JPH0959116A - Anti-microorganismic waterproof agent and waterproofing using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject agent capable of inexpensively and readily imparting both anti-microorganismic property and waterproof property to a material to be treated with excellent continuity by combinedly using a specific alkoxysilane with a specific quaternary ammonium salt. SOLUTION: This waterproof agent combinedly contains an alkoxysilane of formula I (R<1> is a 1-4C alkyl; (n) is 1 or 2) or its partially hydrolyzed condensation product and a quaternary ammonium salt of formula II (R<2> and R<4> are each an alkyl; R<3> is an alkyl; X<m-> is a halogen ion, a sulfuric acid ion or a sulfurous acid ion; (m) is 1 or 2; R<5> is an alkylene, etc.; R<6> is an alkyl) or its partially hydrolyzed condensate. Preferably, a partially hydrolyzed condensation product of a trialkoxysilane expressed by formula I wherein (n) is 1 and R<1> is a 1-3C alkyl and a quaternary ammonium salt expressed by formula II wherein X<m-> is a halogen ion are used. The waterproof agent is penetrated into a material to be treated for 1min-24hrs, and in the process, concentration of the compound of the formula II in the last 1/10-1/2hr of the whole penetrating time is made higher than that before this time.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to wood, pulp,
By impregnating or coating a cellulosic material such as paper or fiber (hereinafter referred to as “material to be treated”), both antimicrobial property and waterproof property are imparted without impairing the texture of these materials. The present invention relates to an antimicrobial waterproofing agent that can be used, and an antimicrobial waterproofing method using the same.
The antimicrobial waterproofing agent of the present invention is suitable for wood and paper, especially wood applications. The term "antimicrobial property" as used herein refers to performance such as antibacterial property and antifungal property.

[0002]

2. Description of the Related Art Cellulosic materials such as natural fibers such as wood, pulp, paper, and cotton are naturally easy to absorb water,
Further, since microorganisms easily propagate, problems such as decay, discoloration, and unsanitary conditions are likely to occur. Therefore, antimicrobial treatment and waterproof treatment have been tried by various methods for a long time.

For example, a series of quaternary alkylammonium compounds represented by DDAC (didecyldimethylammonium chloride) have high antibacterial and antifungal effects,
Moreover, since it has low toxicity to the human body, it has recently attracted attention as an antimicrobial agent for wood, fiber, paper and the like. However, since these series of alkylammoniums are all water-soluble, they have a drawback that when the material to be treated is used under conditions of moisture and humidity, it is easily leached and loses its effect. It was

To solve this problem, JP-A-4-178302 relates to an antibacterial and fungicide for wood which uses a residue of an acid having a polymerizable vinyl group as an anion for an alkylammonium cation. After impregnating the solution with wood, a method of preventing leaching of alkylammonium by polymerizing acid residues is disclosed. However, this method inherently has a problem common to wood treating agents to which a polymerizable vinyl group is applied.

That is, when the concentration of the polymerizable agent is low, the polymerization does not proceed sufficiently, the leaching is not improved, and the problem of toxicity of the residual monomer occurs. In addition, when the concentration of the polymerizable agent is high, an infinite number of gaps are formed between the material to be treated and the material due to curing shrinkage during polymerization, which rather causes a state in which water and fungi are easily retained.

On the other hand, Japanese Unexamined Patent Publication No. 3-200793 discloses that a compound in which a hydrolyzable alkoxysilyl group is bonded to one of the alkyl groups of alkylammonium and an alkylalkoxysilane are mixed and used to form a rock, Disclosed is a method for imparting both waterproofness and antimicrobial properties to an inorganic material such as concrete. However, this method has unique problems when using alkylalkoxysilanes.

That is, since the alkylalkoxysilane has a very slow hydrolysis rate, it is necessary to use a hydrolysis catalyst such as an acid, an alkali or a metal compound, and the treatment method is complicated and expensive, and these catalysts are used. There was a possibility that the material to be treated had adverse effects such as discoloration and strength reduction. When alkylalkoxysilane is used,
There was a drawback that the treated material turned into a color that absorbed oil. Further, as disclosed in JP-A-3-200793, which is directed to inorganic materials, alkylalkoxysilane has a drawback that it is difficult to react with materials to be treated such as cellulosic materials such as wood, pulp, paper or fibers. It was

[0008]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention is an antimicrobial waterproofing material that exhibits both high antimicrobial property and waterproofing property in a material to be treated and which can be continued for a long period of time. It is an object of the present invention to provide an antimicrobial waterproofing agent which can impart the effect by an inexpensive and simple method.

[0009]

Means for Solving the Problems As a result of diligent studies on the above problems, the present inventor has found that an alkoxysilane represented by the following formula (1) or a partial hydrolysis and condensation reaction product thereof and the following formula (2) When an antimicrobial waterproofing agent comprising a quaternary ammonium salt represented by or a partial hydrolysis-condensation product thereof is used as a material to be treated, it exhibits both high antimicrobial resistance and waterproofness, and Has been found to continue for a long time.

[0010]

(Equation 3)

[0011]

(Equation 4)

[0012]

Specific examples of R ^{1 in} the above formula (1) are methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl or t-butyl groups. R ¹ is 1
Although there are two or three in the molecule, these may be the same or different types, but the same type is preferable because of easy production. Although it is possible to mix using a plurality of types of alkoxysilanes having different R ^1, when recovering the alcohol by-produced in the reaction and curing with the hydrolytic condensation reaction or during the treatment material, R ¹ is the same Is preferred. R
^{As 1} has a smaller number of carbon atoms, the hydrolysis reaction is more likely to occur, so that the hydrolysis / condensation reaction proceeds faster when reacted with the material to be treated, and in the case of bulky material such as t-butyl, the hydrolysis reaction occurs. It is difficult and takes a long time to react with the material to be treated, but on the other hand, there is a tendency that the stability in the case of forming an aqueous emulsion described later increases.

Considering the reactivity with the material to be treated, R ¹
Is preferably an alkyl group having 1 to 3 carbon atoms, and an ethyl group is particularly preferable in that the reaction by-product is harmless ethanol. When n = 2, the monomer before the partial hydrolysis-condensation reaction is chemically unstable and industrially difficult to handle. Therefore, n = 1 alkoxysilane, that is, trialkoxy. Silane is preferred.

The alkoxysilane used in the present invention can be easily obtained as a partial hydrolysis-condensation reaction product by mixing and stirring in water under appropriate conditions already known. However, since the odor is small, it is easy to handle, and the curing in the material to be treated is fast, it can be used more preferably than the alkoxysilane monomer itself. As the partial hydrolysis-condensation reaction product, a single alkoxysilane may be used, or two or more kinds may be used. The polymer chain of the partially hydrolyzed condensation reaction product may be branched or linear, and either of them can be used in the present invention.

The average degree of polymerization of the partially hydrolyzed condensation reaction product is
Dimers to 100-mers are preferable. The higher the degree of polymerization, the smaller the combustibility of the reaction product, the smaller the odor, and the faster the curing in the material to be treated. However, if it is too large, the viscosity becomes high, etc. It tends to be bad. Therefore, a dimer to a 10-mer is more preferable, and a dimer to a pentamer is still more preferable.

Next, the quaternary ammonium salt represented by the above formula (2) will be described. Where R ² and R ⁴
Each represents a C ₁ -C ₆ alkyl group. These may be the same as or different from each other, but the same type is preferable from the viewpoint of easy production. When the carbon number is too large, the compound itself becomes unstable due to steric hindrance. Therefore, the preferable carbon number is C _{1 to} C ₃ , and the economically most preferable one is the C ₁ methyl group.

R ³ represents a C ₃ -C ₂₀ alkyl group. For protection of the central N ⁺ ion of the quaternary ammonium group,
It is preferable that the alkyl chain is long to some extent, and conversely, if it is too long, the alkyl chain itself becomes unstable. Therefore, the preferable carbon number is C _{10 to} C ₁₈ .

R ⁵ is a C ₁ -C ₉ alkylene group or a group containing the alkylene group and a phenylene group, specifically, [Si side]-(CH ₂ ) _p- PH- (CH ₂ ) _q- [ N
Side] (wherein PH represents a phenylene group, p = 1 to 4.
q = 1 to 7. p + q = 2-8. ).

R ⁶ is an alkyl group having 1 to 4 carbon atoms and 1
A plurality of R ⁶ in the molecule may be the same or different. R
^{As 6} has a smaller number of carbon atoms, the hydrolysis reaction is more likely to occur, so that the hydrolysis / condensation reaction proceeds faster when it is reacted with the material to be treated. When it is bulky like t-butyl, the hydrolysis reaction is difficult to occur and it takes time to react with the material to be treated, but on the other hand, there is a tendency that the stability of the aqueous emulsion is increased.

Considering the reactivity with the material to be treated, R ⁶
Is preferably an alkyl group having 1 to 3 carbon atoms. When the alcohol by-produced during the hydrolysis-condensation reaction or when reacting / curing with the material to be treated is recovered, if the R ^{1 in} the compound of the above formula (1) is matched, the recovered alcohol will be the same. preferable.

Specific examples of X ^m- are halogen ion, sulfate ion, sulfite ion, nitrate ion, nitrite ion,
Examples thereof include carbonate ion, hydrogen carbonate ion, and acetate ion. Among them, halogen ion is preferable, and chlorine ion is more preferable, from the viewpoint of easy production and high stability of the obtained compound.

Specific examples of the quaternary ammonium salt represented by the above formula (2) include triethoxysilylpropyldimethyloctadecylammonium chloride, trimethoxysilylpropyldimethyloctadecylammonium chloride and {4- (3-trimethoxysilyl). Propyl) benzyl} dimethyl dodecyl ammonium chloride, triethoxysilylpropyl dimethyl undecyl ammonium bromide, etc., and triethoxysilylpropyl dimethyl octadecyl ammonium octadecyl and triethoxysilylpropyl dimethyl octadecyl chloride due to their high stability and easy availability. Ammonium chloride is preferred. Similarly to the compound of the formula (1), the compound of the formula (2) can easily obtain a partial hydrolysis-condensation reaction product by a known method, but compared with the compound of the formula (1), Since the amount used is extremely small, there is almost no difference in use between the reaction product and the compound of the formula (2) itself.

In the antimicrobial waterproofing agent of the present invention, the compound of formula (1) develops waterproofness by penetrating into the material to be treated and cured, and at the same time strengthens the compound of formula (2). Play a role in fixing. As a result, a high antimicrobial property, which cannot be obtained when the compound of the formula (2) is used alone, and long-term maintenance of its effect are exhibited.
Further, the presence of the compound of the formula (2) improves the waterproofing effect as compared with the compound of the formula (1) alone, and both of them have an unexpected synergistic effect.

The amount of the compound of the formula (2) to be used is preferably 0.1 to 100 parts by weight based on 100 parts by weight of the compound of the formula (1) in terms of effects. Considering that the compound of the formula (2) is more expensive than the compound of the formula (1), the amount of the compound of the formula (2) used is more preferably 0.1 to 30 parts by weight, Particularly preferably 0.1 to 1
0 parts by weight.

The compound of the formula (1) and the compound of the formula (2) may be mixed in advance or used separately. First, the compound of the formula (1) is treated. Or the concentration of the compound of formula (2) in the mixed solution to be treated is gradually increased. A method of performing a hardening treatment after permeating while increasing the temperature (hereinafter referred to as "B
Method ”. ) Is preferred. As a result, the compound of the formula (1) waterproofs the surface to a deep layer, and the compound of the formula (2) has a high concentration near the surface although a small absolute amount, and exhibits high antimicrobial properties near the surface. It is possible to make it.

The time of permeation varies depending on the type, shape and size of the material to be treated and the concentration of the waterproofing agent, but a total of 1 minute to 24 hours is preferable. There is a limit to the amount of penetration even if it takes a long time, and it is not economical. It is preferably 5 minutes to 2 hours. Specifically, in method A, the time of 1/10 to 1/2 before the end of the total infiltration time is
It is applied to permeation by the quaternary ammonium salt represented by the formula (2) or its partial hydrolysis-condensation reaction product, or in Method B, 1/10 to 1 before the end of the total permeation time.
The time of / 2 is more preferably such that the concentration of the quaternary ammonium salt represented by the formula (2) in the mixed solution is higher than the concentration in the preceding time.

Examples of the method of permeating the material to be treated include permeation by impregnation and coating. As a method of impregnation, the material to be treated may be simply immersed in the material to be treated at room temperature and normal pressure, but may be impregnated with a chemical vapor in a gas phase in addition to the vacuum impregnation, the pressure impregnation, the known chemical liquid injection method for wood, and the like. . When it is permeated by coating, it may be applied to the surface of the material to be treated by a known method such as spraying, coater or brush coating, and then allowed to stand for a while.

After coating or penetrating or impregnating, the material to be treated is simply air-dried at room temperature to cause the antimicrobial waterproofing agent of the present invention to harden and exhibit high antimicrobial and waterproofing properties. You can speed it up. The preferable heating temperature in this case varies depending on the material to be treated, but the compound of the formula (2) is easily decomposed at 125 ° C. or higher, and therefore cannot be increased so much, preferably from room temperature to 120 ° C.
C., more preferably 50 to 110.degree.

In the prior art (Japanese Patent Laid-Open No. 3-200793), 0.1 to 10% by weight of tin dibutyl dilaurate or tetrabutyl titanate is used as a catalyst in order to cure the alkylalkoxysilane. Is disclosed.
When using an alkylalkoxysilane that has strong hydrophobicity and slow hydrolysis and condensation, it is common knowledge to add a hydrolysis catalyst to accelerate curing, but as described above, it causes discoloration or deterioration of the material to be treated. There is a problem that is easily caused. On the other hand, when the alkoxysilane of the formula (1) of the present invention or its partial hydrolysis-condensation reaction product is used, it is characterized in that it is not necessary to use a catalyst because hydrolysis easily occurs.

However, if it is desired to accelerate the curing particularly, the following catalysts can be used. Examples of the catalyst include inorganic acids such as hydrochloric acid and phosphoric acid, organic acids such as formic acid, acetic acid and p-toluenesulfonic acid, and organic metal compounds such as dibutyltin dilaurate, lead naphthenate, zirconocene chloride and titanocene chloride, Aminosilanes, amines, amine salts and the like can be mentioned, and these may be used alone or in combination of two or more. The concentration of the catalyst when used is 0.001 to 0.0 with respect to the compound of the formula (1).
It is preferable to make the concentration as low as about 1% by weight, and at such a low concentration, there is almost no possibility of causing discoloration or deterioration. Originally, the alkoxysilane of the above formula (1) or its partial hydrolysis-condensation reaction product does not have an alkyl group that discolors the material to be treated, so that the color of the material to be treated after treatment is treated. There is almost no fear of changing from before.

The antimicrobial waterproofing agent of the present invention may be used as it is, or may be diluted with a solvent. Preferred dilution concentration (antimicrobial waterproofing agent / (antimicrobial waterproofing agent + solvent)
The (%) is generally 1 to 100% by weight, preferably 10 to 100% by weight, although it varies depending on the type of solvent and the impregnation method. The antimicrobial waterproofing agent of the present invention comprises a compound represented by the above formula (1) and a fourth compound represented by the above formula (2).
When the primary ammonium salt is used separately, the preferable concentration of each component is generally 1 to 1 like the above mixed solution.
It is 00% by weight, preferably 10 to 100% by weight.

Examples of the solvent that can be used include alcohols such as methanol, ethanol and isopropanol, and general organic solvents such as ether, methyl ethyl ketone, toluene, benzene and hexane, and one or more of them can be mixed. Can be used. Although the type of preferred solvent varies depending on the material to be treated, alcohol is produced as a by-product when the antimicrobial waterproofing agent reacts and cures with the material to be treated, so this by-product alcohol should be industrially recovered and reused. When considering such a process, the use of the same alcohol as the by-product alcohol as a solvent has an advantage that recovery and reuse are facilitated.

The antimicrobial waterproofing agent of the present invention or the compound of the above formula (1) or (2) can form a stable emulsion with an aqueous solvent by using an appropriate emulsifier, pH adjuster and the like. Therefore, it is possible to use an aqueous treatment agent, but the solvent solution is preferable from the viewpoint of good storage stability.

The antimicrobial waterproofing agent of the present invention includes a solvent,
If necessary, dyes, pigments, resins, fillers and the like can be added.

The preferred amount of the antimicrobial waterproofing agent of the present invention to be used in the material to be treated is largely different depending on the material to be treated, and therefore cannot be generally stated, but it is not limited to wood, pulp, fiber or paper. When used by impregnating into a permeable material, it is apparent when 0.1% or more by weight of the alkoxysilane of the above formula (1) or a partial hydrolysis and condensation reaction product thereof is used with respect to the weight of the material to be treated. Can be used up to 100% or more,
Considering the magnitude of the effect and the economical aspect, 0.1% to 50% is preferable.

Further, in addition to the above-mentioned permeable treated material such as wood, pulp, fiber or paper, a non-permeable material such as metal, plastic, glass, etc. can be treated with the antimicrobial waterproofing agent of the present invention. By coating the surface, a transparent and hard antimicrobial waterproof film can be formed, and it can be used, for example, as an antibacterial and antifungal antireflection and anti-scratch treatment for optical lenses and contact lenses.

When used for a material having no permeability, the amount used is determined by the film thickness formed on the surface. That is, when the formed film thickness is 0.01 μm or more, a clear effect is exhibited, and when the film thickness is increased, the antibacterial property and the durability are increased. However, considering the economical aspect, the preferable film thickness is 0.01 μm to It is 0.1 mm.

[0038]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples. Example 1 50 g of water was added to 1000 g of triethoxysilane, and the mixture was stirred to obtain a partial hydrolysis-condensation product of triethoxysilane having an average degree of polymerization of 2.3. The formation of the partially hydrolyzed condensation reaction product was confirmed by gas chromatography analysis. To this, add 5 g of triethoxysilylpropyl dimethyl octadecyl ammonium chloride and add 50%.
Acetone solution was used as the treating agent of Example 1.

Length 30 mm × width 30 mm × length 5 mm
6 pieces of the two test pieces of Example 1 were immersed in the above treatment agent for 10 minutes at room temperature and atmospheric pressure, and then dried at room temperature for 24 hours. It was The weight increase rate after the treatment with respect to the weight of the untreated wood is 1 on the average of 6 test pieces.
It was 1.8%, and the material color was not changed at all before the treatment.

The following water absorption test was carried out on these test pieces. The test piece was immersed in water having a depth of 5 cm so that the fiber direction was parallel to the water surface, taken out after 24 hours, and the water absorption rate was measured by the following calculation formula (1). Value. Calculation formula (1) Water absorption rate = (W−Wo) / Wo × 100 (%) Wo; weight of test piece before water immersion (g) W; weight of test piece immediately after completion of water immersion (g) After the completion of the water absorption test, three out of the six test pieces were immersed in an outdoor water tank in which a water stream circulates for 3 months, and then the appearance was examined.

Example 2 74 g of water was added to 1000 g of trimethoxysilane and the mixture was stirred to obtain a partial hydrolysis-condensation product of trimethoxysilane having an average degree of polymerization of 2.7. This production was confirmed by gas chromatography analysis. 5 g of trimethoxysilylpropyldimethyloctadecyl ammonium chloride was added thereto, and a 50% acetone solution was used as the treating agent of Example 2. When 6 test pieces were produced by the same method as in Example 1, the weight increase rate after the treatment was 12.1% on average for the 6 pieces, and the material color was not changed at all before the treatment. Then, as in Example 1, a water absorption test and an appearance test after immersion in a water tank were performed.

Example 3 To 1000 g of triethoxysilane, 5 g of triethoxysilylpropyldimethylundecyl ammonium bromide was added, and a 50% ethanol solution was used as the treating agent of Example 3. When six test pieces were prepared by the same method as in Example 1, the weight increase rate after the treatment was 8.1% on average of the six specimens, and the material color was not changed at all before the treatment. Then, as in Example 1, a water absorption test and an appearance test after immersion in a water tank were performed.

Comparative Examples 1 to 3 In Comparative Example 1, 6 untreated cedar sapwood having the same dimensions as those used in Example 1 were used as test pieces. As Comparative Example 2, 1000 g of tetraethoxysilane partially hydrolyzed and condensed reaction product
Then, 5 g of triethoxysilylpropyldimethyloctadecyl ammonium chloride was added, and then a 50% acetone solution was used as the treating agent of Comparative Example 2 to prepare 6 test pieces in the same manner as in Example 1. The weight increase rate after the treatment was 2.0% on average for 6 pieces, and the material color was not changed from that before the treatment. Then, as in Example 1, a water absorption test and an appearance test after immersion in a water tank were performed.

As Comparative Example 3, 65 g of water and a catalytic amount of ammonia were added to 1000 g of methyltrimethoxysilane, and the mixture was stirred to obtain a methyltriemexisilane partial hydrolysis condensation reaction product having an average degree of polymerization of 1.6. This production was confirmed by gas chromatography analysis. 5 g of trimethoxysilylpropyldimethyloctadecyl ammonium chloride was added thereto, and a 50% acetone solution was used as a treatment liquid of Comparative Example 3. Six test pieces were prepared in the same manner as in Example 1, and the weight increase rate after the treatment was 1.7% on average for the six pieces, and the material color was yellow and changed like impregnated with oil. Was there. Then, Example 1
Similarly to the above, a water absorption test and an appearance test after immersion in a water tank were performed.

The water absorption rate (%) in the water absorption test of the test pieces of Examples 1 to 3 and Comparative Examples 1 to 3 is shown in Table 1, and the result of the appearance test after immersion in the water tank is shown in Table 2.

[0046]

[Table 1]

These results show that in Comparative Examples 2 and 3 in which tetraethoxysilane or methyltrimethoxysilane, which is difficult to hydrolyze, is used, the rate of increase in weight after treatment, that is, the amount of the fixed agent, when used on wood without a catalyst. It shows that there is little and the waterproof effect is also less.

[0048]

[Table 2]

These results show that in Comparative Examples 2 and 3,
When soaked in running water for a long period of time, the antibacterial component elutes and the antibacterial effect disappears, whereas in Examples 1 to 3, the antibacterial component does not elute and the effect continues.

Example 4 To 1000 g of triethoxysilane, 5 g of triethoxysilylpropyldimethyloctadecyl ammonium chloride was added, and a 50% ethanol solution was used as the treating agent of Example 4. Vertical 10 cm x Horizontal 10 cm
The treatment agent solution was sprayed onto 6 sheets of the analysis filter paper of, and dried at room temperature for 24 hours to obtain 6 test pieces. The weight increase rate after the treatment with respect to the weight of the filter paper before the treatment was 1.3% on average for the six test pieces, and the color of the filter paper was not changed at all from that before the treatment.

First, the following water absorption test was conducted on these test pieces. That is, the test piece was immersed in water having a depth of 5 cm so as to be parallel to the water surface, taken out 24 hours later, and the water absorption rate was calculated by the following calculation formula (1).
The dimensional stability value was measured with and the average value of 6 test pieces was used as the representative value. Calculation formula (1) Water absorption rate = (W-Wo) / Wo x 100 (%) Wo; Weight of test piece before water immersion (g) W; Weight of test piece immediately after completion of water immersion (g) Calculation formula ( 2) Dimensional stability value = (Sc-St) / Sc x 100 (%) Sc; Area swelling ratio of untreated paper (%) St; Area swelling ratio of treated paper (%)

Further, the test piece after the water absorption test was given a diameter of 1c.
It was punched out into a circle of m, placed on the center of an agar medium in which Staphylococcus aureus was inoculated, and cultured at 37 ° C. for 24 hours to examine the growth of bacteria around the test piece (antibacterial property test).

Example 5 To 1000 g of trimethoxysilane, 5 g of trimethoxysilylpropyldimethyloctadecyl ammonium chloride was added, and a 50% methanol solution was used as the treating agent of Example 5. Six test pieces were prepared in the same manner as in Example 4, and the weight increase rate after the treatment was 2.
2%, and the color of the filter paper did not change at all from that before the treatment. Then, a water absorption test and an antibacterial property test were conducted in the same manner as in Example 4.

Comparative Examples 4 to 6 In Comparative Example 4, six untreated filter papers of the same type as in Example 4 were used as test pieces. As Comparative Example 5, 5 g of triethoxysilylpropyldimethyloctadecyl ammonium chloride was added to 1000 g of tetraethoxysilane, and a 50% ethanol solution was used as the treating agent in Comparative Example 5. Six test pieces were produced in the same manner as in Example 4, and the weight increase rate after the treatment was 0. 6 on average.
It was 1%, and the material color did not change at all before the treatment.
Then, a water absorption test and an antibacterial property test were conducted in the same manner as in Example 3.

As Comparative Example 6, 5 g of trimethoxysilylpropyldimethyloctadecyl ammonium chloride was added to 1000 g of methyltrimethoxysilane and 5
The treatment agent of Comparative Example 6 was a 0% methanol solution. Six test pieces were produced by the same method as in Example 4, and the weight increase rate after the treatment was 0.2 on average of the six pieces,
The color of the filter paper was yellow and changed as if soaked with oil. Then, a water absorption test and an antibacterial property test were conducted in the same manner as in Example 3.

The water absorption rate (%) and the dimensional stability value in the water absorption test of the test pieces of Examples 4 and 5 and Comparative Examples 4 to 6 are shown in Table 3, and the results of the antibacterial test using Staphylococcus aureus are shown. 4 shows.

[0057]

[Table 3]

These results show that, in Comparative Examples 5 and 6 in which tetraethoxysilane or methyltrimethoxysilane, which is difficult to hydrolyze, is used, the weight increase rate after treatment, that is, the fixed amount of the drug, when used on wood without a catalyst. It shows that there is little and the waterproof effect is also less.

[0059]

[Table 4]

These results show that in Comparative Examples 5 and 6,
In the 24-hour water absorption test, the antibacterial component is eluted and the antibacterial effect is lost, whereas in Examples 4 and 5, the antibacterial component is not eluted and the effect is maintained.

[0061]

INDUSTRIAL APPLICABILITY The antimicrobial waterproofing agent of the present invention is impregnated with or applied to a material such as wood, pulp, fiber or paper, and has both antimicrobial property and waterproofing property without impairing the texture of the material. The excellent properties of can be imparted.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D21H 19/32 D21H 1/34 P 21/36 5/22 // B27K 3/50 D06M 13/50

Claims (4)

[Claims] 1. An alkoxysilane represented by the following formula (1) or a partial hydrolysis-condensation product thereof, and the following formula (2):
An antimicrobial waterproofing agent comprising a quaternary ammonium salt represented by or a partial hydrolysis and condensation reaction product thereof. (Equation 1) (Equation 2) 2. The alkoxysilane represented by the formula (1) or a partial hydrolysis-condensation product thereof is n = 1, R ¹
Is a partial hydrolysis-condensation reaction product of a trialkoxysilane represented by an alkyl group having 1 to 3 carbon atoms, and the formula (2)
The antimicrobial waterproofing agent according to claim 1, wherein the quaternary ammonium salt represented by is a quaternary ammonium salt in which X ^m- is a halogen ion. 3. An alkoxysilane represented by the formula (1) or a partial hydrolysis-condensation product thereof is permeated into a material to be treated, and then, a quaternary ammonium salt represented by the formula (2) or a salt thereof. The partial hydrolysis-condensation reaction product is permeated into the material to be treated, in which case the total total permeation time is from 1 minute to 24 minutes.
Time and 1/10 to 1/1 before the end of the total infiltration time
An antimicrobial waterproofing method, characterized in that the time of 2 is applied to permeation by the quaternary ammonium salt represented by the formula (2) or a partial hydrolysis-condensation reaction product thereof. 4. An alkoxysilane represented by the above formula (1) or a partial hydrolysis and condensation reaction product thereof, and the above formula (2).
A mixed solution with a quaternary ammonium salt represented by or a partial hydrolysis-condensation reaction product thereof is allowed to permeate the material to be treated for 1 minute to 24 hours, at which time 1/10 to 10 times before the end of the total permeation time.
The anti-microbial waterproofing method characterized in that the concentration of the quaternary ammonium salt represented by the formula (2) in the mixed solution is set to be higher than the concentration in the preceding period for 1/2 time. .