JPH03197404A - Use of additive in isothiazolone-containing solution - Google Patents

Abstract

PURPOSE: To prevent a timber from excess isothiazolone absorbing by adding a poly quarternary ammonium compound, a thickener, a nonionic surfactant having oxyalkylene units, a simple quarternary compound, etc., to a solution containing the isothiazolone as a preventing agent of extraction. CONSTITUTION: (A) A poly quarternary ammonium compound, (B) a thickener or a disperser, (C) a nonionic surfactant having 3-12 oxyalkylene units (preferably oxyethylene unit) and (D) one or more kinds of a simple quarternary compound of at least an amount equal to that of isothiazolone are used as additives in a solution containing the isothiazolone for preventing the isothiazolone from being excessively extracted from the solution containing the isothiazolone when the isothiazolone solution is used as a composition for treatment for preventing sap-staining by bringing the composition into contact with a timber.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an anti-sample treatment for wood with AA solution.
(petain treatmθnt) Newly felled timber feeds on nutrients for fungi, such as sugars. These, together with the high moisture content contained in the wood, therefore make it extremely susceptible to attack by blue stains and fungi. To prevent wood from discoloration caused by such fungi, the wood is usually treated by spraying the wood with a preservative9, soaking the wood in a preservative, and, for example, using loam and wood.・Rohm and Haa
Germicidal isothiazolones such as those marketed as KathOn 893 by KathOn 893! It is known to impregnate wood with a preservative as component E.

A problem that has been observed when soaking wood in solutions of isothiazolone fungicides is that the wood tends to preferentially extract isothiazolone from the treatment mixture. As a result, the isothiazolone backing in the treatment mixture rapidly degrades. In addition, wood soaked in a newly prepared treatment mixture will be overtreated with isothiazolone, whereas wood immersed in a treatment mixture that has already been used will be overtreated with isothiazolone. Wood or the treatment mixture'il! Jliad wood contains almost all isothiazolone kills from a treatment mixture that has been depleted of isothiazolone in 7 to 1 days! I can't get anything. Obviously, if obtaining the isothiazolone with the treatment mixture p≧wood is substantially the same as obtaining it with the other components of the mixture,
When the mixture is used, the concentration of isothiazolones in the mixture will remain substantially the same.

By using a polymer to thicken the wood treatment liquid and increase the contact layer of the treatment liquid to the wood surface, the amount of the 8-strand wood preservative increased. It is known to cause

However, by incorporating a glaze additive into the sap control mixture, the present invention substantially reduces the isothiazolone yield from the mixture by the wood! * can be practically excluded.
6 However, this is something that is contraindicated in the experience of conventional wood treatments.The present invention therefore provides, in its first aspect, isothiazolone-containing iI! Make sure to put the alkaline back into contact with the wood in the liquid! (al polyquaternary compound, tCl thickener or dispersant, (cl 3~ A non-ionic surfactant having alkylene 12 oxide units, preferably dispersed ethylene units, or one or more of the simple m41ii compounds of a chemical composition at least equal to the amount of isothiazolone in said solution. All you need to do is provide.

As will be apparent to those skilled in the art, anti-infiltration agents (antist
ripping agθnt) (hereinafter referred to as ``additives'') to prevent the additive from affecting the composition of the wood, isothiazolone, or other optional ingredients found in the mixture used in the invention. For example, if it is intended to paint the wood, then the additive should be selected to give a negative impression to the wood. It should be selected so as not to adversely affect paint application performance. Choosing additives with these things in mind is
It is within the purview of those skilled in the art.

Both polyquaternary compounds and simple quaternary compounds are
Preferred is a nitrogen-containing compound. However, other potential functional groups for additive reservoirs useful in the present invention include:
Phosphonium functional groups and other suitable compounds are guanisine and its related compounds.

Preferred polyquaternary compounds for incorporation into hardware are (1) polyamines and polyamine ethers; (2) polyamines and polyamine ethers;
Preferred simple quaternary compounds are polyvinylpyrrolidone, (3) polyquaternary ammoeoxylates, (2) block polymers of ethylene oxide and propylene oxide, and have the formula: (1) Gafquat 755 N: Copolymer of vinylpyrrolidone and dimethylamine ethyl methacrylate, (2) Polyquart H81: polyamine/polyglycol condensation resin, and (31Rhop
1θx IJ 1126: A combination of cationic ethyl acrylate.

Suitable thickeners and dispersants include water-bathable polymers and water-dispersible polymers, including: homoelectropolymers and copolymers of (meth)acrylic acids and their esters; vinyl homopolymers and copolymers, glycol monomer-based polymers, and ether monomer-based polymers.

Suitable nonionic surfactants include: i
l+ alkylphenols, alcohols, amines,
and a polyalhalogen of alkanolamides].

Generally, a suitable ratio of isothiazolone to anti-drawing additive is from 1:20 to 1:0.1, preferably from 1:10 to 1.
m 0.5, preferably from 1:5 to 1:1.

However, for simple quaternary compounds, an isothiazolone:additive ratio of 1:1 or less (i.e. more bulking agent) is essential, and the preferred ratio is The ratio is 1:345 to 1:20. It should be noted that varying these ratios may be necessary depending on the molecular weight of the additive. For example, the minimum ratio of isothiazolone:additive is 1:3.
5 has been found to be necessary in some cases, so this is the preferred endpoint (en4 paint ) of each of the ratio ranges.

The resulting #8 liquid antifouling treatment composition for use is:
In general, the soaking mixture'! F′fc is in the form of a singing fatigue mixture, and contains 0.005 to 0.005 of isothiazolone.
6% by weight, preferably 0.05-1.5% by weight, more preferably 0.075-1% by weight, most preferably 0.1%
Contains ~0.5% by weight. Alternatively, the composition contains a total of 1 to 80% by weight, more usually 10 to 40% by weight, of isothiazolone, and where the treatment is carried out, a treatment containing a content of isothiazolone as described above is applied. Isothiazolones useful in the present invention, which can also be in the form of concentrates that can be diluted into commercial mixtures, include those suitable or preferred as described in the following patent specification by Rohm and Haas Company: Includes any of the isothiazolones described as: British Patent No. 14749
No. 83, No. 1590446, No. 1488891, No. 1575226, U.S. Patent No. 4325201, No. 4322475, British Patent No. 0095907, Japanese Patent No. 5870795, No. 4396413, No. 3761488 No. 40
No. 67878, No. 3755224 of the same prefecture, No. 38015 of the same prefecture
No. 75, No. 4067878, No. 3849430, No. 3870795, No. 6887552, No. 4031055, No. 4105431, No. 412
No. 9448, No. 4062946. Preferably, isothiazolones having low solubility in water are used.

Such isothiazolones have the formula (wherein Y is (C1-018) alkyl or (C3
-c 2) Cycloalkyl (wherein each optionally includes hydroxy, halo, cyano, alkylamino, sialkylamino, arylamino, carboxy, carbalkoxy, alkoxy, alkylthio, arylthio, haloalpoxy, cycloalkylamino, Carbamoxy, tfc may be substituted with one or more of inthiazolonyl); unsubstituted or unsubstituted (0
2-Os) alkenyl or alkynyl; (07-0
0°) Aralkyl [However, optionally, halogen, (0
□-04) alkyl, or (OX-04)alkoxy (1 fc may be substituted with more than 1); or aryl, but optionally no-rodene, nitro, (Ox-04)alkyl , (Ox-Ot)alkyl-
acylamino, carbo(0□-04)alkoxy, or sulfamyl], and R1 and R2 are each independently I(, /% rogene, or (01 -Ct) has 17 alkyl.

Preferred substituents for Y are substituted or unsubstituted C alkyl or cycloalkyl, R2 is preferably %MIa, or , H'ff17c is a minister.

Examples of such preferred yt substituents include methyl, ethyl, propyl, dichlorobutyl, hexyl, octyl, cyclohexyl, pencil, 6.4-dichloropentyl, 4-methoxypencyl, 3.4-dichlorophenyl. , 4-methoxyphenyl, hydroxymethyl, dimethyl, chloropropyl, hydrogen, etc. As is often said, such isothiazolones are
Generally, a wide variety of stabilizers are used to stabilize the deterioration, some of which are described in the above-mentioned patent specifications. Other advantageous stabilizers and isothiazolones are
No. 11, European Patent Application No. 0194146.2 and European Patent Application No. 88610390.5.

Particularly good 11. Ln intiazoloy is 4,5-sifurone, and most preferably 2-n-octyl-6 isothiazolone. 1, 5-chloro-2-methyl-
6-isothiazolone and 2-methyl-6-inteagron can also be used.

The isothiazolones used in the present invention may be in any known form, including those described in the pending European patent application I! Small breasts 1 @ dare mo as described in IIl No. 88307123.5 are included.

In another aspect, the invention provides the following:
unsubstituted"! - - (C2-08) alkenyl or μ alkynyl with mouth substitution; and (
Cy-C1o)aralkyl [optionally optionally substituted with one or more of halogen, (C1-04)alkyl or (CI-04)alkoxy]
and R1 and R are each independently either B1 halogen I or (Ox-04)alkyl), and (ii) (at polyquaternary compound). , (b) a thickener or dispersant, or a violet simple quaternary compound at least equal to the amount of fcJ isothiazolone.

Preferred ratios of (old:(1) are those as described above in connection with the first aspect of the invention, and preferred compounds (al, (t+1 and (cl) and preferred isothiazolones.

The invention is illustrated in connection with the following examples. In these examples, all parts and percentages are expressed by weight unless otherwise indicated.

In the following Examples 1 to B, the active ingredient 2-octyl-6
- Canon 893 (K) containing isothiazolone
athon 895)
- 1000 ppm or 2000 Pp of isothiazoquaternic biocide sold by Haas Φ Company
The active ingredient in a water bath solution, together with the additives to be tested, contains a non-ionic surfactant (30 ppm or 6 Q
Oppm) and anionic surfactant (600pp
m or 1200 ppm).

In Example 4, where surfactants were tested, no emulsification was necessary; each solution was total determined for isothiazolone content.

2.5% W/W k of sawdust
'! The resulting mixture 1c was left at 26° C. for 3 hours. Next, filter it from the bath liquid t,
The total isothiazolone content was measured.

Without any additives present to prevent stripping, isothiazolone losses are typically between 40 and 60
%, but the exact value depends on the wood used, analysis error, error due to experiment name, etc.

Example 1 The following poly quaternary salt was completely removed and used as an additive μJ agent for preventing salt 9.

Luviquat HM 552: Modified copolymer of vinylpyrrolidone and imidazolium methochloride.

Gafquat 755 N: Quaternary co-conjugation of vinylpyrrolidone and dimethylaminoethyl methacrylate.

Polyq, uart H81: polyamine-polyglycol condensation resin.

Busan 77: Poly[oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene 1 2 Table 1 below shows the isothiazolone (T):additive ratio in each case, the isothiazolone to additive ratio in each case. child, and the isothiazolone child [parts/million (ml) present before and after the test.
ion)), the loss (%) was shown.

Table 1 M-B: N-octyl-3-isothiazolone and dimethylpensylammonium chloride (12,5%
) pickling liquid.

1mpigen BAO: Alkylzomethelbenzammonium chloride.

Luviquat Mono OF: Cetyl-cymethyl<,2)-hydroxyethylammonium zohydrocienphosphate.

All the results are shown in Table 2.

Table 2 Example 2 The following simple quaternary compounds were tested as in Example 1.

The effect of increasing the proportion of 6 4 additives is clearly shown in this Table 2.

Example 6 The dispersant was tested as follows:

RH-D: Sodium salt of polyacrylic acid.

RH-1: low molecular weight polyacrylic acid.

The results are shown in Table 6.

Table 6 No activator was required.

8A1: Noni/I/Phenoxypolyethoxyethanol (10 caps: 8.5).

8A2: Octylphenoxypolyethoxyethanol (
10 including children - 8).

8A6: Octylphenoxypolyethoxyethanol (
]]1IIO content: 15-16゜8A4: Octylphenoxypolyethoxyethanol (II!0 content: 60)
.

The results are shown in Table 4.

Table 4 Example 4 The following nonionic surfactants were tested as in Example 1. However, the additional interface for emulsification 5 6 This Table 4 shows that two nonionic surfactants with IO contents outside the range of the present invention
SA1 and 8 had no significant effect on SA1 and SA8.
All indications are that the combination A2 is extremely effective.

Claims (1)

[Scope of Claims] (1) As an agent for resisting the extraction of isothiazolone from the solution when used as a sap contamination prevention treatment composition that is brought into repeated contact with wood in an isothiazolone-containing solution ( a) a polyquaternary compound; (b) a thickener or dispersant; (c) a nonionic surfactant having 3 to 12 alkylene oxide units, preferably ethylene oxide units; (d) in said solution. A method using one or more simple quaternary compounds in an amount at least equal to the amount of isothiazolone. (2) The thickener or dispersant is a homopolymer and/or copolymer of (meth)acrylic acid and/or ester, a vinyl homopolymer and/or copolymer, and/or a glycol monomer and Claim (1) consisting of water-soluble and/or water-dispersible polymers comprising:
the method of. (3) Nonionic surfactants include ethylene oxide and propylene oxide, alkylphenols, alcohols,
Claim (1) consisting of amines, polyalkoxylates of alkanolamides, or block polymers.
Or method (2). (4) The method according to any one of claims (1) to (3), wherein the polyquaternary compound comprises a nitrogen-containing compound or a phosphonium compound. (5) The method of any one of claims (1) to (3), wherein the simple quaternary compound consists of a nitrogen-containing compound or a phosphonium compound. (6) The polyquaternary compound consists of one based on polyamines or polyamine ethers, polyvinylpyrrolidone, polyquaternary ammonium polymers, or cationic copolymers based on acrylates (
The method according to any one of 1) to (3). (7) Claim (1) in which the simple quaternary compound consists of an ammonium halide having the formula:
The method according to any one of (3) to (3). (8) The ratio of isothiazolone to anti-spilling agent is 1:20 to 1:0.1, preferably 1:10 to 1:0.5, more preferably 1:5 to
1:1, and when the anti-spilling agent is a simple quaternary compound, the amount present is at least equal to the amount of isothiazolone. Section method. (9) Isothiazolone has the following formula: ▲ Numerical formula, chemical formula, table, etc. Halo, cyano, alkylamino, dialkylamino, arylamino, carboxy, carbalkoxy, alkoxy, alkylthio,
unsubstituted or halo-substituted (C_2-C_8) alkenyl or alkynyl; (C_7-C_1_0) aralkyl However, halogen, (C_1-C_4) alkyl, or (
C_1-C_4) alkoxy]; or aryl [optionally substituted with halogen, nitro, (C_1-C_4) alkyl, (C_1-C_4) alkyl-acylamino, carbo (C_1-C_4) may be substituted with one or more of alkoxy or sulfamyl],
The method of any one of claims (1) to (8), wherein R^1 and R^2 are each independently H, halogen, or (C_1-C_4)alkyl}. . (10) Isothiazolone is 4,5-dichloro-2-n
-octyl-3-isothiazolone, 4,5-dichloro-
2-cyclohexyl-3-isothiazolone, and 2-
10. The method of claim 9, comprising one or more n-octyl-3-isothiazolones. (11) (i) Formula ▲ Numerical formulas, chemical formulas, tables, etc. unsubstituted or halo-substituted (C_2-C_8) alkenyl or alkynyl; and (C_7-C_1_0)aralkyl [but optionally halogen, (C_1-C_4)alkyl or (
optionally substituted with one or more of C_1-C_4) alkoxy], and R^1 and R^2 are each independently H, halogen or (
C_1-C_4) alkyl} and (ii) an amount at least equal to the amount of (a) a polyquaternary compound, (b) a thickening agent or dispersant, or (c) an isothiazolone. A composition containing one or more simple quaternary compounds. (12) The thickener or dispersant is a homopolymer and/or copolymer of (meth)acrylic acid and/or ester, a vinyl homopolymer and/or copolymer, and/or a glycol monomer and Claim (1) consisting of water-soluble and/or water-dispersible polymers consisting of:
1) Composition. (13) Claim (11) wherein the polyquaternary compound consists of one based on polyamines or polyamine ethers, polyvinylpyrrolidone, polyquaternary ammonium polymers, or cationic copolymers based on acrylates. Or the composition according to any one of (12). (14) A simple quaternary compound has the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Ph is O_2H_5 or O_6H_4R, and R is H or (C_1-C_3) alkyl, and R^2 is (C_1-C_3) alkyl, R
^1 is (C_6-C_1_8) alkyl and X is halogen.
) to (13). (15) Claim (11) or (1) wherein the polyquaternary compound consists of a nitrogen-containing compound or a phosphonium compound.
2) Composition. (16) Claim (11) or (16) wherein the simple quaternary compound consists of a nitrogen-containing compound or a phosphonium compound.
12) Composition. (17) The ratio of isothiazolone:sampling prevention agent is 1:
20-1:0.1, preferably 1:10-1:0.5,
More preferably, the ratio is 1:5 to 1:1, and when the anti-spilling agent is a simple quaternary compound, the amount present is at least equal to the amount of isothiazolone. The composition according to any one of (16). (18) Isothiazolone is 4,5-dichloro-2-n
-octyl-3-isothiazolone, 4,5-dichloro-
2-cyclohexyl-3-isothiazolone, and 2-
Any one of claims (11) to (17) consisting of one or more n-octyl-3-isothiazolones.
composition of the term.