to claim 1 ◇12 The polymer is at least partially made of tin-free ethylene. Claim 1 derived from at least 1 amount of unsaturated compounds stabilizer. 13.Tin-free ethylenically non-leprosy compound has acrylic acid or methacrylic acid and carbon number It is an ester with 1 to 8 alcohols. Stability according to claim 12 Agent・14・R1 and R2 are lower argyl groups having 1 to S carbon atoms, and n is Ot or 2, the stabilizer according to claim 1. R5, R' and R2 are a methyl group, an ethyl group or an n-propyl group. # The stabilizer Qit's according to claim 14, which is an organotin compound, has the general formula: a2snx''- or (bow5n)2y [wherein R4 is -ido-carbyl group or It is a substituted -idolocarbyl group, and X is )~logen, -OH, -8R? Or 10R 5 (R5 is an argyl group having 1 to 20 carbon atoms), and Y is oxygen or :A The stabilizer 0 according to claim 1, which is a compound represented by * 17, R' is a phenyl group, an inertly substituted phenyl group, a carbon number of 6 to 8 Cycloalkyl group, lower alkyl group having 1 to 4 carbon atoms, or substituted lower alkyl group The stabilizer according to claim 16, which is 18. Organotin compounds include bis(t!J-n-butyltin) oxide, triphenylene It is d bis(triphenyl tate) oxide. Patent claim The stabilizer according to item 16. 1iL tt) At least a portion of ethylenically unsaturated acids and (2) cuprous oxide, zinc oxide. or a mixture of cuprous oxide and zinc oxide; (3) a natural S pigment; and (3) the claims. An antifouling paint comprising the viscosity stabilizer described in Items 1 to 18 (Ode 1). 20, sticky! The concentration of the stabilizer is 0.1 to 10 wt-i% based on the weight of the polymer solids. It is. Obstetrics according to claim 19 21. The degree of viscosity stabilizer is about 0.5 to about 6 times 1 width based on the weight of the polymer solids. The paint according to claim 20, which is ■・Part 1 of the claim 19 characterized by a non-reactive solvent・