JPS62263279A - Water repellent composition - Google Patents

Abstract

PURPOSE:The titled inexpensive composition, obtained by blending a silicone oil with a nonvolatile paraffinic compound and a specific compatibilizing agent and having high water repellency and improved alkali resistance as well as adhesive property to oil based paints. CONSTITUTION:A composition, obtained by blending (A) a silicone oil, preferably aminomethylpolysiloxane, etc., with (B) a nonvolatile paraffinic compound or low-molecular weight hydrocarbon based resin and (C) a compatibilizing agent, e.g. perfluoroalcohol, etc., capable of reducing the separation index of the components (B) to (A) to <=0.4 in, e.g. a homomixer, etc. The blending ratio of the components (A) to (B) is preferably 60/40-20/80. The adjustment of the separation index of the components (B) to (A) is preferably carried out by adding 0.1-50wt% component (C) to a blend of the components (A) with (B).

Description

[Detailed description of the invention] [Fields of application of V Tojo] The lubricant composition of the present invention, mainly organic or inorganic fibers, paints, inorganic hydraulic substances such as gypsum, gypsum slag, calcium silicate, concrete, lightweight foam. The present invention relates to a composition that imparts water repellency to molded bodies such as concrete.

[Conventional technology]

Compounds such as paraffin, fatty acid metal salts, asphalt, and silicone have been used as water repellent agents for these substances.

[Problem that the invention seeks to solve]

However, paraffin does not have sufficient water repellency in applications where processing is carried out at high temperatures, and fatty acid metal salts and asphalt have disadvantages in that they reduce the strength of molded products and cause coloration. Although silicone compounds are excellent in these respects, they are expensive, are susceptible to alkalis, and have poor compatibility with oil-based paints.

[Means to solve the problem]

The inventors of the present invention conducted intensive studies to obtain a water repellent that is inexpensive while taking advantage of the characteristics of silicone compounds, and also solves the above-mentioned drawbacks. Conventional silicone oil water repellent ( Silicone oil 10θ%) K comparison,
The present inventors have discovered that even if the amount of silicone oil used is reduced to 70% or less, the above-mentioned problems can be overcome without deteriorating water repellency, and the present invention has been achieved. That is, the present invention provides silicone oil, a substantially nonvolatile paraffinic compound or low molecular weight hydrocarbon resin, and a separation index of the paraffinic compound or low molecular weight hydrocarbon resin with respect to the silicone oil. A water repellent composition comprising a compatibilizer that lowers θ and μ to below.

The present invention will be explained in detail below.

Various known silicone oils can be used as the silicone oil constituting the water repellent composition of the present invention, but examples include linear polydimethylsiloxane and modified products thereof that are liquid at a temperature of about % Polymers in the form of

Specifically, 8I (-100 (trade name, manufactured by Toshi Silicone ■, dimethyl polysiloxane), KF-54! (trade name, manufactured by Shin-Etsu Chemical Industrial, methylphenyl polysiloxane), KF-99 ( (Product name, Shin-Etsu Chemical Co., Ltd., Methylhydrodienepolysiloxane), 8F-? Four siloxanes, etc. are available.

The substantially non-volatile paraffinic compound used in the present invention includes a paraffinic compound Q'a f which is liquid at o-tio°C, for example, separated and purified from petroleum, and whose main component is a paraffinic compound Q'a f. lubricating oils such as turbine oil and machine oil, paraffin oils such as liquid paraffin, melting point ≠
Examples include paraffin wax separated from petroleum at θ°C to 100°C, or solid paraffins such as natural beeswax and carnauba wax.

Substantially non-volatile low molecular weight hydrocarbon resins usually have molecular weights of up to -fks 000 and θ
Examples include i≠1,4 convex polybutadiene which is liquid at ~≠Q°C, epoxidized polybutadiene, low polymers of α-olefins having carbon atoms of /6 to //, petroleum resins, coumaron-intene resins, and the like. Note that "substantially non-volatile" means that when the water repellent composition of the present invention is applied to an object! Shi A
¥1fJ This means that the paraffinic resin or low molecular weight hydrocarbon resin in the composition does not volatilize over a long period of time.

In the present invention, the paraffinic compound and the low molecular weight all-hydrocarbon resin have a separation index of 0.0 with respect to silicone oil. It is necessary that the The separation index of paraffin compounds and low molecular weight hydrocarbon resins is 0. If the water repellency is exceeded, the water repellency becomes insufficient, so in the present invention, a compatibilizer is added to adjust the separation index to 0. Adjust to below Hiroshi.

Specific examples of such compatibilizing agents include sorbitan dialkyl esters, sorbitan trialkyl esters, alkylphenol polyethylene glycol condensates, fatty acid polyethylene glycol condensates, aliphatic alcohol polyethylene glycol condensates, aliphatic amide polyethylene glycol condensates, and polypropylene glycol polyethylene. Glycol metal products, etc.! (LBO~B surfactants, also perfluoroalcohol polyglobylene glycol isocyanate 8 compound, fatty acid monoalcohol ester, fatty acid polyhydric alcohol monoester, fatty acid polyhydric alcohol diester, carbon atom number 6 A phase of silicone oil such as a copolymer of α-olefin and maleic acid monoester or maleic acid diester of ~j-, a modified product of ethylene-vinyl acetate copolymer, and a paraffinic compound or a low molecular weight hydrocarbon resin Examples include those that increase solubility.

The separation index of paraffinic compounds and low molecular weight hydrocarbon resins can be easily adjusted by adding the above-mentioned compatibilizing agent to a mixture of silicone oil and paraffinic compounds and/or low molecular weight hydrocarbon resins. preferable. In that case, the compatibilizer is usually added to the above-mentioned mixture at 0. /~SO!
You can select as appropriate from the range of scenery.

In the present invention, the separation index refers to mixing silicone oil and the above-mentioned various compounds (for solid paraffin, at a temperature above their melting point) at a ratio of 3 to 1 by weight, and then adding a compatibilizer within the above range. Liquid added with! ? of! Place the mixture in an O- beaker and mix with a magnetic stirrer at p/200RPM for j minutes using a Teflon stirrer (#20m, diameter 4~rwatt) while heating as necessary. Transfer to a 7trrm test tube,
fK is the value obtained by dividing the height of the transparent layer formed by the height of the total liquid.

In the water repellent composition according to the present invention, the mixing ratio of silicone oil and paraffinic compound or low molecular weight hydrocarbon resin is preferably in the range of 30 to 70 to 2θ to 0 by weight.

In particular, a range of 10:440 to 20:♂0 is preferred.

If the silicone oil is less than the above ratio, the water repellency will be insufficient, and if it is more than the above ratio, the price of the water repellent composition will be high, which is undesirable.

In the present invention, the silicone oil, the paraffinic compound or the low molecular weight hydrocarbon resin, and the compatibilizing agent,
A water repellent composition can be obtained by dispersing and mixing using a turbine blade stirrer, homomixer, etc., or by dissolving in an organic solvent such as toluene or benzene, according to a known method.

117'? It is also possible to emulsify the water repellent composition by adding water and, if necessary, a surfactant, and use it as an emulsion. In addition, when making it into an emulsion,
It is also possible to simultaneously mix silicone oil, paraffinic compound or low molecular weight hydrocarbon resin, compatibilizer, surfactant and water without preparing the above water repellent composition in advance. In addition, it is advantageous for the formation of an emulsion to mix the compatibilizing agent with silicone oil, paraffinic compound, or low molecular weight hydrocarbon resin in advance.

As the surfactant used in preparing the emulsion, in addition to the surfactants exemplified above as the compatibilizer, those commonly used as emulsifiers can be used. The surfactant used for emulsification is 1'I
There is no problem even if it is larger than LB4.

Specifically, for example, polyethylene glycol condensates of sorbitan alkyl esters, fatty acid polyethylene glycol condensates, aliphatic amide polyethylene glycol condensates, aliphatic amine polyethylene glycol condensates, aliphatic alcohol polyethylene glycol condensates, and alkylphenol polyethylene glycol condensates. Nonionic surfactants such as metal products, polypropylene glycol polyethylene glycol condensates, anionic surfactants such as sodium alkylsulfonates and sodium dialkylsulfoconomonolinates, furthermore, brewed paraffins, ester waxes, α-olefin-maleic anhydride copolymer, α-olefin-maleic anhydride adduct, styrene-maleic anhydride copolymer, α-olefin-fatty acid anhydride adduct, derivatives thereof, or salts thereof are also used. can. The use of these surfactants is preferably the minimum amount necessary to emulsify the mixture of silicone oil and paraffinic compound or low molecular weight hydrocarbon resin in water, but usually 2 to 30% of the amount is used for the water repellent composition. *Additional amount, preferably 2 to 20, is added. As a method for emulsifying the above composition, conventionally known methods such as a homomixer, a colloid mill, a pulp homogenizer, and an ultrasonic wave can be applied.

Furthermore, for the purpose of thickening or increasing the stability of this emulsion system, synthetic polymer compounds such as polyvinyl alcohol, polyethyleneimine, polyacrylic acid, styrene-maleic anhydride copolymer, or salts thereof, methyl cellulose, carboxymethyl cellulose are added. , a water-soluble polymer compound such as a cellulose derivative such as hydroxymethylcellulose may be added. The water-soluble polymer compound is used in the water repellent composition at a ratio of usually 1 to 10%, preferably O0θ/%% to 6% jttIa. If the amount added is less than 0.0/weight, no significant improvement in stability can be expected.

If the amount exceeds 10 ji, it is not preferable because it may not have an adverse effect on water repellency.

Conventionally known methods can be used to apply the water repellent composition of the present invention to organic or inorganic fibers, paints, and inorganic hydraulic substances. For example, an internal addition method in which the water repellent composition is added and dispersed in a slurry of an inorganic hydraulic material such as mineral or pulp, a method in which it is applied or sprayed onto the surface of paper, #fiber, an inorganic molded body, etc.; Examples include a method of immersing the above-mentioned base material in a water repellent composition. Furthermore, there are no restrictions on the combined use of various additives during the above-mentioned processing.

[Function] As described in detail above, the water repellent composition of the present invention combines silicone oil and a paraffinic compound or a low molecular weight hydrocarbon resin by using a compatibilizer to bind the paraffinic compound or low molecular weight hydrocarbon resin to silicone oil. By lowering the separation index fO of the molecular weight hydrocarbon-based resin to less than 90% and creating a composition of 9), the amount of silicone oil used can be reduced compared to the conventional 7 Ricoh/oil-based water repellent. It has the same high water-repellent effect as conventional products, and is also cheaper than conventional products. Furthermore, conventional silicone oil-based water repellents may not be able to impart sufficient water repellency when the base material to which water repellency is imparted is cotton, paper, etc.; however, the water repellent composition of the present invention Water repellency can be imparted without being limited to the type.

Furthermore, it has superior alkali resistance compared to conventional silicone-based water repellents, making it possible to maintain water repellency for a long period of time even when applied to concrete and the like.

In addition, it is thought that the water-repellent base material and oil are compatible with each other, and good adhesion can be obtained even when an oil-based paint is overcoated.

Compared to conventional paraffin-based or oil-based emulsions, it has superior heat resistance and can withstand curing in autoclaves, while also imparting sufficient water repellency even when added internally to concrete etc. and dried at room temperature. be able to.

Next, the present invention will be explained in more detail with reference to Examples, Comparative Examples, and Test Examples. In the following description, "parts" and "chi" mean "parts by weight" and "chi". It was,
The silicone oils used in the examples and comparative examples were all 19H--200 (east silicone crack, viscosity: 0Q).
cSt 725°C).

Example/ Separation index θ, 4! 0 parts to the 4c turbine oil (Mitsubishi Oil Co., Ltd., Diamond Turbine Oil Well 6t) and HLB 2.0 parts to the silicone oil Hiro θ part. 4 parts of sorbitandiolate was added and mixed and dispersed in a homomixer to obtain an oily composition (a). :Obtained.

The separation index of turbine oil is increased by the addition of sorbitan diolate J) 0. J/ has been adjusted to vI4.

Comparative Example/Manufacturing Example/Turbine oil and silicone oil were mixed and dispersed in a homomixer without adding sorbitandiolate to obtain an oily composition (b). The separation index of turbine oil is 0. It was ≠≠.

Example 02 parts of the composition (a) obtained in Example 2 and 700 parts of demineralized water were emulsified in a homomixer to reduce the solid content! 0.3
% emulsion ((ri t-obtained 7'?-0 Example 3 α-olefin with carbon atoms/g ~/r (Mitsubishi Chemical ■, Dialene/l, r), 2J parts (/mol)
and hismaleic acid diethyl ester/r portion (/,/m
ob) was charged into a four-liter flask and heated to 760°C under a nitrogen atmosphere.
srt-butyl peroxide, oottobe (o, θt t
mol) was added at 20 minute intervals, and after the addition, the reaction was further carried out at the same temperature for 7 hours.

After the reaction is completed, light boiling components and unreacted monomers contained in the reaction mixture are distilled off under reduced pressure of /~JmHg, and α
-Olefin 7 (Css~18)-diethyl maleate copolymer (hereinafter abbreviated as PAR#/let) was obtained.

The obtained PAR/4/It ψ part, 4 tO parts of turbine oil (diamond turbine oil #4?), and 40 parts of silicone oil were mixed and dispersed using a filter mixer to obtain an oily composition.

The dispersion index of the turbine oil is adjusted to θ, // by adding PAR/4/Et. Propylene oxide ethylene oxide copolymer (HLB/
2 parts of /, j) and 2 parts of demineralized water/θ were added and emulsified with a homomixer to obtain an emulsion (d) having a solid content of 4C, 9 parts and J%.

Example 57 parts of coumaron-indene resin with a separation index of O0 and 3 parts of silicone oil were mixed with perfluoroalkyl group-containing polyalkylene glycol isocyanate condensate (Dainippon Ink Chemical ■, trade name Nimegafac F/?≠)
0. j parts (separation index is adjusted to 0.10) K and oxidized paraffin (mp = 70
℃, acid value = ≠ 3), 74 parts of dimethylethanolamine salt, 2 parts of aliphatic amide ethylene oxide adduct (Lion Axie, trade name: Esomide HT) were added to 20
After melting at 30°C, 200 parts of demineralized water at 20°C was added and emulsified with a homomixer to reduce the solid content to 30. Flathead emulsion (f
) was obtained.

Comparative example Separation index: 0. After mixing and dispersing Hirobe's turbine oil (diamond turbine oil #t φθ part and 10 parts silicone oil in a homomixer, emulsifier (product name: Pluronic Lμ)
2 parts of ethylene oxide/propylene oxide copolymer (manufactured by Koasahi Denka Kogyo ■) and 10 parts of demineralized water were added to obtain an emulsion (ω) with a solid content j of 0.4°C%.

Comparative Example 3 100 parts of silicone oil, propylene oxide and ethylene oxide copolymer () II as emulsifiers, B4.
j) Emulsify 2 parts and 700 parts of demineralized water with a homomixer to obtain solid content! A 0.2% emulsion (h) was obtained.

Example! 36 parts of paraffin wax with a melting point of 49°C and 0, /IK
Furthermore, oxidized paraffin (mp = 70°C, oxidation = = 44j) was added to the oxidized paraffin (mp = 70°C, oxidation = = 44j) rod, polyethylene glycol lauryl ether (HLB = HLB = 200 parts of demineralized water was added and further hydroxylated). Add 0.1 part and emulsify with a homomixer to reduce the solid content to 33. ≠I obtained Emulsion (1).

0. IA/adjusted) are examples! An emulsion (,+) having a solid content of jJs% was obtained in exactly the same manner as above.

Test example/~≠ Emulsion (d), (g) or (h) with a solid content of 7
% diluted with water (ρ=o
, o2s), and after draining for 1 hour, it was dried at 0° C. for 2 hours. This was sprayed with water according to the L1092 spray test method from J, and the results for the system without the addition of Y water agent are also shown.

It can be seen from the table that water repellent compositions with separation indexes of less than o and p exhibit water repellency almost equivalent to that of silicone oil.゛Test example! ~? 4.7 t of cotton broadcloth, emulsion (d), (
g) or (h) 't-in solid content! The sample was immersed in a bath containing water and treated with water at a dipping, nip, and squeezing rate of 7. Then, after pre-drying at 20°C for 3 minutes, it was cured at 730°C for 5 minutes using a pincher. Furthermore, this was heated in a dryer at 10° C. for 4 hours. Regarding this item, its water repellency was measured in accordance with J-K8L-1004/- and at the same time? Measure the water absorption rate after aqueous evaluation and list the results.
It was shown to. For comparison, the results for a system without any water repellent added are also shown.

Test example ~ // 31 tsubo / -2J f / @' sizeless paper is immersed in a bath containing emulsion (J, (g) or (h) in solid content / ) for 7 minutes, and then rolled. After measuring the amount of pink-up, press at 20℃ for 2 to 3 minutes, and then press at 0℃.
After heating in a dryer for 4 hours, pretreatment was performed in accordance with J Engineering 5P-4///, and then water resistance (Stekcht seconds) was measured in accordance with JxSP-dr/22. The results are shown in Table 3.

Test example/Co~/4A Commercially available vinyl acetate emulsion paint (Kansai Paint■
Add emulsion (d), (g) or (h) to the non-volatile content of 52% (solid content: 52%) [7] and apply to the surface of the plasterboard at approximately 700 f/m'. did. After drying this at 60° C. for 7 hours, demineralized water/go was added dropwise to it, the top surface was covered with a watch glass, and the time until the water droplets disappeared was measured to determine water resistance. The results are shown in the table.

Test example/! ~23 Portland cement/60 parts, powdered silica/Hiroshi 3 parts, metal aluminum Ecum 0. The water repellent composition shown in Table 5 was mixed into a slurry consisting of 200 parts of water and 200 parts of water so that the nonvolatile content was 6.7 parts, and the mixture was poured into a mold. After foaming and curing, it was removed from the mold and placed in an autoclave at 710°C, 10 pieces/7.
Hydrothermal curing was performed for 5.5 hours under the conditions of G, and further 10
! 'C:.

After drying for 10 hours, lightweight aerated concrete was obtained.

This was placed in -0°C water at 30 trrm below the water surface, and the water absorption rate was determined from the weight change after being left for 2 hours. The results are shown in Table 5.

Test Example 2μ~27 Emulsion (c
), (g) or (h) was applied at a rate of /00 f/m' and dried at room temperature for 3 days. Water resistance was determined by adding water droplets after drying and covering with a watch glass to prevent evaporation, and measuring the time until the water droplets completely disappeared. The water resistance was similarly measured in the case where no water repellent was applied, and the results are shown in Table 6.

Test example, 2! , Kota Portland cement/bu 0 parts, powdered silica/Hiro 3 parts, gold i1 aluminum 0. Emulsion (d) or f7r (h) was mixed into a slurry consisting of one part and 200 parts of water so that the nonvolatile content was j,/part, and the mixture was poured into a mold. After foaming and curing, the mold was removed and placed in an autoclave at ♂O℃.
Hydrothermal curing was carried out for 5 hours under the conditions of AIF/-G, and then dried for 10 hours at I/C 10.7℃ to obtain lightweight cellular concrete. ! r.

These were placed in water at -0°C or at 0.5°C. /H caustic potash aqueous solution at a depth of 30 mm below the water surface, the weight change after standing for 2 hours was used to determine the water absorption rate, and the alkali resistance index (the higher the better) was determined using the following formula.

Alkali Resistance Index (API) Here, Ay (alkali) and AW (in water) indicate the water absorption rate in an alkaline aqueous solution and in water, respectively.

Furthermore, the contact angle of these samples (unsoaked) with respect to liquid paraffin was measured, and the mowing ability with respect to oil was measured. The results are shown in Table 2.

Table/Note/) The (%) of the water repellent composition represents the silicone content in the active ingredients.

Note 2) The amount added means the value obtained by dividing the nonvolatile content of the water-repellent composition adhered to the base material by the weight of the base material x 700.

Below, the expressions in each table have the same meaning.

Table a Table 3 Table μ Table j Table 6 appearance

Claims (5)

[Claims] (1) Silicone oil, a substantially nonvolatile paraffinic compound or low molecular weight hydrocarbon resin, and a separation index of the paraffinic compound or low molecular weight hydrocarbon resin with respect to the silicone oil of 0.4% or less A water repellent composition comprising a compatibilizer that reduces compatibilization. (2) The water repellent composition according to claim 1, wherein the compatibilizer is a nonionic surfactant with an HLB of 0 to 6. (3) The water repellent composition according to claim 1, wherein the compatibilizer is a perfluoroalcohol/polypropylene glycol/isocyanate condensate, a fatty acid monoalcohol ester, a fatty acid polyhydric alcohol monoester, or a fatty acid polyhydric alcohol diester. thing. (4) A patent in which the compatibilizer is a copolymer of an α-olefin having 6 to 52 carbon atoms and maleic acid, a monoalkyl maleate, or a dialkyl maleate, an ethylene-vinyl acetate copolymer, or a modified product thereof. The water repellent composition according to claim 1. (5) The water repellent composition according to any one of claims 1 to 4, wherein the water repellent composition is an aqueous emulsion.