JPS6343976A - Filler and finishing coat material containing said filler - Google Patents

Abstract

PURPOSE:To obtain a filler suitable for use in a finishing coat material which has excellent adhesive strength, substrate hiding effect, and storage stability, and gives a coating film having excellent waterproofness and suffering neither peeling nor blistering, by surface treatment of SiO2 or Al2O3 with a long-chain alkylalkoxysilane. CONSTITUTION:A surface-treated filler is obtained by mixing a solution made by adding a long-chain alkylalkoxysilane of, e.g., formula I or II (wherein n is 10 or greater) in an amount sufficient to provide a concentration of 0.1-0.5wt% to e.g., an 8/2 water/isopropyl alcohol solvent with an SiO2 or Al2O3 filler of a particle diameter of 50-200 mesh in a weight ratio of the filler to the alkoxysilane of 100:1 in, e.g., a Henschel mixer, and drying the mixture. 100pts.wt. emulsion copolymer made from 100pts.wt. of at least two kinds of monomers having vinyl groups in a molecule and 10-20pts.wt. colloidal silica is mixed with 50-4,000pts.wt. this surface-treated filler and 5-40pts.wt. water-dispersible alkyd copolymer of an acid value of 10-30 thus giving a finishing coat material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a filler and a finishing coating material suitable for blending into a finishing coating material suitable for use on a ceramic base of a building or a workpiece.

More specifically, it relates to finishing coating materials that are applied using construction methods such as rollers and spraying for both waterproofing and design purposes in areas where ceramic exterior wall panels such as mortar, concrete, lightweight aerated concrete, and calcium silicate panels are used in vertical areas. .

[Prior Art] Various finishing coating materials have been studied to improve waterproofness. Its base material and performance values are based on JIS A 6910.
This is as shown in "Multilayer Finishing Material" etc.

However, if the binder base of the finishing material was chosen in order to improve waterproofness, many of them inhibited water vapor permeability.

To improve water vapor permeability, the amount of binder in the finishing material can be reduced and the amount of aggregate can be increased to make the coating of the finishing material porous.

However, such finishing coating materials have relatively low adhesive strength, good permeability, but at the same time poor waterproof properties.
It is unsuitable for waterproofing buildings, etc., or as a decorative finishing coating.

[Problem to be solved by the invention] If the water vapor permeability of the coating film is poor, the underlying mortar layer,
If a finishing coat is applied while the concrete is insufficiently dry, water droplets will form at the interface between the base and the paint film during the evaporation process of the remaining water, resulting in accidents such as peeling of the paint film or blistering. It is easy to cause Also, when heating is performed in winter, the temperature and humidity increase simultaneously. In addition to causing similar accidents due to the movement of internal water vapor, dew condensation may occur within the walls, causing adverse effects such as water absorption, rusting, and decay on the gutter structures and interior materials.
It also caused mold growth.

Such accidents occur quite frequently in buildings, etc., and are a major problem in terms of durability or aesthetics.

In addition, even with finishing materials that are water vapor permeable, it is possible to satisfy the workability, design, and price with the current civil engineering, architectural technology, and construction technology using i% water, while maintaining the performance that the finishing materials should have, such as waterproofness, It must have a combination of adhesive strength, ability to conceal the base, and storage stability.

The present invention attempts to simultaneously satisfy these multiple conflicting conditions.

[Means for solving the problems] The structure of the present invention for solving the above problems is as follows:
A filler according to claim (1), further comprising:
The finishing coating material described in claim (2) is used.

That is, the filler is made of silica or alumina that has been surface-treated with a long-chain alkyl-based alkoxysilane having 10 or more carbon atoms. Specifically 50-20
Suitable materials include 0 mesh silica or alumina particles surface-treated with the alkoxysilane described above.

Among the components of the finishing coating material of the present invention, component A is an emulsified compound consisting of two or more types of monomers having vinyl groups in the molecule and 10 to 200 parts by weight of colloidal silica per 10 parts by weight. It is a polymer.

Component B is a silica or alumina filler whose surface has been treated with a long-chain alkyl-based alkoxysilane having 10 or more carbon atoms. This filler is often referred to as component A, and has the effect of increasing the adhesive strength of the finishing coating material, improving adhesive force, and increasing waterproofness without decreasing moisture permeability.

However, even if component B is mixed with component A using a conventional method, it lacks long-term storage stability, and precipitation of solids, gelation of the solution, or color separation of pigments occurs during storage, so it is not practical. Not suitable.

On the other hand, the C component, that is, the acid value is 10 to 3
By blending a water-dispersible alkyd copolymer with a water dispersibility of 0.0, long-term coating stability can be obtained, and for the first time, it is possible to produce 1 q of finishing coating material with a balance between coating performance and stability.

The monomer having a vinyl group in the molecule, which is a component of the emulsion copolymer (component A) of the finishing coating material of the present invention, is an acrylic ester, a methacrylic ester, or a monomer copolymerizable with these. These include acrylic acid, methacrylic acid, itaconic acid, maleic acid (anhydrous), fumaric acid, crotonic acid, acrylamide, methacrylamide, styrene, α-methylstyrene, vinyltoluene, acrylonitrile, and methacrylnitrile.

In addition, the above acrylic esters or methacrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, 2-ethylhexyl methacrylate, Examples include uryl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, dihydroxyethyl methacrylate, and glycidyl methacrylate.

It is also another component of this emulsion copolymer (component A).

The colloidal silica is suitably an aqueous dispersion having SiO2 as a basic unit and has a particle size in the range of 4 to 100 μm, and the particle size is determined using an electron microscope.

The alkyl-based alkoxysilane used to surface-treat silica or alumina as component B to produce a filler has a general formula of C, H2n, 13 i (OCl-13>3 or Cn H2n + IS i (OC2t15)3). The alkyl alkoxysilanes shown are suitable, preferably long chain alkyl alkoxysilanes ranging from CI6 to C+a.

Many of the alkoxysilanes commonly used as surface treatment agents have functional groups such as vinyl groups, chloro groups, amine groups, mercap groups, and epoxy groups. However, when silica or alumina is treated with a coupling agent made of these alkoxysilanes, the emulsion copolymer (component A) has high reactivity with the water-dispersible alkyd copolymer (component C), resulting in poor stability. harm the

In contrast, the alkyl group represented by C1H2n+1 in the surface treatment agent used for the construction of the filler of the present invention has good compatibility with the organic binder, but does not react with the organic binder, so it can be used as a treatment agent for filler production. The most effective ten other components of the finishing coating material of the present invention include acid values of 10 to 10.
There are 30 water-dispersible alkyd copolymers (component C).

Normally, these materials are difficult to form into a good water-soluble resin when neutralized with ammonia and amines unless the amount of each resin is about 60 to 100. When water is uniformly dispersed in a neutralized product of the copolymer, which generally has a low acid value, it becomes a colloidal dispersion, which becomes cloudy and exhibits intermediate properties between a dissolved state and a dispersed state. However, the colloidal dispersion resulting from ionic dissociation at the terminal of this copolymer is
It is thought that it functions effectively as a colloid of the emulsion copolymer (component A) and improves its stability.

The water-dispersible alkyd copolymer is obtained from the desired condensation product of a polyhydric alcohol and a polybasic acid, including lylunic acid, linoleic acid, eleostear 1. !
Fatty acids such as ricinoleic acid, ricinoleic acid, and dehydrated ricinoleic acid can be used.

These fatty acids are found in drying oils such as tung oil, linseed oil, and soybean oil, although suitable drying oils are dehydrated castor oil and tall oil.

Polybasic acids such as phthalic acid, maleic acid, sebacic acid, trimellitic acid and adipic acid or their anhydrides can also be used in conjunction with the above-mentioned fatty acids.
- Also, as the polyhydric alcohol, glycerin, pentaerythritol, ethylene glycol, propylene glycol, diethylene glycol, 1.5-bentanediol, etc. can be used.

Incidentally, although the water-dispersible alkyd copolymer described above is highly effective in increasing stability as a protective colloid, it has little thickening effect, so it is necessary to use some kind of thickener in combination.

Examples of substances used as thickeners include synthetic polymers and cellulose derivatives.

Synthetic polymers include polyvinyl alcohol, sodium polyacrylate, polyvinylpyrrolidone, styrene maleic acid copolymer, polyvinyl methyl ether, polyacrylamide, vinyl methyl ether maleic anhydride free copolymer, and polyethylene oxide.

As the cellulose derivative, methylcellulose, hydroxymethylcellulose, hydroxypropylmethylcellulose, and hydroxypropylmethylcellulose are used.

In addition to these substances, inorganic substances such as bentonite and asbestos may also be used.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.

Component A (emulsion copolymer) This is an emulsion copolymer of a monomer having a vinyl group in the molecule and colloidal silica, and commercially available products listed in Table 1 below can be used.

Surface treatment method for component B Using a solvent with a water/isopropyl alcohol ratio of 8/2, alkyl-based alkoxysilane [C+a Hco7Si (OCH2CH3
) A solution with a concentration of 0.1 to 0.5% by weight is prepared and mixed with silica or alumina filler having a particle size of 50 to 200 mesh.

) The appropriate amount is such that the weight of the alumina-based alkoxysilane is 1% by weight relative to the silica or alumina filler.

The mixing method is to add the above solution while stirring the filler using a Henschel mixer or a V-type blender. After stirring for about 30 minutes, the contents were taken out, dried and heated to 110
Dry at ~120°C for 5 to 10 minutes to obtain a surface-treated filler.

Synthesis Example of Component C A synthesis example of a water-dispersed alkyd copolymer, which is component C, is as follows.

Components of copolymer Trimellitic anhydride 375 parts Dehydrated castor oil fatty acid 360 parts 1.5-bentanediol
235 parts Butyl cellosolve 30 parts Total i ooo parts Above copolymer 1000 parts Aqueous ammonia (28%) 45 parts Water 172
6 parts total: 2771 parts Solid content: 35% Acid value: 20% Each component is placed in a polymerization reaction vessel and heated to approximately 60°C while stirring in a nitrogen atmosphere.

Next, gradually heat the ladle to 180'C until the rIi value is 20.
Maintain this temperature for approximately 8-9 hours until the temperature is reached. It is then cooled to the lowest temperature. Aqueous ammonia is added to the obtained copolymer and water is mixed in with stirring to obtain a desired colloidal dispersion.

Table 1 below shows examples of composition of components in Examples and Comparative Examples of the present invention.

Note that the unit for the amount of each component is duram (q).

Table 1 Table 2 below shows test results of viscosity (poise), adhesion strength, water permeability, and moisture permeability of the formulations shown in each Example and Comparative Example.

The test results in Table 2 are based on the following method.

Adhesion strength JIS A 69095. According to the test method specified in S, each finishing coating material in Table 1 is applied to a mortar plate of 70 x 70 x 20 mm, and the coating film, which is left to dry for 14 days, is adhered to a refining jig for upper tension with epoxy resin. . Next, this upper tension rope jig is fitted into the lower tensile refining jig, and a tensile force is applied in the vertical direction to the sample surface to determine the maximum tensile load, and the adhesion strength is calculated using the following formula.

Adhesion strength kqf/cm2) = T/1BT is maximum tensile load (kg・f) Water permeability test JIS^69095, 10, JIS^5403
A finishing coating material is applied to a flexible board with a thickness of 4 mm specified in (asbestos slate), a cylinder containing fresh water is attached to it in a watertight state, and the amount of water permeation is read from the scale on the cylinder after 60 minutes.

According to moisture permeability JIS Z 0208, the coating applied to the polyethylene film is peeled off in a film after drying, and a cup containing a moisture absorbent is covered with the peeled coating, and the water vapor that passes through the coating of unit area in a certain period of time is It was calculated using the following formula.

Moisture permeability (g/m2.24) = 240-m/l, s
S is the moisture permeable area cm2, t is the total time of the last two weighing intervals during which the test was conducted (
h) m is the total mass increase in the last two scale intervals tested (IIlg) Table 3 shows the results of the storage stability test for each Example and Comparative Example.

The storage stability test is a method in which the paint is left in an atmosphere at a temperature higher than room temperature for a certain period of time to promote thickening and gelation of the paint. It has been confirmed that one month of storage at 40°C is equivalent to approximately one year under normal storage conditions.

Table 2 m' According to the adhesion strength test of JIS-A6909 "m3 according to the water permeability test of JIS-A6909"
Table 3 (Effects of the Invention) Based on JIS-20208 Moisture Permeability Test As explained above, the surface of concrete, mortar, light matrix cellular concrete, etc. can be painted using the finishing coating material containing the filler of the present invention. If this is done, sufficient waterproofness can be ensured, and the passage of water vapor contained in these substrates during construction is less likely to be obstructed.Therefore, it is effective in preventing peeling of the paint film that floats on the number of steam valves. .

In addition, even if the water vapor pressure inside the seedling increases due to heating etc. in winter,
There is little obstruction to the movement of water vapor outdoors. For this reason, it is effective to use lightweight aerated concrete, which has low resistance to water vapor transmission, for wall materials and to paint the external surface. , it is possible to improve stains and frost damage on internal and external wall materials.

As described above, the present invention is significant in that it can significantly improve the durability of buildings and workpieces.

Claims (2)

[Claims] (1) A filler made of silica or alumina whose surface is treated with a long-chain alkyl-based alkoxysilane having 10 or more carbon atoms. (2) Add 5 parts of the following component B to 100 parts by weight of the following component A.
A finishing coat characterized by containing 0 to 4000 parts by weight and 5 to 40 parts by weight of the following component C. (A) An emulsion copolymer consisting of two or more types of monomers having vinyl groups in the molecule and 10 to 200 parts by weight of colloidal silica per 100 parts by weight of these monomers. (B) A filler made of silica or alumina whose surface is treated with a long-chain alkyl-based alkoxysilane having 10 or more carbon atoms. (C) A water-dispersible alkyd copolymer having an acid value of 10 to 30.