JPS62226902A - Mildewproofing composition - Google Patents

Abstract

PURPOSE:A mildewproofing composition which has improved mildewproofing performance and can provide a cured molded article and a coating film capable of preserving the performance for a long period, obtained by blending a composition comprising a hydroxyl group-containing liquid diene polymer, etc. with a metallic salt of naphthenic acid. CONSTITUTION:A hydroxyl group-containing liquid diene polymer such as terminal hydroxyl group-containing liquid polybutadiene, etc., is blended with a polyisocyanate compound such as diphenylmethane diisocyanate, etc., an aniline polyol compound such as N,N'-di(hydroxyalkyl)aniline, etc., shown by the formula (R is alkyl) and a metallic salt of naphthenic acid such as zinc naphthenate, etc., and uniformly mixed. The composition may be blended with a polyol compound and a polyamine compound as reinforcing agents. The composition is preferably used as an electrical insulating material for electrical and electronic devices, a sealing material for printed circuit board or a coating material for steel pipes and resins, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel antifungal composition. More specifically, the present invention can provide cured molded products and cured coatings that have excellent anti-mildew properties and can maintain this performance for a long period of time, such as insulating materials for electrical and electronic equipment and printed materials. The present invention relates to an anti-mildew composition suitable for use as a sealing material for wiring boards, or as a coating material for steel pipes, resin pipes, etc.

[Conventional technology]

Most materials such as paper, wood, rubber, plastics, and metals are susceptible to mold attack under certain environmental conditions, and for this reason, phenols and their chlorides, metal salts of organic acids such as naphthenic acids, and quaternary ammonium Anti-mildew measures are taken by incorporating an anti-mildew agent such as salt into the material, or by coating the material with a composition containing an anti-mildew agent.

However, depending on the purpose of use of the material, the above-mentioned anti-mold measures may not be sufficiently effective. In underground steel pipes, etc., L/Rubbles due to the growth of mold are occurring frequently, and measures to prevent 1L are an urgent issue.

In response to such problems, a mildew-resistant +A material has recently been proposed that can provide a cured molded body and a cured film with good mildew-proofing performance (Japanese Patent Application Laid-Open No. 16809/1983). This anti-mold material contains a liquid diene polymer containing active hydrogen groups, an organic isocyanate compound and an aniline polyol compound as essential components, and has anti-mold performance even if no anti-mold agent is added. It is possible to provide a cured molded body or a cured film having the following properties.

However, in this anti-mildew material, although the obtained cured molded product and cured coating have relatively excellent anti-mildew properties, the maintenance of anti-mildew properties over a long period of time is not necessarily satisfactory.

[Problem that the invention seeks to solve]

Under these circumstances, the present invention provides a mold-resistant composition that can provide a cured molded product or a cured coating that has excellent mold-proof performance and can maintain this performance for a long period of time. The purpose is to provide goods.

[Means for solving problems]

As a result of extensive research to achieve the above object, the present inventors discovered that a composition comprising a specific composition containing naphthenic acid metal salts was suitable for the purpose, and based on this knowledge, the present invention was developed. The invention was completed.

That is, the present invention provides an anti-mildew composition comprising (A) a hydroxyl group-containing liquid diene polymer, (B) a polyisocyanate compound, (C) an aniline polyol compound, and (D> naphthenic acid metal salt). This is what we provide.

In the composition of the present invention, the hydroxyl group-containing liquid diene polymer used as component (A) has a number average molecular weight of 300 to 250 and has a hydroxyl group in the molecule or at the end of the molecule.
00, preferably 500 to 10,000. There is no particular restriction on the content of the hydroxyl group, but it is usually 0.1 to 10 meq/g.
, preferably in the range of 0°3 to 7 meq/g.

Examples of the liquid diene polymer include diene polymers and diene copolymers containing hydroxyl groups and having 4 to 12 carbon atoms, and furthermore, diene monomers and α-olefinic addition-polymerizable monomers having 2 to 22 carbon atoms. Examples of such copolymers include hydroxyl group-containing butadiene homopolymer, isoprene homopolymer, pucdiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2- Examples include ethylhexyl acrylate copolymer and butadiene-n-octadecyl acrylate copolymer.

These hydroxyl group-containing liquid diene polymers may be used alone or in combination of two or more. In addition, the hydroxyl group-containing liquid diene polymer can be easily produced by, for example, heating a desired mutually beneficial diene monomer or this with other copolymerizable monomers in the presence of hydrogen peroxide in a liquid reaction medium. can do.

In the composition of the present invention, the polyisocyanate compound used as component (B) is an organic compound having two or more isocyanate groups in one molecule, and is It has a reactive isocyanate group. Examples of this polyisocyanate compound include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate-1-(M
DI), liquid modified diphenylmethane diisocyanate,
Polymethylene polyphenylisocyanate, xylylene diisocyanate, cyclohexyl diisocyanate,
Examples include cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isoprobylhenzene-2゜4-diisocyanate-1, and addition reaction products of polypropylene glycol and tolylene diisocyanate, especially MDI, liquid modified diphenylmethane diisocyanate, and tolylene diisocyanate. etc. are preferable.

There is no particular restriction on the blending ratio of component (A) and component (B) in the composition of the present invention, but usually,
B) Component polyisocyanate I/compound has an isocyanate group ratio (NCO/QH) of 0.2 to 25 in molar ratio,
It is desirable to mix both components so that the ratio is preferably 0.5 to 15.

If this molar ratio deviates from the above range, it is not preferable because the composition becomes difficult to cure.

In the composition of the present invention, the aniline polyol compound used as component (C) is N,N'-di(hydroxyalkyl)aniline represented by the general formula (R in the formula is an alkyl group). Preferably. Among these N,N'-di(hydroxyalkyl)anilines, N,N'-di(2-hydroxyethyl)aniline represented by the following formula (1), N, N'-di(2-hydroxyethyl)aniline represented by the formula (n), N'-di(2-hydroxypropyl)aniline is preferred. These aniline polyol compounds may be used alone or in combination of two or more.

H (1) (II) The N,N'-di(2-hydroxyethyl)aniline can be prepared by reacting aniline with ethylene oxide, and the N,N'-di(2-hydroxypropyl)aniline can be prepared by reacting aniline with ethylene oxide. It can be easily produced by reacting aniline and propylene oxide.

There is no particular restriction on the content of the aniline polyol compound as component (C) in the composition of the present invention, but usually (
The amount is selected in the range of 5 to 30 parts by weight, preferably 7 to 25 parts by weight, per 100 parts by weight of the hydroxyl group-containing liquid diene polymer of component A). If this amount is less than 5 parts by weight, the strength of the cured product will not be sufficient, and if it exceeds 30 parts by weight, the cured product will become too hard, which is not preferable.

In the composition of the present invention, examples of naphthenic acid metal salts used as component (D) include cobalt salts, manganese salts, zinc salts, aluminum salts, lead salts, copper salts, sodium salts, and potassium salts of naphthenic acid. Among these, zinc naphthenate and copper naphthenate are preferred from the viewpoint of anti-mildew performance.

These naphthenic acid metal salts may be used alone or in combination of two or more, and there are no particular restrictions on their content, but they are usually used in the hydroxyl group-containing liquid diene system of component (A). 1 per 100 parts by weight of polymer
-30 parts by weight, preferably 3 to 20 parts by weight. If this amount is less than 1 part by weight, the long-term antifungal performance of the cured product will be poor, and if it exceeds 30 parts by weight, the long-term antifungal performance will be poor compared to the amount, and the physical properties of the cured product will be poor. I don't like it because it makes it worse.

A polyol compound or a polyamine compound can be added to the composition of the present invention as a reinforcing agent if desired,
It is also possible to add various other additives.

As the polyol compound, any of -class polyols, secondary polyols, and tertiary polyols may be used, and specifically, 2-propylene glycol, dipropylene glycol, 1.2-butanediol, 3-butanediol, 2.3-butanediol, ■, 2-bentanediol, 2゜3-bentanediol, 2.5-hexanediol, 2.4-hexanediol, cyclohexanediol, glycerin, N, N'- Mention may be made of low molecular weight polyols containing a hydroxyl group bonded to at least one secondary carbon, such as bishydroxyisopropyl-2-methylpiperazine, propylene oxide adduct of bisphenol A.

Furthermore, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-bentanediol, 1,6-hexanediol, etc. that do not contain a hydroxyl group bonded to a secondary carbon can also be used as the polyol. . Diols are usually used as polyols, but triols and tetraols may also be used, and those having a molecular weight in the range of 50 to 500 are preferred.

Further, the polyamine compound may be any of diamine, triamine, and tetraamine, and furthermore, any of -class polyamine, secondary polyamine, and tertiary polyamine can be used. Examples of polyamine compounds include aliphatic amines such as hexamethylene diamine, 3,3'-
Alicyclic amines such as dimethyl-4゜4'-diaminodicyclohexylmethane, aromatic amines such as 4,4'-diaminodiphenyl, triamines such as 2,4.6-)li(dimethylaminomethyl)phenol, etc. can be mentioned.

When blending these polyol compounds or polyamine compounds, there is no particular restriction on the blending ratio, but usually 1 to 1 to 100 parts by weight of the polyol compound or polyamine compound is added to 100 parts by weight of the hydroxyl group-containing liquid diene polymer as component (A). It is blended in an amount of 100 parts by weight, preferably 3 to 200 parts by weight.

Other additives that may be added as desired include fillers such as mica, graphite, vermiculite, calcium carbonate, and slate powder.

Furthermore, plasticizers such as dioctyl phthalate are added as viscosity modifiers, softeners such as aromatic, naphthenic, and paraffin oils are added, and alkylphenol resins, terpene resins, and terpene resins are added to adjust adhesive strength and adhesive strength. Tackifying resins such as phenolic resins, xylene formaldehyde resins, rosins, hydrogenated rosins, coumaron resins, aliphatic and aromatic petroleum resins can also be added. Also, curing accelerators such as dibutyltin dilaurate, stannous octoate, polyethylene diamine, etc. can be added. Furthermore, an anti-aging agent can be added to improve weather resistance, and a silicon compound or the like can be added as an antifoaming agent.

The composition of the present invention can be obtained by blending the above-mentioned components and mixing them uniformly. Usually, first, the components excluding the polyisocyanate compound are blended,
Stir and mix at a temperature of 15-120°C, preferably 70-100°C for 5-240 minutes, preferably 30-180 minutes, then add the polyisocyanate compound to this mixture and heat at 0-70°C, and 15-240 minutes. 0.5 seconds to 180 minutes, preferably 1 second to 120 minutes at a temperature of 50°C
A liquid composition of the present invention can be obtained by stirring for a minute to mix uniformly.

The antifungal composition of the present invention can be cured and molded into a desired shape and used as a molded product for various purposes, and can also be used as a coating material that is applied to the surface of a material to be treated and cured to form a film. It can also be used as There are no particular restrictions on the conditions for curing, but the curing temperature is usually selected in the range of 0 to 120°C, preferably 15 to 70°C, and the curing time is 0.5 to 75 hours, preferably 1 to 7 hours.
Selected within 2 hours.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

In addition, the antifungal performance of the composition was evaluated according to the method shown below.

That is, a test piece specified in JIS Z291-76 and ASTM G 21-75 was prepared using the antifungal composition, and mold spores were inoculated into the test piece and cultured for 5 months according to the following test method. The resistance to mold was evaluated.

(1) Test method [1] A test piece is inoculated with mold spores, and cultured in a petri dish with a diameter of 90 m.

Test strain Aspergillus niger (Kanto Usama■Hocho1 etc.) ATC
C6275, IAM3001 Penicillium citrinum
rlcitrinum) AT CC9849, IA
M7316 Rhizopus nigricans (1 set of 1 side, once sealed) ATCC 10404, IAM 6070 Thallatosborium herbalum (Clados riu
IAM F517 Chaetomium globosum ATCC6205, IAM8059 Evaluation: Visually observe the growth state of mycelium on the surface of the test piece,
Evaluate according to the following display.

72
No growth is observed at all.

1. Growth is observed.

(Area 1/20 to l/I 0) (2) Test method (II) Prepare an agar medium in a Petri dish with a diameter of 150 mm, paste a test piece on it, and then inoculate both the medium and the test piece with mold spores. and culture.

Test strain Aspergillus niger (b and pressure) ATCC9
642, IAM3002 Penicjllium
funiculosum) AT CC9644, r
, a, M731 Chaetomium globozum (I Red Ridge) AT CC6205, IAM8059 Trichoderma sp.
645, IAM5061 Aureobasidium pullulans (obsidium U11) ATCC9348, I
AM5060 evaluation: Observe with the naked eye the growth state of mycelium that has formed on the surface of the test piece,
Evaluate according to the following display.

, Front - Two threads, growth pattern 9 2. No growth at all.

l Slight growth (area 10% or less) Example 1~
3. Comparative Examples 1 to 3 Using each component of the types shown in the attached table, first, the components excluding the polyisocyanate compound were mixed in the proportions shown in the line table,
After stirring at 80°C for 30 minutes, a polyisocyanate compound was added to the mixture in the proportion shown in the table, and the mixture was heated at 25°C.
The mixture was stirred for 30 minutes to prepare a uniform antifungal composition.

The antifungal performance of this antifungal composition was evaluated, and the results are shown in a chart.

As is clear from this table, the antifungal composition of the present invention is
It can be seen that it maintains its excellent anti-mildew performance over a long period of time.

〔Effect of the invention〕

The anti-mildew composition of the present invention has an excellent feature of having excellent anti-mildew performance and being able to provide a cured molded article or a cured coating that can maintain this performance for a long period of time. For example, it is suitably used as an insulating material for electric/electronic equipment, a sealing material for printed wiring boards, or as a coating material for steel pipes, resin pipes, etc.

Claims (1)

[Claims] 1. An anti-mildew composition comprising (A) a hydroxyl group-containing liquid diene polymer, (B) a polyisocyanate compound, (C) an aniline polyol compound, and (D) a naphthenic acid metal salt. thing. 2. The ratio of component (A) to component (B) is the molar ratio of isocyanate group of component (B)/hydroxyl group of component (A) of 0.
2 to 25, and the contents of component (C) and component (D) are 5 to 30 parts by weight and 1 to 30 parts by weight, respectively, per 100 parts by weight of component (A). The antifungal composition according to item 1.