TW299327B - 2-alkyl or 2-aralkyl-bit Compound, composition comprising same and use thereof - Google Patents

Abstract

A 2-alkyl or 2-aralkyl-BIT compound of formula 1, a composition comprises a plasticiser or stabiliser and the compound of formula 1, a composition comprises a plastics material and the compound of formula 1, and the use of the compound of formula 1 as a fungicide for plastics materials, in which the compound of formula 1 is as follow: (see claim 1) in which R is C3-5-alkyl, cycloalkyl or aralkyl which contains at least 2 carbon atoms linking the aryl group to the nitrogen atom and where the alkyl or aryl group may be optionally substituted.

Description

A7 A7 Employee's Consumer Cooperative Printing of the Central Central Bureau of Economic Affairs B7 i. Description of the invention (1) The present invention relates to 2-alkyl- and 2-aralkyl · ι, 2 · benzyl isopyrazoline _ 3_ Ketones and their compositions' are used as biological bactericides for protecting plastic materials, especially as bactericidal agents. 1,2-Different p Selin Linming (BIT " below) and its use as a biocide are well known in the art. GB 848,130 discloses BITs containing 2-alkyl substituents particularly containing at least 4 carbon atoms or 2-phenyl substituted by halogen. These compounds are said to have useful antibacterial and mycobacterial activity and can be used as biocides in pharmaceuticals, veterinary medicine and agriculture. US 3J17,022 discloses a BIT 'containing a 2-alkyl substituent particularly having from 4 to 24 carbon atoms and the benzene ring of the BIT may be substituted with a free radical, a c14-alkyl group or an A_4_alkyl group. These compounds are said to be industrially useful biocides, especially agricultural fungicides and also insecticides. GB 1,53 1,43 1 publishes 2-((^ 3-burn-based) -BIT and its use as an industrial biocide including fungicides in water-soluble systems and paint films. Recently 'EP 475, 123 has proposed the use of 2- (n-C6_8 • alkyl) -BIT as an industrial biocide, especially as a fungicide for paints and plastic materials. These compounds are said to be resistant to short-stem brooms Broom fungus is particularly ill. In addition, it is said that the activity of 2- (n-C6_8-alkyl) -BIT against hyphomycetes is higher than that of GB 1,531,431-2_ (C Bu 3-burn-based) -BIT. In fact, the data also showed that 2_n-octyl · BIT is more active than 2-n-hexyl-BIT, and the activity of the two against spores and yeasts is significantly higher than that of 2-methyl-BIT High. It has been found that some 2-alkyl-BIT derivatives have very strong activity against degrading bacteria of plastic materials. This and EP 475,123 have recently been announced. These -4 CNS) Μ specifications (210X297 Gongchu) ------------- (please read the precautions on the back before filling in this page) Order 4 A7 B7 V. Description of the invention (2 Compounds are important in combating plastic materials The activity of the bacteria decreases with the increase in the number of carbon atoms in the 2-alkyl chain. Another important property required for plastic material bactericides is that the powder is resistant to the manufacturing process during shape processing, such as extrusion The ability to hang is included when the temperature exceeds 14 °. (: The plastic material is heated at this time. Therefore, it is important that the fungicide has high-temperature capability and low volatility in this case. It has been found that BIT with higher activity • Derivatives have too high volatility and are not suitable for manufacturing fungicides as plastic materials. The 2-block group must contain not less than 3 carbon atoms. 2-Aralkyl-BIT derivatives are acceptable and Favorable low volatility. The antimicrobial agent of the plastic materials department is also an important requirement. The staff must be able to formulate with plasticizers and stabilizers commonly used in the plastics processing industry, and the antimicrobial agent is used when It is highly resistant to discoloration, and the treated plastic materials will show a long-lasting effect when used. Some 2-alkyl and 2-aralkyl BIT derivatives (hereinafter referred to as " ABIT " have been found ) In line with the foregoing In particular, in terms of volatility and activity against the deterioration of plastic materials such as mycobacteria. Central Ministry of Economic Affairs Staff Consumer Cooperative Printed According to the present invention, it provides 2-alkyl- and 2-aralkyl groups of formula 1 The use of BIT derivatives as fungicides for plastic materials.

NR A7 B7 V. Description of the invention (3) R1 is hydroxy, halogen, 4-alkyl or Cm-alkoxy; R is C3_5-alkyl, cycloalkyl or contains at least 2 carbon atoms to connect the aryl group Aralkyl to nitrogen atom, where alkyl or aryl can be optionally substituted; and η is from 0 to 4. The halogen is preferably bromine, and especially gas. The substituent R1 is preferably located at the 5- and 6- positions of the BIT molecule, especially at the 6-position. In a particularly preferred embodiment, n is 0. When R is an alkyl group, it may be linear or branched, but linear is preferred. Examples of these alkyl groups are n-propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl , N-pentyl, isopentyl and 2-methylbutyl. When R is cycloalkyl, cyclopentyl is preferred. When R is an apical group, it preferably contains 4 carbon atoms, especially n-butyl group. When R is aryl tiger group, 2-arylethyl is preferred, and especially 2-phenylethyl. When R represents an alkyl or aryl part of an aralkyl group, the substituent is preferably a mesyl group, a southern group or a benzyl group. However, it is preferable that the pit and aryl parts are not substituted. ^ IT ------ (Please read the precautions on the back before filling in this page) Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs when R is n-butyl and especially 2-phenylethyl The effect is particularly good. From the concentration at which ABIT can control the growth of some fungi to a higher concentration, ABIT is mixed into the plastic material to be protected. The weight percentage of the ABIT amount is preferably less than 1.5% of the weight of the plastic material, more preferably less than 1 _ Q%, and less than -6- This paper scale is applicable to China National Sample Rate (CNS) 8 Technology, A7 A7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -----_____ V. Description of the invention (4) '~~~-0.7% is particularly good, and less than 0.5% is particularly good. When the amount of eight dices is less than 0.25% by weight of the plastic material, or even less than 〇1%, a useful effect can be obtained. ABIT must be stable at this temperature when forming plastic materials. Stability is better at i80 ° C or higher, better at 20 ° C and above, and particularly better at 25 ° C or higher. At a heating rate of 1 (TC / min, from 25 to 16 °. (: Weight when heated) The loss is preferably less than 10%, more preferably less than 6%, and more preferably less than 2%. As mentioned above, the ABIT is usually formulated with a plasticizer or stabilizer suitable for the plastic material to be protected. According to another aspect of the present invention, a composition comprising a plasticizer or stabilizer and ABIT is provided. Plasticizers or stabilizers are often used in the plastic forming industry. It is best to use liquid and special mono- and di- Several acids and esters derived from straight or branched alcohols, epoxidized fatty acid esters, and epoxidized vegetable oils. Examples of these plasticizers and stabilizers are phthalates, especially dialkyl phthalates, such as dialkyl Octyl S acetic acid ester 'di- (2-ethylheptyl) gj: acetic acid ester' dinonyl g acetic acid ester and di-isodecyl phthalate, epoxidized octyl stearate and cyclic Oxidized soybean oil; with phosphate ester of the general formula 0 = P (0R2) 3 where R2 is a hydrocarbon group, especially an aryl group such as phenyl, and more particularly can be a straight bond or branched chain c1-4 alkyl β Examples of these alkyl groups are methyl, ethyl, isopropyl, butyl and tertiary butyl. Examples of other vinegars are adipic acid vinegar, sebacic acid vinegar and especially those containing 8 Straight-chain or branched alcohol trimellitic acid with up to 10 carbon atoms The paper size is applicable to the Chinese National Standard (CMS) A4 specification (2 丨 0 297mm) i— (please read the precautions on the back before filling this page) -1¾ A7 B7 Employee Consumption Cooperation Duty Print 5. Description of the invention (5) The composition may contain more than one ABIT, and may also contain other fungicides and / or algaecides to increase its activity range. Other fungicides Examples of and / or algaecides include 2-alkyl_BIT, s, such as 2- (n-hexyl) -BIT, 2- (2-ethylbutyl) -BIT, 2- (2-ethylhexyl ) -BIT, 2-octylisodihydrothiazol-3-one, oxo-bis-10,10 · phenylarsine, trichloromethine thiamine; pulses such as 2- (3,4-digas Phenyl) -l, l-dimethyl vein and 2- (4-isophenylpropyl) -1 1-Dimethylurea; 4-dentated alkylsulfonic acid pyridine, such as 2,3,5,6_tetragas_4- (methylglycolic acid) -pyridine and 2,3,6-trigas-4 -(Isopropyl) -sulfonic acid pyridine; tetrachloro_isopoliminic acid nitrile; tolbenzimidazole-carbamic acid; thiocyanothiobenzophenazole; methylene dithiocyanate, iodopropynyl_ N-Butyl-carbamic acid; tri-, such as 2-second-butylamine_4_ethylamine · 6_methyl gas thiol_1,3,5-trimethylbenzene and 2-methylthio- 4-Third-Butylamine_6-Cyclopropylamino_ι, 3,5-Sanken; n- (ι_methyl_1_ stubble) cis-butyric amine compound; difluorofluoroamine compound ” (Captan and (fluoro) -folpet. When the composition contains added fungicide and / or algaecide, the amount is preferably less than 50% of the relative weight percentage of ABIT, more preferably less than 30%, and more preferably less than 10%. As mentioned above, plastic fungicides need to carefully balance the microbial activity and volatility, and then any added fungicides and / or deodorants should not significantly harm the nature and performance of the ABIT used. For this reason, it is preferred that the composition contain only one ABIT. The 2-alkyl-BIT's of Formula 1 are usually 'liquid' at 20 to 25 ° C and are easily soluble in plasticizers and stabilizers. Aralkyl-BIT'S is a solid skeleton at 20 to 25 ° C, but it can be heated to make it easily soluble in plasticizers and stable residues if needed. -8-I_— _________ This paper scale is subject to the Chinese National Standard (CNS ) A4 specification (210X297 epidemic) --- --------- 〇 ----- i. ^ .------ 0 (Please read the precautions on the back before filling this page) 5. Description of the invention (6 A7 B7 When the plasticizer or stabilizer requires a higher concentration of ABITM to exceed its solubility, ABIT will be dispersed in the plasticizer or stabilizer by a suitable dispersant, especially a non-ionic dispersant. There is a preferred dispersant is the product of the reaction of hydroxycarboxylic acid and amine compound or its salts. The dispersant of formula 2 is particularly preferred, YCO.ZR3 2 where Z is a bivalent link to the carbonyl group through an oxygen or nitrogen atom Bridge bond; R3 is the first, second or third amine group or salt with acid, or the fourth ammonium salt The Ministry of Economic Affairs Central Standards Bureau employee consumer cooperative printing Y Y is a multi-vinegar bond with the residue of C 0-group The group is derived from the hydroxycarboxylic acid of formula 3 HO-X-COOH 3 where X is containing at least 8 carbon atoms, and at least 4 carbon atoms are located between the meridian group and a few groups, A divalent saturated or unsaturated aliphatic group derived from such a mixture of hydroxycarboxylic acid and hydroxyacrylic acid. X is preferably an alkenyl group or a vinylene group, and most contains no more than 30 carbon atoms, In particular, it does not exceed 20 carbon atoms. Examples of hydroxycarboxylic acids suitable for formula 3 are 12-benzyl stearic acid, grate oleic acid, 1 2- # to decanoic acid, and 6-lexyhexanoic acid. The bivalent bridge bond is preferably of the formula T1 or —N—A— —Ο—A— H--J I. I ·---II I-g- 一---I -1--, 0 S1- ---I---1 · —II I--., -A ·· (Please read the precautions on the back before filling out this page) S-This paper size is applicable to China National Standard (CNS) A4 specification ( 21DX297 a public celebration)

Where T1 is a hydrogen atom, Ci_22-alkyl or vinyl, and A is a hydrocarbyl group, a cycloalkenyl group, a heterocycloalkenyl group or a hydrocarbyl group containing from 2 to 6 carbon atoms. When T1 is an alkyl group, it is preferably Cn-regular group, and when a is a heterocyclenyl group, hexahydropyrrolidine is preferred. When both T 1 and A are vinyl groups, T 1 and A together with the gas atom to which they are connected and the nitrogen atom of the amine group R 3 form a six gas t? B ring. Examples of the group represented by T 1 may be methyl, ethyl, n-propyl, n-butyl and octadecyl. In the example of the group represented by A, it may be ethylene, trimethylene, tetramethylene, hexamethylene, and Θ-hydrocarbon trimethenyl. The first, second, or third represented by R 3 The following formula is better for amine groups (please read the precautions on the back before filling in this page) —N. T2, Ding 3-Ordered by the Ministry of Economic Affairs, Central Standards Bureau, employees to invest and cooperate to print T2 and T3 are not related. Hydrogen, cU22-alkyl, substituted Ch22-alkyl, aralkyl, cycloalkyl, or T2 and T3 together with the attached nitrogen atom form a 5- or 6-film ring. When T 2 and T 3 are alkyl groups, it is preferable to use a C 6-alkyl group such as methyl. When τ 2 and T 3 are cycloalkyl groups, it is preferably hexyl, and when T 2 and T 3 form a ring At the time, hexahydrop is preferred to phenyl, morpholinyl, or especially hexahydropyridine. When T 2 and T 3 are aralkyl, phenyl is preferred. The fourth ammonium represented by R 3 Based on the following formula: D-H-T3 -10-t paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of Gongchu _ A7 ~ --- ~ _ B7 5. Description of the invention, \ 一 '~ _8} where T 4 is gas, Cl-22_alkyl, substituted Ci_22-alkyl, aralkyl or yialkyl, and w is an anion. D 4 is preferably a Ci_6_alkyl group like methyl. In a special case, T2 and T3 will be connected to a nitrogen atom and form a hexahydrogen ratio with them. Both or one of the nitrogen atoms can be alkyl Any cyclic gas can form salts or a fourth ammonium compound. Examples of the groups represented by τ ′ T 3 and τ 4 can be alkyl groups, such as ethyl, n-propyl, n- -Butyl and octadecyl, low-carbon carboxyl 1 group For example, Wan-hydroxyethyl and cyclohexyl. The acid used to form salts with amine groups or containing anions w can be any inorganic or organic acid, such as hydrochloride, sulfate, methane benzenesulfonate, sulfonic acid Or benzoic acid. The anion w is preferably formed with a fourth ammonium group, such as fluorine, bromine or methosulfate. The preparation of these dispersants is described in the previously issued patent GB 1373660. In addition, the dispersant is poly ( The reaction product of a lower alkenyl) imine and a polyester with a free carboxylic acid group. The preferred polyester is derived from the hydroxycarboxylic acid HO-X-COOH 3 of formula 3 as defined above. The weight ratio of poly (lower alkenyl) imine reaction is preferably between 1: 1 and 50: 1, and more preferably between 2: 1 and 20: 1. The term "lower alkenyl" refers to Containing from 2 to 4 carbon atoms, the preferred poly (lower alkenyl) imine is substantially straight or branched polyethyleneimine. The polyethyleneimine is best It is branched, and especially -11-winter paper is again applicable to China National Standard (CNS) A4 specification (210X297mm), ------------ Q -(Please read the precautions on the back before filling in this page) Order Ψ. Printed A7 _____B7 by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of invention (9) At least 20% of nitrogen atoms are based on the third amino group The presence of highly branched. The molecular weight of suitable poly (low carbon women's) imines is usually greater than 500, but preferably greater than 5000, and more preferably in the range of 10,000 to 100,000. ) The reaction product of the imine may be salts or aminated compounds depending on the intensity of the reaction used ◊ The salts and / or aminated compounds can be partially neutralized with acids, especially mineral acids; or In the case of alkylation, the added alkyl group can be substituted at will and react with pit sulfates such as dihexyl sulfate, thus also forming a salt. The preparation of the reaction product of methacrylic acid and poly (low-brokenyl) imine is described in GB 2,001,083 0 from about 2 mole poly (12-methacrylic stearic acid) with 35 mg KOH / g of acid, and 1 Molar dimethylaminopropylamine and dimethylsulfuric acid, as described in Comparative Example c of EP 127,325, after quaternization, the reaction product obtained is a particularly useful dispersant. The dispersion is referred to herein as "dispersant 1". From about 3.3 equivalents of poly (12-hydroxystearic acid) and 1 equivalent of polyethyleneimine with a weight average molecular weight of about 20,000, the product obtained by reacting together is another A particularly useful dispersant. The preparation method is similar to that of GB 2,001, 〇83, reagent A, and this dispersant is denoted by "dispersant 2" herein. If a dispersant is present, it will range from 0.1% to 20% of the total weight of the composition. / 〇 is preferably from 1 to 10. /. More preferably, it is from 3 to 10 (? /. It is particularly good, and most preferably from 3 to 7%. The composition also preferably contains a stabilizer that can suppress the Shen Temple during storage. Examples of stabilizers are natural The resulting clay, such as loaded soil 'and specially modified organically modified pulp clay and high molecular weight polymer, _____-12- This paper scale is applicable to the Chinese prisoner's ladder (CMS) M specification (2.10X297 / ^') " — ---- ο.— (please read the precautions on the back before filling in this page) Order ΦΙ. A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of invention (%) For example PVC. As previously announced Yes, ABIT is used as a biocide and is especially a fungicide for protecting plastic materials, especially it can prevent microorganisms from degrading organic polymerized plastic materials. The ABIT is especially suitable for polyurea substances, Especially organic polymer materials containing plasticizers or stabilizers, such as polyethylene halides derived from polymerization, such as polyethylene gas (PVC). Plasticized PVC is widely used in homes and industries, and also used For clothes, furniture, bath Curtains, floors, waterproofing membranes, and similar items that are or are made of PVC when exposed to moisture or moisture. The amount of plasticizer present in plastic materials varies widely, and is determined after processing The required flexibility of the material is determined. It is typically between 1 and 50% by weight of the plastic material. Therefore, another aspect of the present invention is to provide a composition containing ABIT and plastic material. The ABIT It is a method known in this art, for example, GB 484,130 describes those methods in which 2-gas thiobenzoic acid is reacted with alkylamine or aralkylamine. Some ABIT are new. Therefore, the present invention Aspects also provide compounds of formula 1, wherein R is -CH (CH3) CH2C.H2CH3, -CH (C.2H5) CH2CH3, -ch2ch2ch (ch3) ch3, -ch2ch (ch3) ch3, -ch2ch (ch3) c2h5 And cyclopentyl, and R1 and n are as defined above. All of the present invention is further shown and described in the following examples, unless otherwise stated, where each part is a percentage by weight.

Example 1 and Comparative Example A -13-This paper scale is applicable to the Chinese National Standard (CNS> M Specification (21〇Χ2 ^ ϋ .-II ------- ο —I (Please read the notes on the back before filling in This page)-° ^ 1. A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of the invention (11) The maize potato dextrose agar (2 copies; ex Oxoid), the pancreatic protein gland soy broth ( 10 parts; ex Oxoid) and adipose fat (14 parts; ex Oxoid) add water to 1 liter to prepare an agar formulation with an acid-base value of 6.5. Add a weight percentage of 0.1% dissolved in dioctyl phthalate and pass After the test, the ABIT aqueous solution was diluted to 3 ml with dioctyl phthalate to obtain agar formulations with final concentrations of 1.25, 2.5, 5, 20 and 30 ppm. Add the ABIT solution to the agar and mix it evenly, then pour into the flat It is allowed to solidify in the dish. These flat dishes are then incubated with a suspension of spores of less than 105 plastic materials. Aureobasidium pullulans (AP) CM1 145194 Fusarium solanii (Fusarium solanii ( FS) CM1 172506 Penicillium funiculosum (PF) CM1 114933 short light hug Scopulariopsis brevicaulis (SB) CM1 49528 waksmanii Streptoverticillium waksmanii (SW) NCIB 1091 Incubate the dish at 20 ° C for 4 days, and when the growth of the candida is inhibited, ABIT can be determined The results are shown in Table 1 below, which refers to ABIT of Formula 1, where η is 0 and R is as described in the table. Compared with the control group, 2-ethyl- and 2- (n-propyl ) -BIT has better anti-AP and SB activity. 2-Methyl-BIT has higher anti-FS activity. Table 1 Examples or Comparative Examples R AP FS PF SB SW A Ethyl 20 5 1.25 20 1.25 1 Positive-propyl 20 20 1.25 20 1.25 Control group- 30 20 1.25 30 1.25 -14- This paper scale is applicable to China National Standard (CNS) A4 specification (210X 297mm) 0 ^ .— (Please read the notes on the back first (Fill in " this page) Ύ · 1 Printed A7 s ------ B7 ____ support and invention description by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (12) N-propyl) · iso, sezoline-3-one.

Repeat Comparative Examples B to D. Repeat Example 1 according to the ABIT described in Table 2 below, and determine the concentration of the chemical when inhibiting mycobacteria. The results are shown in Table 2. The 2_ (positive • BIT ratio EP 475, 123 is published Of, including 2_ (n_hexyl) and 2_ (n-octyl) • BIT compounds with higher anti-SB activity, especially when compared with 2_ (n · octyl) · BIT, in the fight against five kinds of plastic materials The bacteria are degraded and have higher activity. Generally, the 2- (n-butyl) -BIT is similar to the control group. The results of Reference Example 1 show that when the length of ABIT alkyl chain increases, the resistance to plastic materials is five. The general trend of the activity of the species of degrading bacteria. The 2-phenyl-BIT has an activity between the 2- (n-hexyl)-and 2- (n-octyl) -BIT. These plastics As a material deteriorating pathogen, the increase in the number of carbon atoms in the 2-alkyl chain of ABIT will decrease the activity, which is contrary to that published in EP 475,123 for the Mycobacterium for example, aspergillus niger. Table Ί Examples or Comparative Examples R AP FS PF SB SW 2 n-butyl 5 20 1.25 1.25 5 B n-hexyl. 5 > 30 2.5 2.5 20 C n-octyl > 30 > 30 > 30 20 > 30 D Phenyl 30 > 30 2.5 5 30 Control group 1.25 20 1.25 2.5 2.5 -15-: The standard is applicable to the Fyuan National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling the nest page )

Printed example or comparative example of the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs R ΑΡ. FS PF SB SW 3 n- 戌 基 5 20 1.25 1.25 1.25 Ε 2-ethylbutyl 5 30 20 1.25 20 F n-heptyl 20 > 30 2.5 1.25 > 1.25 4 2-phenethyl 1.25 1.25 1.25 1.25 1.25 control group 2.5 20 2.5 '1.25 1.25 A7 ____ B7 5. Description of the invention (13) The control group is as described in Example 1

Examples 3 and 4 and Comparative Examples E to F In addition to replacing the dioctyl phthalate used in Example 1 with a 50/50 mixture of i-dioctyl i-octanoate and S-taurate adipate, according to Table 3 below The listed ABIT repeats Example 1 again. The results in Table 3 below show that n-pentyl_BIT has similar activity to that of the control group, especially its activity against AP and FS is better than that of n-heptyl-BIT. These results are again consistent with the fact that when the 2-alkyl chain length of ABIT increases, the activity decreases accordingly. The branched chain compound 2-ethylbutyl-BIT (Comparative Example E of Table 3) has a linear analogue (Table Comparative Example 2 of 2) Similar activity, but will lose some anti-PF activity. The 2-phenethyl compound has a very high activity against all five deteriorating agents, and is superior to 2 · (n-alkyl) -BIT'S and 2-phenyl-BIT in this respect (Comparative Example D of Table 2). A__3 Note to Table 3 The control group is described in Table 1. -16-This paper scale applies the Chinese National Standard (CNS) A4 specification (2ΙΟX297mm) -------- 〇II (Please read the precautions on the back before filling in this tile)

., 1T Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperative Printing Policy A7 _______B7_ V. Description of the invention (14)

Examples 5 to 7 and Comparative Example A The ABIT, s listed in Table 4 below were heated on a differential scanning calorimeter (DSC) using empty milk from 25-300 C at a heating rate of 10 C / min, and occurred The above-mentioned temperatures of evaporation together determine the stability of the temperature; and the weight loss before 160 ° also represents the temperature required for the PVC forming process. These results indicate that at least 3 carbon atoms in the burned chain of ABIT need to be thermally stable to resist the temperature at which PVC plastic materials are formed. When these results are combined with ABIT's anti-mycobacterial data where R represents C3-5 · alkyl in Examples 1 to 4, it is the best compromise for protecting mycobacteria from plasticized PVC plastic materials. method. 2-Phenethyl-BI-D has both physical properties and activity such as thermal stability, showing that this compound is superior to 2-burn-bit-bits as an anti-septic agent for PVC plastic materials, especially in Example 2 The activity of green 2-phenyl-BIT is compared "Table 4 Example number R Stability Temperature evaporation weight (° 〇) before 160 ° C (.〇Quantity loss 5 n-propyl 240 130 5.5 6 n-Butyl 260 96 * 5.1 7 2-phenethyl> 250 > 200 0 A ethyl 235 107 10.6 Note to Table 4 • Solvent impurities may cause low number values. T Examples 8 to 1 5 and comparative examples A, G and Η -17- Melon paper Langfandu is applicable to the Chinese National Standard (CMS) Α4 specification (210Χ297 mm) ^^ Clothing. '· (Please read the precautions on the back before filling this page.) A7 B7 5. Description of the invention (15) The mycoesterase activity in PVC is determined by the following steps of fluorescent ethyl acetate ethyl acetate. Adding dioctyl phthalate and adipic acid phthalate dissolved in 50/50 Ester, ABIT in a 1% by weight aqueous compound solution to obtain chemicals with final PVC concentrations of 100, 250, 750, 2250 and 6750 ppm , And prepare a PVC flat plate. The PVC flat plate has the following composition: 100 parts, 2 parts of PVC resin (Corvic S 67/100), 3 parts of zinc / Mo stabilizer (Lankromark LN 138), 3 parts of plasticizer (LankroflexED6) 25 parts, plasticizer (di-iso-octyl phthalate) (DOP) 25 parts, plasticizer (di-octyl phthalate (DOA)

0.5 parts, 0.2 parts of calcium stearate dispersant, ppm stearic acid mildew remover ppm ABIT Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) Mix the above ingredients, Then, at 160 ° C, the PVC board was prepared by rolling and mixing on a two-roll mill for 90 seconds. After that, the board was cut into several pieces, and pressed at 8 tons at 160 ° C between the steel plates for 5 minutes to form a flat plate (2 cm X 5 cm). Place the double-layered PVC flat disc on the surface of the wet tortuous bed and spray it with 105 suspensions of the five species of mycetes listed in Example 1 which contain 2.0 parts of sodium nitrate in 1 liter , 0.7 parts potassium dihydrogen phosphate, 0.3 parts dipotassium hydrogen phosphate, 0.5 parts gasification bell, 0.5 parts sulfuric acid heptahydrate and 0.01 parts ferrous sulfate heptahydrate, with a very low concentration of 6 to 6.5 Salt-soluble -18- This paper scale is applicable to the national standard (CNS) Λ4 specifications (210X297 mm) of A country. A7 2 ^ 93 ^ 7 B7 5. Description of invention () 16 liquid preparation "(please read the notes on the back first Please fill in the details on this page) and then incubate the culture plate at 21 ° C for 7 days. Afterwards, the flat plate was taken out and placed into a mixture containing 0.06M disodium hydrogen phosphate (862.5 ml) and 0.06M sodium dihydrogen orthophosphate (137.5 ml) and 1 ml of fluorescent acetic acid dissolved in dry acetone. Individual bottles of 6 ml of pH 7.6 buffer prepared with ethyl acetate (FDA). The sample was then incubated at 37 ° C for 30 minutes to produce a color reaction. Using a spectrometer at 490 nm, measure the absorbance of each solution. The color reaction is used to measure the esterification of spores and show the deterioration of the spores on plasticizers. Prior to FDA analysis and evaluation, after incubating for 1 month at 25 ° C and 95% relative humidity, the growth of the spore fungus in the plate can also be visually estimated using a stereo microscope. After using Atlas ES-25 weather meter at cam setting of 7, and after 10 minutes of water circulation and weathering for 2 hours every 10 minutes, the parallel experiment was continued on the plate irradiated with ultraviolet rays. The results are shown in Tables 5 and 6 below. The FDA analysis of unweathered samples of 100 and 250 ppm in the printed form 5 of the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs confirmed that the resistance of the five plastic materials to mycelia deteriorated the original activity, along with the 2-alkyl chain carbon The number increases and decreases. However, it should be clarified that even low-carbon alkyl chain analogues will have some ABIT losses in the case of flat plate forming. However, after weathering, there is an opposite trend. As the number of carbon atoms in the 2-alkyl chain increases, its protection against Candida also increases. This phenomenon is most clear when the ABIT amount is 750 ppm. Although again with the increase in the number of carbon atoms in the 2-alkyl chain, the activity decreases -19- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0 X 297 mm) A7 B7 V. Description of invention ( π) 17 The trend is low, but the data on the growth trend of Candida in Table 6 are not clear. The unweathered data for 250 and 750 ppm ABIT shows the clearest. The weathered Zhao Shi is less clear. However, when combining the data in Tables 1 to 6 and considering the temperature stability, volatility and anti-mycobacterial activity, ABIT's is the most suitable for plastic materials. In the case of ABIT's containing 2-alkyl chains, this consideration is for 2- (C3_j · -alkyl) _BIT's. A__5_ FDA analysis of the example of the printing of the consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs and the chemical roll (ppm) to be measured Comparative example R Weathered 100 250 750 2250 6750 8 n-propyl U si tr--ND W ++ ++ sl -ND 9 n-butyl U si si--ND W + ++ tr-ND 10 n-pentyl U tr---ND .... W tr si--ND 11 2-epoxy-ethyl U-- --ND W i tr _--ND A ethyl U tr---ND W ++ si ~ i ~~ h-ND GU ND si sl--W ND + sl--Η U + W 十 + control group U 十 + W 十 + -20- This paper scale is applicable to the Chinese National Standard (CNS). M size 210 X 297 mm) (please read the precautions on the back before filling this page) -a Ψ. Α7 Β7 5. Invention Description (4.) 18 Note to Table 5 u is unweathered w is weathered ND is undecided G is trichloromethane thiol imine H is oxygen-bis-10,10-phenylarsine-is at 490 No absorbance at nm tr is less than 0.1 at 490 nm, si is 0.1-0.25 at 490 nm + is 0.25-0.5 at 490 nm + + is more than 0.5 at 490 nm {please read Of the back Matters needing attention and then fill out this page) Order Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -21-This paper scale is applicable to the Chinese National Standard (CNS) A4At grid (2 丨 0X297mm) V. Description of invention (19 A7 B7

Printed by the Employee Consumer Cooperative of the Central Ministry of Economic Affairs

R Weathering 100 Chemical concentration (ppm) to be just 250 250 750 2250 6750 n-propyl U 3,3 〇, 〇ND 〇, 〇0,0 ND W 5,5 5,5 ND 3,3 0,0 ND positive -Butyl U 1,1 U ND 0,0 0,0 ND W 5,5 4,5 ND 4,5 0,0 ND n-pentyl U 4,4 3,2 ND 2,3 2,1 ND W 4,3 4,4 ND 3,2 3,3 ND 2-phenyl-ethyl U 4,2 0,0 ND 0,0 0,0 ND W 5,5 5,5 ND 3,3 0, 0 ND Ethyl UU 0,0 ND 0,0 0,0 ND W 5,5 3,2 ND 4,2 0,0 ND U ND 2,2 ND UU 0,0 W ND 4,3 ND 2,2 1,1 0,0 U 4,4 ND 0,0 ND ND ND W 5,5 ND 5,5 ND ND ND U 5,5 ND W; 5,5 ND:-^ „---- ^- -0 ------, 玎 ------ * V (Please read the precautions on the back before filling in this page) Examples and Comparative Examples 12 13 14 15 AG Η Control Group Table 6 Note n, w and The description of ND is the same as the meaning of Table 5. G is tri-gas f-hydrothiosulfonylidene imide H is oxygen-bis-10, 10 · benzoarsine is no growth on the plate to be tested 1 is the growth area is below 1 〇 / 〇22 This paper scale is applicable to China National Standard (CNS) Α4 specification (public product) A7 B7 5. Invention description (20 Central Bureau of Standards of the Ministry of Economic Affairs 『Peigong Consumer Cooperatives’ Innolux 2 is the growth side The product is 1-10% 3 is the growth area of 10-30% 4 is the growth area of 30-70% 5 is the growth area of more than 70% Example 1 6 a) Preparation 2,2'-disulfide-positive- ( 3-Methylbutyl) · dibenzoic acid was dried at 0 to 5C, dithiodibenzoic acid gas (6 · 86 parts, 0.02M) was divided into several times, and isoamylamine was dissolved while stirring ( 3.47 parts, 0.04M ex Aldrich) and triethylamine (4.04 parts, 0.04M ex Aldrich) in the ethyl mystery solution immediately formed a hall. The reaction mixture was searched for 16 hours while allowing the temperature to rise to about 20 ° C. Then The ether was evaporated and the product was rinsed with methanol (mL) and water (50 mL). Finally, the product produced white solid crystals in methanol (6 parts, theoretical value 69%, melting point = 181-183 ° C. Basic Analysis: Theoretical value: -64.8% C, 7.3% H, 6.3% N, 14.4〇 /. 8 Found values: -64.1% C, 6.9% H, 6_3% N, 14.40 / 〇S B) Preparation of 2- (3-methylbutyl) -benzyl-isothiophene. Lin_3_one The bis-amide (5 · 7 parts, 0.0128 M) prepared by the above method was dissolved in pyridine (75 ml) and added in portions (3% parts) with stirring at 20 to 2yC '0 · 0128M). Initially, iodine decolorizes quickly, but when the iodine is added, the reaction mixture becomes yellow-brown. After stirring at 20 to 25 ° C for another 2 hours, the reaction mixture became almost colorless. However, the pyridine was evaporated, and the product dissolved in benzene was washed with an aqueous solution of sodium trisulfate and then with water to remove residual iodine. Then, toluene is evaporated to produce pale yellow oil 23 (please read the precautions on the back before filling in this page) Order> I-A7 B7 V. Description of invention (21 Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (5.3 Parts, the theoretical value is 94%), and leave it to a solid state. The product is recrystallized in hexane with a melting point = 55_56 ° C. Basic analysis: The theoretical value: -65.1% C, 6.6% H, 6.4% N, 14.6 〇 / 〇S found value: -65.1% C, 6.8% H, 6.3% N, 14.50 / 〇s Example 1 7 Preparation of 2- (1-methylbutane) arisopyridazoline-3- Ketone At 0 to 3 ° C, dissolve 2-gas thiobenzoic acid (6 parts, 0.029M) in ether (30 ml), and add the stirred methyl butylamine (7.36 parts) dropwise , 0,84M ex Aldrich) in Ethylene (30 ml). Stir the reaction for 16 hours, at which time the temperature can be allowed to rise to about 2.0. Then the acid solution is screened, rinsed with water and Dry on sulfuric acid. After evaporating the ether, a product like light yellow gum (5.5 parts, theoretical value 86%) is obtained, which gradually forms a solid after standing. This product is recrystallized in hexane with a melting point = 52_54 ° C 》 Basic analysis theory value: -65.3% C, 7.2% H, 6.5% N, 14.40 / 〇S found value: -65.1% C, 6.8% H, 6.3% N, 14.5% S Example 18, preparation 2-Π-ethylpropyl) benzylpyrimazolin-3-one except using 2-gas sulfonic acid gas (6.21 parts, 0.03M) and ethyl butylamine (8.7 parts, 〇_2M ex Aldrich ), Except that it was prepared in a similar way as described in Example 17, the product obtained was like a light yellow gum (6.4 parts, 96% in class), and left to form a solid state. This product is reconstituted in its own pit with a melting point = 80-82 ° C. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ——. M ^ in ^ — n ^ i «In —m tm I • 1¾ (please read the precautions on the back and fill in page 35) Order- ^ wl. V. Description of invention 22. A7 B7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics. Basic analysis theory value: -64.8% C , 5.7% Η, 6.3% Ν, 14.5% S found value: -65.1% C, 6.8% H, 6.3% Ν, 14.5% S, especially Example 1 9 Preparation of 2-cyclopentyl isocyanine -3-Copper. It was prepared in a similar manner as described in Example 17 except that 2-gas sulfurbenzene gas (5 · 175 parts, 0.025M) and cyclopentylamine (8 52 parts' 0.1 M ex Aldrich) were used. The obtained product and light yellow oil (5.9 parts) were recrystallized in hexane with dazzling point = 87 · 88 < ^. Example 2 0 I prepared 2- (2-methylpropyl) benzimidazolin-3-one in addition to the use of 2-gas sulfurbenzene gas (4.14 parts' 0.021 \ «1) and isobutylamine (7 95 Parts, 0.08M), prepared by the method described in Example 17. The product obtained (4 parts, theoretical value is 97%) is like pale yellow oil. Example 2 1 to 2 5 The following bisamides of Formula A were prepared by the method described in Example 19 (a) and converted to the substituted benzoisodeazoline of Formula B by the method described in Example 19 (b) -3-one (BIT). ,

A

1 ---------------- order ------ ^ 1 • 0 (please read the precautions on the back before filling in this page) 25 This paper size is suitable for China Standard (CNS) A4 see grid (210 X 297 mm) A7 B7 23 V. Description of the invention (Analysis data and melting point are shown in the following table 7 & and 7b, where the position of the substituent Rl is the position of BIT. Slope base BIT'S and 2 The preparation of -alkylaryl-BIT'S is described in Examples 21 to 25, and it has a similar protective effect to 2_n-butyl-BIT against the degradation of plastic materials. N! | (1—-11—1-- I —I- ——- III -1 I ..... I-I 1 ·--! I i 1--1 -I- ♦ * (Please read the precautions on the back and fill in this X) Ministry of Economic Affairs Central Bureau of Standards and Staff's Consumer Cooperation. Printed by the company-26- This paper has no scales and is applicable to the Chinese National Standard (CNS) A4 ^ US · (210X29./mm 2 ^ 93 ^ 7 a7 ___B7 V. Description of invention () 24 ^ 7a Economy Basic analysis of bisacetamide printed on paper by the Consumer Cooperative of the Ministry of Standards of the Ministry (./〇) Melting point (. 174-5 240-2 230-2 found value C0 12.8 Ο τ— 13.9 2: CO CO σ > Seven CO uo Industry CO ιη — in 〇65.1 62.0 55. 1 Theoretical value 14.4 ρ τ— τ— 13.2 Z CO ζ〇00 oo in X CN ιη Tf l〇〇64.9 62.0 55.2 〇: Engineering 6CI- 6CI- 6CI- 5CI- Q1 ιο ο "? Ο X ο nf ο * » · &Quot; —- S ζΓ ο ζΓ q, ο 3f q, O 3 27 (please read the precautions on the back before filling in this page)

SN Ligong V. Description of invention (A7 B7 Table 7b Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 25 9 44- 4 §δ LO 〇SS os N Increase ω τ—? CD CO t— CO t— * T— CO CN — it- ο CD CO < do LO o CD o CD work οο CD in; ·: · ο CO s' CO LO 卜 c \ j CD in in to t— i8 increase μ Ctiil w (Ο LO t— 七T ~ qt— CO CO ^ r- CO CO 2: CO CO Csi CO CO ^ r * 〇〇LO 00 in X CO CD inch · S ol〇ο CM UO CO 00 CN CN CO s' 卜 X 〇CD 0 CD 0 CD Ό ID OC fin 5 55 ◦ og '1 nf g5 S Csl? O nf oor? Ί o CO CM in CM The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the back side first Note: fill in this page again) Set, top: Application date 84. 12. 26. Case No. 84113867 The sheds above the category are filled in by the Bureau) Supplementary ^ A4 Amendment page (85 years 10 changes) 299327

Itrt-cr Invention β printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy I. New name Chinese English name Nationality invention i-, creative residence, residence name (name) National loan III, applicant residence, residence (office) Representative Person's name 2-alkenyl or 2-phenethyl-BIT compound, composition containing it and its use " 2-ALKYL OR 2-ARALKYL-BIT COMPOUND, COMPOSITION COMPRISING SAME AND USE THEREOF " Peter William. Austin United Kingdom, United Kingdom, Berkeley, Hessen House, PO Box 42, Jellycom Expert Company, British Mercantile Company, London, United Kingdom, 15 Stanhope Road, London, United Kingdom Susan Jane. Zander Benf Paper ft scale Gu Jinque hometown (CNS ) Eight 4 secrets (21Qx297mm) binding line

Claims (1)

々 、 Applicable patent scope 1_ A kind of 2-alkyl or 2-aralkyl group of formula 1 as a plastic material killing BIT, fungus agent Wherein R C: 3 · 5 ·〗 End group, cycloalkyl group or aralkyl group, this aralkyl group contains at least 2 carbon atoms to connect the aryl group to the nitrogen atom, and wherein the alkyl or aryl group can be freely Replace. 2. The 2-alkyl group or 2-aralkyl group according to the i-th item in the scope of the patent application. BIT 'where R contains 4 carbon atoms. • According to the formula 1-alkyl or 2-aralkyl-BIT according to item 1 of the patent application, where BIT is 2- (n-butyl) -BIT or 2-phenethyl-BIT. • A composition comprising a plasticizer or a stabilizer, and 2-alkyl or 2-aralkyl-BIT of formula 1, --1-„------ 'outfit-- (Please read the notes on the back before filling in this page) Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs where R is c3_5-alkyl, naphthenic Aryl or aralkyl group, this aralkyl group contains at least 2 carbon atoms to connect the aryl group to the nitrogen atom, and the alkyl or aryl group can be substituted at will. ^ The size of this paper is applicable to the Chinese National Standard (CNS) A4 specifications (2 丨 0> < 297mm) 6. 'Scope of patent application The composition according to item 4 of Tian's patent application scope, in which plasticizers or stabilizers, tartaric acid or epoxidized vegetable oil. According to the patent application No. 5 of the patent composition, wherein the ester is dioctyl phthalate dioctyl adipate or a mixture thereof. The composition according to item 5 of the patent application scope, wherein the vegetable oil is soybean 8. The composition according to any one of items 4 to 7 of the application patent application, further comprising a dispersant. 9 · —A combination of plastic materials and formula;! 2 • Alkyl or 2 · substance, aralkyl-BIT combination (please read the precautions on the back before filling this page) Pack-0 N-RS .1T Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs where R is C3_5_alkyl, cycloalkyl or aralkyl. This aralkyl contains at least 2 carbon atoms to connect the aryl group to the nitrogen atom. And the alkyl or aryl group can be substituted at will. 1 〇. The composition according to item 9 of the patent application scope wherein the plastics material is polyurethane or plasticized p VC. 11. A compound of formula 1 0 | N * —R 2- This paper music standard uses the Chinese National Standard (CNS) A4 Washing UlOX 297mm) 6. Scope of patent application where R is -CH (CH3) CH2CH2CH3, -CH (C2H5) CH2CH3, -ch2ch2ch (ch3) ch3, -ch2ch (ch3) ch3, -ch2ch (ch3) c2h5 or cyclopentyl. (Please read the precautions on the back first and then fill out this page) Order Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -3-This paper standard is applicable to the Chinese National Standard (CNS) A4 rule. (210X297 mm)