TW416831B - Method of stabilizing biocidal compositions of haloalkynyl compounds - Google Patents

Abstract

This invention is directed to a method for stabilizing a composition which comprises a mixture of a halopropargyl compound. The composition can be used broadly in industrial systems and more particularly with substrates such as paints, coatings, stucco, concrete, stone, cementaceous surfaces, wood, caulking, sealants, textiles, and the like.

Description

Description of the Invention (Printed by the Consumers' Cooperative of the Central Biaohua Bureau of the Ministry of Carriage, this application is part of the application for acceptance of 08 / 479,220 on June 7, 1995. It belongs to the application number _ Background of the Invention 1 Scope of the invention It's against the package. & ^ ^ ^ ^ ^, The biocidal group °, and especially the southern propargyl compound composition 'It already; Ming: Don't target the loss of biocidal activity containing the compound Π :: :::: Degradation of this compound leads to vinegar, such as urethane dibag-like action. The stability of the composition of block propyl butyl ester 2 · Description of related skills External and internal surface and all types of subject Quality, exposed in the same environmental conditions as Cheng Cheng, it is susceptible to many types of microorganisms, including 'monitoring green stream' bacteria and protozoa, invasion, discoloration, and many types of damage. Therefore, it is very needed and required -An effective and economical method to protect the external and internal paving materials and different types of substrates and commercial formulations from prolonged periods from deterioration and damage caused by the microorganism. It is necessary to use a suitable antimicrobial composition to add Protective materials include stucco, concrete, stone, cement surfacing, wood, aged glue, sealers, leather 'plastic' fabrics, biodegradable compositions including paints and other coating formulations , Surfactants, proteins, starch-based compositions, inks, emulsifiers and resins and other materials, as well as other materials and other substances that can be attacked by destructive microorganisms. -4- This paper is applicable to the China National Standard (CNS) Μ specifications (21〇χϊ97mm) 1ΙΪ --- ^ --- ^ --- / τ-(Please read the -Issue on the back before filling in this page)

.In ί — I V. Description of the invention (2) A7 B7 ~ 416831 A very wide variety of materials printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs have been identified as 'they are delaying or preventing the growth of this microorganism' and the causes With varying degrees of effects on destruction, such biocidal compounds include functional compounds, organometallic compounds, quaternary ammonium compounds, phenolic compounds, metal salts, heterocyclic amines, formazan suppliers, organic sulfur compounds And its analogs. Modulation products that are protected against microbial attack through the inclusion of far-killing biologic additives must maintain their biocidal activity optimally for extended periods of time. In fact 'the product is often used to impart biocidal activity to another product or to a substrate' such as wood and its analogs, which itself need to be expanded to strengthen protection against microbial attack. "A well-known class of biocides are those Contains a propargyl moiety, and in particular a karyopropyl moiety. This compound is widely disclosed in patent literature 'including U.S. Patents 3,660,499; 3,923,870: 4,259,350; 4,592,773: 4,616,004, 4,639,460, and the like. Included in such compounds is halopropargyl aminoformate, which was originally known for its fungicidal activity. 3-amino-2-formyl butyl vinegar, also referred to herein as jpg 匸It is one of the most famous and probably the most widely used amino acid, propargyl vinegar, a gastric killer. IPBC is a highly active broad-spectrum fungicide. In addition to its fungicide activity, IPBC has also been associated with cyanobacteria-killing activity. In this regard, British Patent 2, U8,292 and U.S. Patents 4,915,909 and 5,082,722 contain this disclosure. As shown above, the alkynyl compounds, including the propargyl compounds, and especially the amino propargyl succinates, are typically prepared together with many other ingredients in aqueous and organic solvent mixtures. 3 Reason-5- This paper's standard is applicable to China National Standard (CNS) A4 specification (210 '乂 297mm) (Please read the notes on the back before filling this page) --- TI.L --- r— < --- ---: order.-丨 II----A7 416831 ______ B7 V. Description of the invention (3) 'It is expected that these compositions maintain their biocidal activity for a long time. Unfortunately, the composition is sometimes observed to experience a progressive loss of the activity # Until now, the cause of this degradation has not been understood. However, through experiments, Shen 4 has found that one of the common reasons for the loss of biocidal activity in the formulation is the exposure of the alkyne diyl compound to a high level of alkalinity or a high level of acidity. In an aqueous environment, this condition involves extreme pH conditions, both acidic and alkaline. Applicants have discovered that biocidal haloalkyne compounds are prepared by modulating the composition so that the source of acid or base in the composition is buffered, or by buffering of the formulation, which include, in particular, propyl compounds such as IPBC, Degradation can be significantly delayed. The present invention also helps to reduce other problems caused by the degradation of IPBC in solvent-based alkyd paint formulations, such as the formation of metal containers by the formation of tears. Brief description of the invention_ Therefore, the present invention is based on the surprising discovery of a composition and method for stabilizing the biocidal activity of some formulations containing a alkynyl compound. The present invention is particularly directed to a composition and method for stabilizing some The biocidal activity of formulations containing the propargyl compound 'especially the halopropargyl carbamic acid fungicides' suffers from a decrease in biocidal activity over time due to the inclusion of basic or acidic components. There are many aspects of the invention. In a first aspect, the present invention includes neutralizing excessive acid or detection in a water-containing composition containing a alkyne compound with mono- or mono-acid, respectively, to suitably adjust the pH of the aqueous preparation of the composition to a range of 3.0 to 8.0, 4 The range of 0 to 7.7 is better, and the range of 5.5 to 7.7 is better. "On the other hand, 'an acidic or test compound is added to the formulation containing organic solvents, including halopropynyl compounds such as IPBC, Of which -6- This paper size applies to the Chinese National Standard (CNS) grid (210X 297 mm) 1-^ 丨 1 --- Μ 丨 -Packing --------:-Order-^- --Silver: I--_ (Please read the precautions on the back before filling out this page) Central Office of the Ministry of Economic Affairs, Consumer Affairs Cooperatives, Cooperative Cooperatives, Cooperative Cooperatives, Printed by the Ministry of Economic Affairs, Central Standards Bureau, Employee Consumer Cooperatives, printed '-'at i " ^ 16 8 3 1 _______ B7 ~ _ ^ _ 5. Description of the invention (4) The formulation contains alkalinity or acidity to enhance degradation levels, respectively. On the other hand, the present invention employs a buffering agent to maintain the formulation of the halogen-containing propargyl group, either aqueous or based on an organic solvent, which is in the appropriate PΗ range, i.e., at an acceptable level of alkalinity or acidity. Therefore, the present invention provides a biocidal composition comprising a mixture of a propargyl compound and a buffer, wherein the weight ratio of the self-propargyl compound to the buffer is 50: 1 to 1: 1. And, wherein the composition is beneficial to provide biocidal activity to the end-use formulation and stabilize the end-use formulation against the degradation of the propargyl compound at a pH between 3 and 8.0. The present invention also provides a method for stabilizing a biocide formulation containing an amidine propargyl compound, the formulation having an alkalinity or acidity sufficient to cause degradation of the amidine propargyl compound in the absence of added acid, amidine or a buffer, the The method includes adding a sufficient amount of an acid'base or a buffer to the formulation to adjust the pH of the formulation to a range of 3.0 to 8.0 g. The present invention also includes a method for providing a final-use formulation with biocidal activity Method 'which includes mixing a sufficient amount of a propargyl compound with a buffering agent', wherein the weight ratio of the propargyl compound to the buffering agent in the mixture is between 50: 1 and 1: 100, and To the end-use formulation to impart biocidal activity to the mash formulation and raise the formulation to a pH in the range of 3.0 to 8.0. Brief Description of Drawings Figures 1 to 7 show graphically the stability of the formulations of Comparative Examples 1 to 7 and Examples 1 to 6. Detailed description of the invention The paper music scale is applicable ^ National Sample (CNS) A4 regulations ^ Ti〇x297 public Chu) I .---- — u --- Γ —— < equipment --------- 1T .-- ^ ---- 4;-* (Please read the notes on the back before filling out this page) J '4 16831 A7 -________ Bf V. Description of the Invention (5) The present invention is directed to a composition and for stabilization Some formulations containing paint compounds. The present invention is particularly directed to a composition and a formulation for reducing the amount of degradation or the acidity of degradation due to the presence of degradation or acidity, such as high (test) or low (acid) pH. The conditions that cause hydrazine propargyl compounds, especially alkynyl esters such as carbamic acid, degrade your methods. Degradation of activated halides causes loss of biocidal activity. The present invention is particularly directed to a method for protecting biocidal tooth block propyl compounds, and particularly iodine amino block propyl esters, against the degradation of acidic and alkaline environments. The present invention thus provides a stable composition containing a biocidal function propargyl compound. The halopropynyl compound used in the present invention can be identified as the following structure

yc = c- ch2 X where Y is a halogen 'iodine is preferred and X may be (1) oxygen, which is part of an organic functional group; (2) nitrogen, which is part of an organic functional group; (3 ) Sulfur, which is part of the organic functional group: (4) Carbon, which is part of the organic functional group. The functional group of oxygen as a moiety is preferably an ether, ester, or urethane group. The functional group in which nitrogen is a moiety is preferably an amine, amidine, urea, nitrile, or urethane group. The functional group in which sulfur is a moiety is preferably a thiol, thione, or a sulfenyl group. The organic functional group in which carbon is a part is an ester, and a carbamate or an alkyl halide is preferable. • It may be used as the compound of the propargyl compound of the present invention. Example -8-The standard of this paper is at leisure (CNS> A4) (2I0x :: 97mm) n HI I-- ------ j-1! -I 'I:-----. 1 n ^ i--”I l. (Please read the precautions on the back before filling this page) Ministry of Economic Affairs印 Printed by the Consumer Bureau of Standards Bureau of the Consumer Cooperatives of the Ministry of Economic Affairs. Printed by the Central Bureau of Standards of the Consumers' Cooperative of the Ministry of Economic Affairs.% -A? ≫ '4 16831 B7' In this regard, see US Patent Nos. 3,923,870, 4,259,350, 4,592,773, 4,616,004, 4,719,227, and 4,945,109, the disclosures of which are incorporated herein by reference. These iodopropargyl derivatives include derivatives derived from propargyl or iodoalkyne Propyl alcohols, such as esters, amidines, acetals, urethanes and carbonates, and bites, 11 cetolinones, tetraacryl, triazinones, Thioamines, benzoxazoles, ammonium salts, carboxamides, isoammonium acids, and urea propargyl derivatives Preferred among these compounds are halopropyl urethane and 3-iodo-2-propargyl butyl urethane (IPBC). This compound is included in a wide variety of useful compounds having the following general formula Middle: 〇Γ II 1

IC = C- (CH2) iTr0 ~ C-N ~ j-RLH n where R is a selected and unsubstituted hydrogen containing 1 to 20 carbon atoms, substituted and unsubstituted sintered groups, having from 6 to 20 complete substituted and unsubstituted aryl groups, pit aryl groups, and aryl pit groups, and substituted and unsubstituted cycloalkyl and cycloolefins selected from 3 to 10 carbon atoms A group of groups 'and m and η are each independently an integer from 1 to 3', that is, ni and η need not be the same. It is particularly preferable to have the following chemical formula, where m is 1 and η is 1, and this -9- The guilt scale of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) J --- ^-±- ---- 装 --------, ¾ .-- It ---- ^;-(Please read the following on the back: ^ Matters before filling in this page} Γ 4 1 683 1 Α7 — ^ _ V. Description of the invention (7) Formulation of succinyl aminocarbamate: 〇II ^

1C three C—C—10—c ~ N—R Η2 η Suitable R substituents include alkyls, such as methyl, ethyl, propyl, η · butyl, t-butyl, pentyl, hexyl , Heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, cycloalkyls such as cyclohexyl, aryls, alkaryls and aralkyls, such as phenyl, Benzyl, tolyl, cumyl, halogenated tiger and aryl, such as chlorobutryl and phenyl, and alkoxy, such as ethoxyphenyl and the like. Especially preferred are such iodopropargyl aminoformates, such as 3-iodo-2-propargylpropyl aminoformate, 3-iodo-2-propargylbutylaminoformate, 3-iodo-2-propargylhexyl urethane, 3-iodo-2-block propylcyclohexyl urethane, 3-carba-2-phenylpropyl phenyl urethane, and the like Tear compound. The south propargyl compound in the final formulation, which is stabilized in accordance with the present invention, can vary greatly in its amount and the appropriate amount usually affects the desired application and other ingredients of the particular formulation. "Anyway, such formulations usually contain From about 0.001 to about 20 weight percent of the halopropargyl compound. Generally, such formulations contain from 0.01 to 10 weight percent of the compound. The formulation is protected by the inclusion of propargyl aminocarbamate. Applicable to the size of this paper: Chinese National Sample (CNS) A4 Tiege (U0X297)> ^ ---:-^ --- 1- --- install -------- r order ------ line---(Please read the notes on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Economy—Industrial and Consumer Cooperatives: a7 '4 1683 1 _____________ Βί V. Description of the Invention (8) ~~' Anti-microbial invasion can be prepared from highly concentrated compositions of propyl active ingredients of the dental block, for example, by appropriate dilution. Often, a suitable advantageous range is The amino propargyl propargyl esters in the final formulation, when used in end-use systems, may protect paving and other substrates against microbial growth for extended periods of time, for example, against blue-green lotus Printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs for consumer cooperation (please read the notes on the back before filling out this page) The composition of the present invention will usually be prepared by mixing propargyl active ingredients in a liquid carrier or Dentrolyl compound concentrate to dissolve or suspend The carrier can also contain a diluent, an emulsifier and a wetting agent. The general uses of these biocidal compositions include protecting wood, paints and coatings, adhesives, paper, fabrics, plastics, Cardboard, lubricants, quilting adhesives, and the likea A detailed list of possible industries and applications of the present invention can be found in US Patent No. 5,209,930, which is incorporated herein by reference. Tooth propargyl Compositions of compound fungicides, especially iodopropargyl aminoacetate, such as IPBC, are often formulated as liquid mixtures, but can be wettable powders, suspensions, or any other desired and most advantageous Provided in the form of suitable products. In this regard, formulations that are to be stabilized against degradation of the active succinylpropionic acid biocide according to the present invention can be provided as ready-made products, which are aqueous or organic solvent solutions, suspensions, oily solutions and Suspensions, milk custards, spray preparations and their analogs or concentrates in the form of 3 For use with alkynyl compounds, especially preferred aminocarbamic acids Propargyl butyl esters, advantageous liquid carriers, including organic solvents, are water, alcohols such as methanol, butanol and octanol, hexanediols, several glycol ethers, such as poly-11-say scale IKEA Standard (~ ^ s) M Specification (2IGX29? Public Holiday) ~ ----— Printed by the Central Standards Bureau of the Ministry of Economy—Industrial and Consumer Cooperatives 5. V. INTRODUCTION TO THE INVENTION (~~-Propanediol n-butyl test, polypropylene glycol Tertiary, Ding Si, 2- (2-Methoxymethylethoxytripropylene glycol methyl mystery, propylene glycol methyl mystery, dipropylene glycol methyl acid, tripropylene glycol methylamine, propyl alcohol n-butyl bond and esters of the aforementioned compounds Other advantageous solvents are n-methylphosphonium, n-pentyl propionate, bumethoxy-2_propanol, several dicarboxylic acid dibasic esters, and mixed 4 'such as succinic acid , Diisobutyl ester mixture of glutaric acid and adipic acid, Aromatic hard hydrides such as dimethylbenzyl and methylbenzyl, highly aromatic petroleum steamers' such as solvent naphtha, steam tar, minerals Oils, ketones such as propylamine, and petroleum fractions, such as mineral spirits and kerosene. Other suitable organics; the agents are familiar to those skilled in the art3 When preparing the formulations of the present invention for special applications, the composition may also be conveniently used as an adjuvant in a composition intended for that application— Are provided, such as organic binders and polymers, such as alkyd resins, additional fungicides, auxiliary solvents, processing additives, fixatives, desiccants, such as cobalt octoate and cobalt naphthenate, plasticizers, UV -Stabilizers or stabilizers, water-soluble or water-insoluble dyes, pigments, driers, corrosion inhibitors, anti-settling agents, anti-skinning agents and the like. The added fungicide used in the composition is preferably soluble in a liquid vehicle. The stabilizer composition of the present invention may also be an aqueous, latex-based product such as propylene, ethyl acetate, acrylic acid, polyvinyl acetate, styrene-butadiene, and silicone emulsion. They can also be microemulsions or microemulsion concentrates. According to the present invention, the substrate is protected from organisms such as maggots and blue-green algae. -12- The scale of the paper method is applicable to the standard of S. spp. CNS> Λ4 specification (2! 0χ 297 gongjun)-ί ^ ---- 装 ---- 一 ---? 1Τ--. ---- 猓 [Please read the notes on the back before filling out this page.] Printed by the Consumer Cooperatives of the Central Bureau of Probation, Ministry of Economic Affairs, 7 '4 1 6831 __B7 ~ V. Description of the invention (1〇) The formulation handles the substrate. This treatment may involve combining the composition with cultural substance C, coating or contacting the substrate with the composition and the like. As indicated above, representative applications include paints, dyes and other coatings, leather treatment fluids, wood treatment compositions, metalworking fluids, water treatments such as cooling water, adhesives, sealants, personal care products, paper coatings and many more Other applications. Formulations that are stabilized according to the present invention and are susceptible to degradation by odopropynyl are compositions that contain excessive alkali or acid components to make the composition highly alkaline or acidic, but not sufficiently acidic or susceptible. For aqueous formulations, the composition can be easily confirmed by simply measuring the pΗ of the aqueous phase of the composition. Formulations having a pH higher than 8.0 have a p 高于 higher than about 7.8 when better implemented and a ρ η higher than about 7.5 when optimally implemented. They tend to degrade propargyl to different degrees. The formulation can be stabilized by the addition of an acid or a suitable buffer. Alternatively, a composition having a pH of less than 3.0 has a pH of less than 4.0 when it is better to perform, has a pH of less than 5,5 when it is better to perform, and has a pH of less than about 6.5 when it is best to perform. The pH is also prone to the degradation of halopropargyl to varying degrees. Again, the formulation can be stabilized, in this example, by adding a base or a suitable buffer β to the organic formulation 'a composition that is prone to degradation of propargyl groups due to the presence of excess alkali or acidic components It can be confirmed by using equal weight water treatment to measure the amount of the formulation and measuring the ρ Η of the water phase. 3 As shown above, the formulation tested in this method 'is manufactured with a water phase having a pH of 8.0 and higher, higher than It is preferably about 7.8, and more preferably higher than 7.5, or the mono-aqueous phase has a pH lower than 3.0, preferably lower than about 4.0, and more preferably lower than 5.4. Jing-13- ----- 丨 ^ ---- Installation ----'--- vir -------- '--' (Notes on the back of Shi Xiange, please fill out this page } This Chinese standard is applicable to Chinese National Standard (CN.S) Λ4 Specification ί mm) Γ 416831

; AT _______ Β7 ~ 5. Description of the invention (Η) Stabilized by adding an acid or base separately or by adding a suitable buffering agent = result, when used in the entire specification and patent application scope, ρΗ is intended to be applied to The aqueous-based and organic-solvent-based compositions shown above, so the use of pH in the specification and patent application is not intended to exclude organic solvent-based formulations. In some alkyd-containing formulations used as coatings and wood preservatives, the use of desiccants (catalysts that promote or affect the reaction of alkyd with oxygen) can further cause instability in IPBC. This problem is particularly encountered in formulations using cobalt drying tinctures, which are usually acidic in nature. For example, a typical alkyd formulation may include 20-25 weight percent alkyd resin, 65.75 weight percent mineral alcohol solvent, and 0-5% co-solvent such as methoxypropyl acetate. '0 to 1% anti-skinning agent such as methyl ethyl ketone, 0 to 1% anti-settling agent such as bentonite; Dian additive, 0 1 to 1% such as desiccant of caprylic acid, up to 4% by weight of dye And pigments and 0.1 to 5% of IPBC. In order to compensate for the acidic nature of cobalt desiccants and other desiccants often used with alkyds, the present invention provides basic co-desiccants (including buffers such as calcium-10) for common use. In this method, the formulation is stabilized to resist IPBC degradation without significantly changing the drying properties of the alkyd formulation. Conversely, calcium desiccants (including alkaline calcium desiccants) have been widely used in organic solvent-based In alkyd paints, these formulations also contain propargyl compounds such as IPBC to stabilize biocidal compositions. The use of materials has not been identified. According to one aspect of the method of the present invention, a sufficient amount of acid or base is suitably added to the halogen propargyl-containing composition to adjust the pH of the aqueous mixture of the composition to a stable pH 'or a sufficient amount of a suitable buffering agent is added to Keep the preparation level at the desired -14- This paper ft scale applies Chinese National Standard (CNS) A4 specification (2I0X297 mm) ------------- installation -------- Order ------ Ball:. (Please read the back of the page; I will fill out this page before filling out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the Shellfish Consumer Cooperative, Printed by the Ministry of Economic Affairs, the Central Prototype Bureau, printed by the Consumer Cooperative, 416831 Explanation of the invention (* 12) Within the PH range "As used in the article of the present invention, a stable hydrazone is only in the pH range of 30 to 8.0, preferably in the range of 4.0 to 7.7, and more preferably in the range of 5.5 to 7.7 Good, best within 5.5 to 7,5. For aqueous formulations with an excess of acidic or experimental ingredients, the amount of base, acid or buffer to be added can be easily determined by routine experiments similar to acid-base titration. A suitable agent for stabilizing the formulation, that is, an acid, base or buffer, is slowly added to the measurement specimen of the aqueous formulation, and there is no such additive when monitoring the pH range. — It is necessary to adjust the water-based formulation to 3.0 to 8.0 Fanyuan, preferably in the range of 4.0 to 7.7, and more preferably in the range of 5.5 to 7.7. The required relative amount of medicine is determined, and the same relative amount of acid, A base or buffer is suitably added to the complete formulation to stabilize it against degradation of the halopropargyl compound. For organic (non-aqueous) formulations, the same steps can be used, except that at the beginning, the aqueous test composition must be prepared by thoroughly mixing the measured amount of the formulation with an equal weight of water. The subsequent steps are similar to those outlined above. In step 0, the appropriate treatment level of the aqueous formulation is estimated. The use of a suitable buffer is added to ensure that the preparation product is maintained in the appropriate pH range. Excess buffer material can be used without bringing the formulation into the unwanted Benefits in the desired pH range. Therefore, there is no critical point in the total amount added, as long as at least a sufficient amount of buffering agent is added to prevent degradation caused by the level of acidity or verification in the formulation. The use of buffering agents has an additional important benefit. Any strong acids or strong tests that may form under the conditions of the use of the modulation product will also be countered by the addition of additional buffers that persist in the modulation product. Therefore, a particularly important aspect of the present invention is the novel combination of materials. -15- The paper scale is applicable to the Chinese National Standards (CNS) Rule 6_4 (210x297 mm) '-----

In-1 f UJ --- I-i4 ± 衣 --1-t-Γ ----1 '_ · 7-• Factory-VV (please read the' on the back first '; please fill in the items of interest (This page) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs! 41683, A7 _____ V. Description of the invention (13), such as solutions, suspensions, emulsions, and IPBC powders and weakly alkaline materials, such as auxiliary drying Agents (i bows, locks, etc.), organic acid salts, etc., or sold in the form of different products used in end-use formulations and providing insecticidal (biocide) stability buffers in end-use formulations " Alternatively, the present invention can be carried out by adding a suitable buffer or p (R) neutralizing substance to an end use formulation containing IPBC. Suitable acids that can be used to adjust the pH of a composition containing excess analytical ingredients include organic acids, such as formic acid, acetic acid, propionic acid, glutaric acid, 2-ethylhexanoic acid, mesamic acid, lactic acid, p-toluene Acids and their analogs, and inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid and their analogs. Suitable bases include organic bases, preferably tertiary amines such as trimethylamine, triethylamine, triethanolamine, triisopropanolamine and the like, and inorganic bases such as alkali metal hydroxide Species, including sodium hydroxide and ammonium hydroxide, and alkali metal carbonates. It is better to use relatively weak acids and relatively weak bases to complete the pH adjustment shown above. As shown above, it is often better to use a suitable buffer, which can be divided into a weak acid and a weak base at the same time, which can interact with (ie, neutralize) stronger acids and stronger bases. Suitable buffering agents include bicarbonates, carbonates' organic acid carbonate complexes, hydrogen acids, phosphonates, linates, borate, borate, argon sulfate, Specific examples of suitable bases of phosphonates and sulfates include dicarbonate, hydrogen phthalate, potassium hydrogen sulfate, potassium citrate, potassium dicitrate, potassium argonate , Dipotassium hydrogen phosphate, Potassium hydrogen tartrate, Potassium oxalate, Potassium maleate, Potassium hydrogen succinate, Potassium glutarate, Dihydrogen adipate, Potassium tetraborate, 5-16 Dimensions are applicable to Chinese National Standards (CNS) Λ4 specifications (2! 0: < 297 mm) (please read the note on the back first and then fill in this page) f Pack · • ί-ΐτ Central Ministry of Economic Affairs 榡 芈Bureau-industrial-consumer cooperation print J '41683 ^ :, 7 —__ V. Description of the invention (u) Potassium borate, potassium octaborate and all related sodium salts' organic acids (such as caprylic acid) iso-caprylic acid, 2- Ethylhexanoic acid, hexanoic acid, and the like) calcium carbonate complexes, 2- [2-amino-2-oxoethyl) amino] ethane jisuo 'N- [2_ethyl Amido ] -2-Aminoethanesulfonic acid, N, N-bis [2-hydroxyethyl] -2 · aminoethanesulfonic acid, 2- [bis (2-hydroxyethyl) amino] ethanesulfonic acid Acid 'and other similar substances known in the art. As shown above, acids, assays or buffers are added to formulations containing south propargyl compounds, which are free of such additives and will exhibit a level of alkalinity or acidity that can lead to premature degradation of the alkynyl compounds. Composition 3 acid 'base or buffer is added in sufficient amounts to combat such acidic or alkaline ingredients, by adjusting the pH of the formulation of the halogen-containing block propyl compound to a stable range of 3.0 to 8.0' from 4.0 to 7.7 The range is better, and a pH between 5.5 and 7.7 is more preferred. 2 This p Η can be directly measured in the aqueous preparation of the propargyl compound 'or can be appropriately used in organic solvent-based compositions using water. Measurements were performed in a similar manner after treatment. In general, a stabilizing composition comprising a concentrated preparation and a fully formulated product 'may contain from 0.1 to 50 weight percent, more commonly from 1 to 40 weight percent and most commonly from 1 to 25 weight percent of active hapropargyl biocidal Agents' 0.1 to 20% by weight, more commonly 1 to 15% by weight and most often 1 to 10% by weight of acids, bases or buffers for adjustment and balance of solvents or liquid carriers: the total of these three ingredients · Equal to 100% by weight, that is, the total amount of halopropargyl biocide, acids, bases or buffers used for pH regulation, and solvents or liquid solvents that make up the entire composition for percentage purposes. However, as above *, the fully-modulated components will also include other ^ • 17-! National standard extraction grid (21 "Γ ----- install ---- ^ --- ^ order ------- line (Please read the precautions on the back before filling out this page)

B7 printed by Male Workers Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs ---- -------- V. Description of the invention (15) points, especially for excessive alkalinity or acidity in compositions lacking pH adjustment Contributors. A particularly preferred aspect of the present invention relates to a composition containing a halogen propargyl compound and a buffer, as shown above, which can be sold in the form of condensate and which is advantageous as a biocidal additive because it uses the halogen propargyl Compounds, especially IPBC, incorporate acidic and basic end-use formulations to provide stable biocidal activity. Generally, such a concentrate includes a mixture of a sodium propargyl compound and a buffering agent, with a weight ratio of the halopropargyl compound to the buffering agent ranging from 50: 1 to i: 100. This concentrate is conducive to granting biocidal activity to the end-use formulation, resulting in a pH between about 3.0 and 8.0, preferably between about 4.0 and 7.7, and more preferably between 5.5 and 7,7. The modulation product. As used throughout the specification and scope of the patent application, proper names, end-use formulations are intended to include a wide variety of formulations that use block propyl compounds to grant biocidal activity, including paints, dyes and Other coatings, leather treatment fluids' wood treatment compositions, metalworking fluids, water treatments, adhesive goods! 1 'Sealants' Personal Care Products, Paper Coatings, Paper' Fabrics, Plastics, Cardboard 'Lubricants' Caulking Adhesives, and the like s Proper term " End Use Preparation " A detailed list of possible applications can be found in US Patent No. 5,209,930, which is incorporated herein by reference. The following examples are presented to illustrate and explain the invention. Unless stated otherwise ‘All stated parts and percentages are based on weight. Implementation 1 The following comparative examples illustrate the condition of excess alkaline components, that is, the conditions of excessive alkali ____ -18- The silk size is appropriate (exs) ~~ ------- {Please read the precautions on the back first (Fill in this page) 丨 Gutter 5. Description of the invention (16) 'Degradation caused by the composition (specimen) containing iodobutyl butyl aminoformate (IPBC)-the effect is obtained, the specimen is paid Accelerated aging tests by maintaining them at 4 5 I and monitoring the residual amount of IPBC weekly for one month. The child test is believed to be approximately equivalent to one year of aging at room temperature. The level of residual IPBC in the composition was monitored via high performance liquid chromatography (HPLC). The Waters 712 WISP instrument was used with a Waters 486 UV detector and an Alltech Econosphere column (25 cm long and 0.46 cm wide) with C-18 RP filler (5 #). The mobile phase is a mixture of acetonitrile and water in a volume ratio of 6: 4. The mobile phase flows through the column at a rate of 1 ml / min and the detector wavelength is set at A = 230 nm. All pH systems were measured using a Beckman Φ 34 pH meter. Force p = Comparative f. Example 1 This example sets a control group for aging alkaline specimens. A solution containing 100/0 IPBC was prepared by dissolving 5.0 g of IpBc in a quinone compound of 42.5 g of methanol and 2,5 g of water. This solution had an initial pH of 6.7. Figure 1 presents the level of residual IPBC over time. Comparative Example 2 A 10% IPBC solution was prepared by dissolving 5.0 g of IPBC in 1.0 g of tertiary amine. 3 ^ 1 ^ 12 [1 ^ -alkyl ((: 12-(: 16)-: ^, 1 ^ -Dimethylamino], prepared from a mixture of 41.4 g of methanol and 2.5 g of water. The composition has an initial pH of 8.8. Figures 1 and 2 illustrate the residual IPBc content of the composition over time. Comparative Examples 3 A 10% IPBC solution was obtained by dissolving 5.0 g of IPBC in 1.05 g of 2-alkyl-2-fluorenyl-1 -propanol (AMP-95, Angus), 41.5 g of methanol and 2.45 g of water. The standard is the Chinese National Standard (CNS) A4 (10 ×: 97) -Taste ---- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs r 416831 .A7 A / ---_ _ B7 — ___ V. Mixture of Invention Description (17) The composition has an initial pH of 9.8 a. Figures 3 and 3 show the residual IpBC content of the composition after time has passed. Comparative Example 4 A 10% IPBC solution was dissolved by dissolving 50 g of IpBC, Grade Amine, N, N- Methyl-ethanolamine, 415 grams of methanol and 25 grams of water, the composition has an initial pΗ 9.4. Figures 4 and 4 illustrate the residual IPBC content of the composition over time " Comparative Example 5 10% IPBC The solution was prepared by dissolving 50 g] fpBc, 10 g ammonium hydroxide, 42.2 g methanol, and 1.8 g water. The composition had an initial pH of 94. Figures 1 and 5 illustrate the residual jpbc of the composition over time. Comparative Example 6 A 10% IPBC solution was prepared by dissolving 50 grams of IPBC, 0.05 grams of sodium hydroxide, 42.0 grams of methanol and 2.5 grams of water. The composition has an initial 108s. Figures 1 and 6 Explain the residual content of this composition after time has passed. Example 1 A 10% IPBC solution was co-dissolved by dissolving 5.0 g of IPBC, 1.0 g of Barlene 12, 41.1 g of methanol, 0, 4 g of acetic acid, and 2.5 g of water. And prepared. The resulting composition has a p Η 6.9. Figure 2 compares the stability (residual IP BC content) of this composition over time with the composition of Comparative Example 2. Example 2 " 10% The IPBC solution was prepared by adding 5.0 g of IPBC, 1.05 g of AMP-95, and 40.7 g of nail polish. Alcohol, 0.8 g of acetic acid and 2.45 g of water were prepared by co-dissolving. The resulting composition has a pH of 7.1. Figure 3 The safety of this composition after time -20- The scale of this paper is applicable to Chinese national standard (C \ S ) A4 is present (210XZ97 mm) LI L ------ It-if -I —s 1 II sleep ^^ ·--I 1 ^-1 i---ID -1 I ---. 1 (Please read the back of the page; I will fill in this page before filling in this page) Ministry of Economic Affairs_Central Bureau of Standards printed by employee consumer cooperatives f " 416831: A7 B7 ~ V. Description of the invention (18) Qualitative (residual IPBC content) and comparison The composition of Example 3 became a control. Example 3 10% of 1% (: solution was prepared by adding 5.0 g of 1-3 (:, 1.0 g of 1 ^, 1 \ [-dimethyl- Ethanolamine, 40-7 grams of methanol, 0.8 grams of acetic acid, and 2.5 grams of water were co-dissolved to produce a composition resulting from Preparation 3 having p Η 7.4. Figure 4 compares the stability (residual IPBC content) of this composition over time with the composition of Comparative Example 4 as a comparison. Example 4 A 10% IPBC solution was prepared by co-dissolving 5.0 g of IPBC, 1.0 g of ammonium hydroxide, 41.08 g of methanol, 1.12 g of acetic acid, and 1.8 g of water. The composition produced by a had p Η 7 · 5. Figure 5 compares the stability (residual IP BC content) of this composition with time and the composition of Comparative Example 5 as a comparison. Example 5 A 10% IPBC solution was prepared by passing 5.0 g of IPBC and 0.5 g of hydrogen. Sodium oxide, 40.67 g of methanol, 0-83 g of acetic acid and 2.5 g of water were prepared by co-dissolution. The resulting composition has a p Η 7.7. Figure 6 compares the stability (residual IPBC content) of this composition over time with the composition of Comparative Example 6 Comparative Example 7 " A composition widely used for treating wood is prepared according to the following. 81.0 g of 8 & "(13〇2280 (quaternary ammonium compound sold by 1 ^ 〇1 ^ 3 company) and 19.0 g of Troysan Polyphase AF-1 (available from Troy Chemical Co., Ltd.-21) China® National Standard (CNS) A4 (0X 297 mm) (讦 Please read the notes on the back before filling in this education)-Packing. Order. Γ 416831 _ Α7 '' ~~ ____ Β7 V. Description of the invention (19 )-Secondly, d 'its mixture containing 4G weight percent of IPBC) was "dropped out until a homogeneous solution was produced. The resulting composition had a pH of 8.7. Figure 7 presents the residual IpBc content of this composition over time. F Examples 6 For comparison with the composition of Comparative Example 7, 80.0 g of Bardac 2280 '19'0; Kun He 1PBC's Troysan Polyphase AF-1 and 1.0 g of acetic acid are mixed by mixing these ingredients to obtain a homogeneous solution The preparation 3 and FIG. 7 make the stability (residual pBc content) of the composition over time and the composition of Comparative Example 7 a control β. In Comparative Examples 7 and 6, the product was at 4 5 ° C. Heat aging for one month and residual composition The IPBC content is analyzed weekly via hpLc as above. The data presented in Figures 1-7 demonstrate the degradation due to the dangerous pΗ conditions in IPBc-containing aqueous compositions and the degradation-delayed results obtained through acid neutralization .

Example 7a-P A series of experiments (factorial experimental design) were performed to evaluate the effect of several composition variables on the IPBC stability in solvent-based alkyd paints. The basic formulation contains 20% alkyd resin, 76.5% mineral alcohol, 3% POLYPHASE P-20T: 0.06% acid cobalt desiccant (sometimes using cobalt octoate) or 0.06% alkaline cobalt desiccant (cobalt 21) or 0.1% Permadry (cobalt / calcium (Co / Ca) desiccant from Troy Chemical Co., or 0.18% from Troy Chemical Co.

Troymax CZ69 (cobalt / calcium (Co / Zr) desiccant and 0.2% methyl ethyl ketone monthly loss (MEK0) (an anti-skinning agent) were used. Five formulation variables were tested: -22- The iron scale of this paper applies the Chinese National Standard (CNS) A4 specification (21〇_ × 297). T .--. 1.— Γ--Ί1 -pack-f Please read the notes on the back before filling out this page * (-Line printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economics. Γ 4 16831 ： -A7 B7 V. Description of the invention (20) The form of the alkyd resin (a kind with acid値 5.6 (low acidity) and a species with acid 8.0 (high acidity); the level of 鲒 desiccant used (〇〇〇〇 / 〇 and 〇〇２〇 / 〇); the form of the used desiccant (Acid vs. alkaline vs. C / ca vs. Co / Zr); the order in which the dry ingredients are added (that is, the desiccant is added first); and MEK0 = a different composition is thermally aged at 4 (rc for up to 30 days, and the production level of active IPBC (based on the percentage of residuals) in the heat-aging formulation is reported in Tables 1 and 2 below. These results are significant It shows that the presence of acidic components has an adverse effect on the stability of IPBC and the presence of basic substances improves the stability of IPBC in these acidic formulations. Example 8 In this experiment, the conditions of Example 7 a were repeated, except for organic Buffers with suitable solubility in the solvent are added to the formulation. In particular, calcium carbonates such as calcium from Troy Chemical Co., are available at three different levels (00 weight percent, 0.12 weight percent and 0.18 weight). (Percent) were added to the formulation 'which respectively constitute 10: 丨; 5:〗 and 3 3: 丨: ^ ratio buffer in the formulation. The amount of ipBc remaining after heat aging at 4 (rC for 30 days is 78.9 ° / °, 82.3% and 83.3%. As a comparison with the observation result (57_7%) of the untreated Example 73, the stabilization effect of the buffer on the formulation, even when an acidic cobalt desiccant is present, is quite obvious. Although specific embodiments of the present invention have been described in detail herein, it will be recognized that different modifications will occur to those skilled in the art and what is to be understood is that the repairs and differences are included in the outline of this application The spirit and scope of the scope. Green patent-23- This note size applies to China National Standard Extraction (CNS) A4 specifications (2I0X297 male thin), * i; — --------- * 装 __ (Please Read the back of the article first: work idea ^ then fill in ^) i line f 4 16831 V. Description of invention (21) * Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Cra ^ cu1 si 53 to L > Di ί > > 〇〇VO JO o L > '-a Hot bg CA U > to C \ 〇 \ Office ON Μ + 〇 \ to Lf \ ob \ Os P- * \ 〇 W UJ < 1 〇Ν 瘅 〇 >. ίο S U > K > 00 \ 〇〇 > N > * < ί 〇to + v〇ί-Λ i〇-N ON 〇 \ to · -0 UJ > G. UU > S ^ j \ 〇 \ " 〇 \ oo) 0 Ό 〇J S3 (Λ Ο + t— * \ D ON LO U \ ob \ p, ►— · CO \ D to 一 Ν砗 窆 &; spring 〇 \ g LA OJ to H—4 " 'O η 1 CO u > to »— · 00 Ό U) Ή a § m 〇v〇ki g U \ C \ Q \ a \ • K > Oj σ \ g ί-Λ U > ίο 〇 \ * 〇ρϊ OO \ 〇〇 \ v〇t— * L) * 24- (Please read the precautions on the back before filling this page) • 丨 1 bound book Paper fullness applies to Shen Guo National Standard (C \ s) A4 specification (2 丨 0 乂 297mm) f, 416831-& 7 " B7 'V. Description of invention (22) Employees ’cooperation with the Central Bureau of Standards, Ministry of Economic Affairs Women's prints average -σ3 δ3 53 3 ^ 3 Test-17.8 77.4 67.1 83.3 _! 87.0 Low acidity alkyd 59.6 46.8 j 65.3! 59.1 67.1 High acidity + 5,8 65.6 σ \ I 83.3 46.8 65.3 0.06% Zr desiccant 71.4 72.4 87.0) 0 0.23% ·· --1 + 14.3 61.4 • ►-- 72.4 46.8 1_ 59.1, Co / Zr Co Dry punishment 75.7 _1 83.3 87.0 65.3 1 67.1 Co / Ca ί L〇69.2 67.1 83.3 59.1 1__ 〇 \ Zr priority drying Jing 67, 9 72.4 87.0 46.8 65.3 Co priority • 14.3 75.7 83.3 1 87.0 65.3 67.1 1 without 1 _ MEK0 '1 67.1 72.4 46.8 ίΛ νο »— · 丨 Join 1 61.4 67.1 83.3 72.4 87.0 46.8 [65.3 59.1 67. ί reaction. -25- JI —I— -----i I I., order- · --- Silver 'This paper size applies to China National Standard (CNS) Α4 specification (2! 0 乂 297 public love)

Claims (1)

Guangjin—Reporting A8 B8 C8 DS J 68 3 Please specialize in 1¾. 1. A biocidal composition comprising a tooth propargyl compound and a buffer, wherein the weight ratio of the tooth block propyl compound to the buffer Between 50: 1 and 1.100, and wherein the composition is suitable for providing biocidal activity to the end use formulation and stabilizing the end use formulation tpH between 30 and 80 to combat the r | propargyl Degradation of base compounds, 2. Yiyi biological composition according to item 1 of the scope of patent application, wherein the propargyl compound is selected from iodopropylpropyl, iodopropylpropyl ether, iodopropylacetal, amine Iodopropargyl formate and iodopropargyl derivatives of iodopropargyl carbonate. 3. The biocidal composition according to item 2 of the scope of patent application, wherein the halopropargyl aminoformate has the following formula: IC = c—C—0h2 〇IIC ~ N-RΗ I. Ί ------ -Install --------, order ------ line (please read the notes on the back before filling out this page), the staff of the Central Standards Bureau of the Ministry of Economic Affairs, consumer cooperation, R printed from: Hydrogen, substituted and unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted and unsubstituted aryl groups having 6 to 20 carbon atoms, tigeryl aryl group, and aromatic group, and 3 to 10 complete and substituted and unsubstituted cycloalkyl and cycloalkenyl. 1-4. The composition according to item 3 of the patent application park, wherein the buffering agent is selected from the group consisting of bicarbonates, carbonates, organic acids, carbonate complexes, arm 1 acid argon salts, scales Acid esters, phosphonates, borates, borates, 26 ·: Applicable to China Standard (CN: S) 8-4 specifications (2.0 × 297 mm) Employees of the Ministry of Economic Affairs Printed by Consumer Cooperatives: · B8 ί 4 1683 1 C8 " OS 'VI. Application scope of patents' Bisulfate, sulfinate, and sulfate. 5- The composition according to item 4 of the scope of patent application, wherein the buffering agent is selected from the group consisting of potassium bicarbonate, potassium hydrogen phthalate, potassium hydrogen sulfate, potassium dihydrogen citrate, dipotassium hydrogen citrate, potassium dihydrogenate, Field potassium dibasic acid, tartrate completion gas bell 'hydrogen oxalate unloading, potassium maleate, potassium succinate, potassium glutarate, potassium hydrogen adipate, potassium tetraborate, potassium pentaborate, Potassium octaborate, sodium bicarbonate, sodium hydrogen phthalate, sodium hydrogen sulfate, sodium dihydrogen citrate, sodium disodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydrogen tartrate, sodium oxalate, Sodium hydrogen maleate, sodium hydrogen succinate, sodium hydrogen glutarate, sodium hydrogen adipate, sodium tetraborate, sodium pentaborate, sodium octaborate, calcium carbonate complex of caprylic acid, iso-caprylic acid Calcium carbonate complex, 2-ethylhexanoic acid calcium carbonate complex, hexanoic acid calcium carbonate complex, 2 · [2-amino-2-oxoethyl) amino] ethyl Alkanesulfonic acid, N- [2-Ethylamino] -2 -aminoethanesulfonic acid 'N, N -bis [2-hydroxyethyl] -2 -aminoethanesulfonic acid, 2- [bis (2-hydroxyethyl) amino] ethanesulfonic acid and mixed物 6. The composition according to item 5 of the scope of the patent application, wherein the aminoaminoacetic acid acetoacetate is selected from the group consisting of: amino-3-carboxylic acid 2-kidropropylpropyl, aminocarboxylic acid 3-iodine 2-propargyl butyl, 3-amino-2-carboxylic acid, 3-isopropyl hexanoate, 3-iodo-2-aminopropyl carboxylic acid Propyl benzyl esters, and mixtures thereof. 7. The composition according to item 6 of the patent application, wherein the buffering agent is a calcium carbonate complex of isooctanoic acid. 8. — A paint formulation, which includes alkyd resin, dry bath, organic solvent, and a sufficient amount of the composition according to item [] of the patent application park, in order to give 2-27 wood paper scale applicable to Chinese national standards ( CNS) A4 (J10x297 rounded) (please read the notes on the back to save this page and fill in this page), 11 A8 B8 C8 D8- patent application scope biocidal activity for this paint formulation, and provide between 30 to A pH of 80 ° is used to stabilize the desiccant compound against degradation by a stable formulation. 9. The paint formulation according to item 8 of the patent application range, which contains a sufficient amount of the composition according to item 1 of the patent application range to provide a pH between 5 5 and 7 7. 10. The paint formulation according to item 9 of the scope of the patent application, in which the halogen propargyl compound is iodopropargyl aminoformate having the formula: 〇 (Please read the precautions on the back before filling this page) IC = C—C—ο—C—NR h2 Η-Order the consumer cooperation of the China Standards Bureau of the Ministry of Economic Affairs, Du printed where R is selected from: argon, substituted and unsubstituted with 1 to 20 carbon atoms Alkyl, substituted and unsubstituted aryl having 6 to 20 carbon atoms, alkylaryl, and aralkyl, and substituted and unsubstituted cycloalkyl having 3 to 10 carbon atoms And cycloalkenyl. 11. The paint formulation according to item 12 of the application, wherein the buffering agent is selected from the group consisting of bicarbonate cicadas, carbonates, carbonate complexes of organic acids, hydrogen phosphates, and phosphates' phosphonic acids. Esters, borates, collarates, bisulfates, sulfinates, and sulfates ° 12 · The paint formulation according to item 11 of the patent application scope, wherein the buffer is selected from: Potassium bicarbonate, Potassium bicarbonate, Potassium bisulfate, Dihydrogen citrate, Dihydrogen citrate, Potassium dihydrogenate 'Limonium monohydrogenate' tartrate-28- Applicable to Chinese national standards CNS) A4 specification (210X297 mm) Printed bell by the Consumers 'Cooperative of Zhongli Standards Bureau of the Ministry of Economic Affairs: Mouth 1683 1 -DS-1 1 _ Six' application for patent scope acid potassium potassium oxalate potassium hydrogen oxalate, hydrogen maleate Potassium 'potassium hydrogen succinate, potassium hydrogen glutarate, potassium hydrogen adipate, potassium tetraborate, potassium pentaborate' potassium octaborate, sodium bicarbonate, sodium hydrogen phthalate, sodium hydrogen sulfate 'citric acid diargon Sodium, disodium hydrogen citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate 'sodium hydrogen tartrate, sodium hydrogen oxalate , Sodium hydrogen maleate, sodium hydrogen succinate, sodium glutarate, sodium hydrogen adipate, sodium tetraborate, sodium pentaborate, sodium octaborate, calcium carbonate complexes of caprylic acid, iso- Capric acid calcium carbonate complex, 2-ethylhexanoic acid calcium carbonate complex, capric acid calcium carbonate complex, 2- [2-amino-2-oxoethyl) amino] Ethanesulfonic acid, N- [2-ethylamido] -2-aminoethanesulfonic acid, N, N-bis [2-hydroxyethyl] -2-aminoethanesulfonic acid, 2- [ Bis (2-hydroxyethyl) amino] ethanesulfonic acid and mixtures thereof. 13. The paint formulation according to item 13 of the patent application park, wherein the buffer is a calcium carbonate complex of isooctanoic acid. 14. The paint formulation according to item 13 of the scope of the patent application, wherein iododecyl aminoformate is selected from the group consisting of 3-iodo-2-propargylpropylamino, 3-iodoamino 2-propargylbutyl ester, 3-iodo-2-propargylhexyl aminoformate, 3-iodo-2-propargylcyclohexylaminoformate, 3-iodo-2-propargylaminoformate Base vinegar, and mixtures thereof. 15- A method for stabilizing a biocidal formulation containing a southern propargyl compound, the formulation having an alkalinity or acidity sufficient to cause degradation of the halopropargyl compound without adding an acid, base or buffer, the The method includes adding a sufficient amount of acid, alkali or buffer to adjust the pH of the formulation to the range of 3.0 to 8.0 = 16- The method according to item 15 of the scope of patent application, wherein the acid, alkali or buffer- 29- The paper size is suitable for financial affairs $ i CNS) 44 secrets (21GX297 public f _) IT n rl I nl · — n-* n I rL. N ^ 1 '---(Please read the back Note: Please fill in this page again.) A8 .B8 C8 D8- 41683 6. The patent application agent is added in a sufficient amount to adjust the pH of the formulation to the range of 5 5 to 7 7. The method according to item 16 of the scope of patent application, wherein the self-determining propyl compound is selected from the group consisting of: propargyl, iodopropargyl ether, iodine propyl acetal, amino formic acid dibasic ester, and iodoacetyl carbonate Iodopropargyl derivatives of propyl esters 18. The method according to item 17 of the patent application park, wherein the propargyl aminoformate has the following formula: 〇 (Read the precautions on the back before filling in this page) ： IC = c—c—0h2 II 〇-—N-RH The system of consumer cooperation among employees of the China Economic Development Bureau, Ministry of Economic Affairs, where R is selected from: hydrogen, substituted and unsubstituted with 1 to 20 carbon atoms Alkyl groups, substituted and unsubstituted aryl groups having 6 to 20 carbon atoms, alkyl groups, and aryl groups, and substituted and unsubstituted naphthenes having 3 to 10 ling atoms And cycloalkenyl. It is proposed that the method according to item 18 of the scope of patent application, wherein iodopropargyl aminoformate is selected from the group consisting of: 3.iodo-2-propargylpropyl aminoformate and 3-iodo-2-aminoformate Propargyl butyl, 3-iodo-2-bromopropylhexyl carbamic acid, 3-iodo-2-propargylcyclohexyl urethane, 3-iodo-2-propargylbenzene carbamic acid Esters, and mixtures thereof. 2〇.—An improved method for providing biocidal activity for end-use formulations, which _ -30- is set to apply the national standard of China (CNS) A4 (210X297 mm) 8 8 8 0 ^ ABCD Γ 416831 6. The scope of the patent application includes adding a sufficient amount of the composition according to item 1 of the scope of the patent application to the end-use formulation to impart the biocidal activity to the compound, and provide a range between 3.0 and 8.0. PH between rooms. — 7--Γ--K --- pack ---------- *-order- > ------ i (please read the notes on the back before filling this page) Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Education-31-This paper iron standard is applicable to China National Standard (CNS) A4 (210X297 mm)