JPS6341568A - Surface-treating agent for ionroganic construction material - Google Patents

Abstract

PURPOSE:To obtain the title surface-treating agent by polymerizing polymerizable monomers including silanes in the presence of organopolysiloxane bearing terminal hydroxyl groups at a specific ratio, thus giving inorganic construction materials good water repellence by coating. CONSTITUTION:(A) In the presence of 1-80wt% of organopolysiloxane bearing terminal hydroxyl groups, a mixture of (B) 0.05-10wt% of polymerizable silane such as vinyl trimethoxysilane, (C) 0.5-10wt% of unsaturated organic acid such as acrylic acid and (D) 0-98.45wt% of other monomers copolymerizable with them such as butyl acrylate where A + B + C + D = 100wt% are polymerized to give the objective treating agent. EFFECT:The inorganic construction materials treated with the agent according to the present invention improve their resistances to water and efflorescence and maintain their properties for a long period of time.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a surface treatment agent for inorganic building materials.

Specifically, by painting the surface of an inorganic building material, it is possible to impart water repellency, waterproofness, efflorescence resistance, etc. to the surface of the inorganic building material, and the coating film formed by the painting process is also excellent in durability, so that the above properties are achieved. The present invention relates to a surface treatment agent for inorganic building materials that can maintain the properties over a long period of time.

(Prior art) Conventionally, emulsion resins such as acrylic resin, styrene-acrylic resin, and vinyl acetate resin, and solvent-based resins such as urethane resin, epoxy resin, and vinyl chloride resin have been used as surface treatment agents for inorganic building materials. There is.

However, when the above emulsion resin is applied to inorganic building materials, which are generally porous, only water rapidly penetrates into the building material, and the resin itself hardly penetrates into the building material, forming a film on the surface. Because it is a plastic, it has poor adhesion to building materials, and the strong alkalinity of the material causes the resin to deteriorate after it is formed, so it has the disadvantage that it has little effect on reinforcing the weak parts of the surface layer of building materials.

In order to improve such problems, a method of incorporating colloidal silica into emulsion resin is also being considered.

In this method, some of the colloidal silica penetrates into the building material, which can improve the brittleness of the surface layer of the building material to some extent, but since the colloidal silica and resin are hardly bonded, long-term durability may be affected. However, the essential problems of emulsion resins have not been improved yet.

On the other hand, conventionally used solvent-based resins have a large penetration rate into building materials, and can considerably improve the fragility of the surface layer of building materials. It was also not completely satisfactory in terms of performance, durability, etc.

(Problems to be Solved by the Invention) The present invention is intended to improve these drawbacks of the prior art. Therefore, an object of the present invention is to provide an inorganic building material that can impart water repellency, waterproofness, efflorescence resistance, etc. to the surface of the inorganic building material by coating the surface thereof, and can also form a highly durable coating film. The purpose is to provide a surface treatment agent for

(Means and effects for solving the problems) As a result of intensive research in order to solve the problems described above, the present inventors have discovered that a polymerizable monomer containing a polymerizable silane compound in the presence of an organopolysiloxane containing a terminal hydroxyl group When a surface treatment agent containing a polymer obtained by polymerizing a polymer component is applied to an inorganic building material, it forms a coating film with excellent adhesion, giving the building material excellent water repellency, waterproofness, and resistance. The present invention was completed by discovering that the coating film formed has excellent durability and can maintain the above characteristics for a long period of time, while imparting efflorescence properties.

That is, in the present invention, in the presence of 1 to 80% by weight of an organopolysiloxane containing terminal hydroxyl groups (A), 0.05 to 10% by weight of a polymerizable silane compound (B), and an unsaturated organic acid (C
) 0.5 to 10% by weight and other polymerizable monomers copolymerizable with these (D) 0 to 98.45% by weight (However, (A)
, (8), the total of components (C) and (D) is 100% by weight
shall be. ) is provided.The present invention provides a surface treatment agent for inorganic building materials, which comprises a polymer obtained by polymerizing the following.

The terminal hydroxyl group-containing organopolysiloxane (A) used in the present invention has the general formula (wherein R1 and R are each independently a hydrocarbon group that may be substituted with a monovalent halogen, and n is 2 to 20,000. (It is an integer.) Currently, various types are easily available and can be used depending on the purpose. As for the molecular weight of the organopolysiloxane (A) used, n is 2 to 20,000,
Preferably, it is in the range of 8 to 15,000. n
is less than 2, the resulting treatment agent will not exhibit sufficient water repellency;
Further, when n exceeds 20,000, the viscosity becomes high, making handling and polymerization operations difficult, which is not preferable.

Furthermore, in addition to the organopolysiloxane shown in the general formula above, organopolysiloxanes having partially branched side chains can also be used as the organopolysiloxane (^) without any problem.

Organopolysiloxane containing terminal hydroxyl group (A)
The amount used can be determined as appropriate within the range of 1 to 80% by weight depending on the degree of water repellency.

If the amount used is 1% by weight, the water repellency and waterproofness will not be sufficient, and if it exceeds 80% by weight, the adhesion to the substrate will decrease, which is not desirable.

The polymerizable silane compound (B) used in the present invention is a compound having in its molecule at least one polymerizable unsaturated group and at least one group capable of condensation reaction with the organopolysiloxane (A). , such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris(β-methoxyethoxy)silane, allyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxy Propyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyljethoxysilane, γ-
(meth)acryloxypropyl-〇-tris(β-methoxyethoxy)silane, 2-styrylethyl-1-rimethoxysilane, (meth)acryloxyethyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, vinyltriacetoxysilane , vinyltrichlorosilane, etc., and one type or a mixture of two or more types selected from these groups can be used.

The amount of the polymerizable silane compound (B) to be used can be appropriately determined within a range of 0.05 to 10% by weight.

If the amount used is less than 0.05% by weight, the adhesion and durability to inorganic building materials may be insufficient, or the polymer consisting of organopolysiloxane (A), (B), (C) and (DJ acid component) may be insufficient. If the bonding is insufficient, an effective amount of graft reaction will not occur, and the treatment agent will cause layer separation, and it will be difficult to maintain water repellency over a long period of time when used as a surface treatment agent. If the amount exceeds % by weight, gelation during polymerization tends to occur, resulting in poor stability of the composition.

The unsaturated organic acid (C) used in the present invention has the effect of inducing a bond between the organopolysiloxane (A) and the polymer to smoothly proceed with the grafting reaction, and also improves the adhesion of the resulting treatment agent. For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; Examples include saturated sulfonic acids, and one or a mixture of two or more of these can be used.

The amount of unsaturated organic acid (C) to be used can be determined as appropriate within the range of 0.5 to 10% by weight. If the amount used is less than 0.5% by weight, it is difficult to cause an effective amount of graft reaction, and if it exceeds 10% by weight, it becomes difficult to maintain a balance between the polymerization reaction and the grafting reaction, and the resulting treatment This will impair the water repellency and adhesion properties of the agent and the stability of the composition.

Examples of the polymerizable monomer (D) used in the present invention include acrylic esters such as butyl acrylate and acrylic M-2-ethylhexyl; methacrylic esters such as methyl methacrylate and butyl methacrylate; (Meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acid and 2-hydroxyethyl methacrylate; Vinyl esters such as vinyl acetate and vinyl propionate; Aromatic vinyls such as styrene and vinyltoluene; Acrylonitrile , unsaturated nitriles such as methacrylonitrile; unsaturated amides such as acrylamide and N-methylolacrylamide; α-olefins such as ethylene, propylene, and isobutylene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and t-butyl vinyl ether. ; Halogen-containing α such as vinyl chloride, vinylidene chloride, vinyl fluoride, and vinylidene fluoride.

β-unsaturated monomers: trifluoroethyl (meth)acrylate, 2.2.3.3-tetrafluoropropyl acrylate, 11-(, IH, 2H, 2H-hebutadecafluorodecyl acrylate, 18. 1H.

Fluorine-containing (meth)acrylic acid esters such as 5H-octafluoropentyl acrylate: 2.3.5゜6-
Titrafluorophenyl acrylic acid ester, 2, 3.
Examples include aromatic fluorine-containing (meth)acrylic esters such as 4.5.6-pentafluorophenyl methacrylic ester, and one type or a mixture of two or more of these can be used.

The amount of polymerizable monomer (D) used is 0 to 98.45% by weight.
It can be determined as appropriate within the range. 98.45% by weight
If the amount used exceeds the above-mentioned organopolysiloxane (
A), polymerizable silane compound (B) or unsaturated organic acid (
The amount of C) used is less than the above-mentioned range, which is undesirable because the above-mentioned drawbacks occur.

The polymer that is an essential component of the treatment agent of the present invention is a polymerizable silane compound (B), an unsaturated organic acid (C), and others copolymerizable with these in the presence of an organopolysiloxane containing a terminal hydroxyl group (^). It can be produced by polymerizing the polymerizable monomer (0) by a conventionally known polymerization method. For example, solvents that can be used when employing the solution polymerization method include toluene, hexane, methyl ethyl ketone, ethyl cellosolve, ethyl acetate, isopropyl alcohol, etc. One type or a mixture of two or more of these can be used. You can. Examples of the polymerization initiator include common radical polymerization initiators such as azobisisobutyroni-1-lyl and benzoyl peroxide.

The reaction temperature is room temperature to 200°C, preferably 40 to 120°C.
℃ range.

The polymer thus obtained can be used as it is as the surface treatment agent for inorganic building materials of the present invention, but in consideration of the workability of the painted surface, it may be used after being dissolved or dispersed in various media. is preferable. In particular, a solvent solution of a polymer obtained by a solution polymerization method can be used as it is as a processing agent of the present invention with good workability. Furthermore, when preparing the treatment agent of the present invention, in addition to the polymer or a solution of the polymer, commonly known curing catalysts, colorants, pigments, toners, wetting agents, leveling agents, penetrating agents, antistatic agents, etc. There is no problem in adding various additives as long as they do not impair the purpose of the present invention.

Furthermore, if necessary, general-purpose resins conventionally used for inorganic building materials can be used in combination without impairing the characteristics of the treatment agent of the present invention. Examples of such resins include acrylic resins, epoxy resins, urethane resins, vinyl chloride resins, polyester resins, olefin resins, and alkyd resins, depending on the required physical properties. , these resins can be selected and used as appropriate. The amount used can be at most 1000 parts by weight (in terms of non-volatile content), preferably not more than 500 parts by weight (in terms of non-volatile parts) per 100 parts by weight (in terms of non-volatile parts) of the surface treatment agent of the present invention.

Inorganic building materials that can be coated with the surface treatment agent for inorganic building materials of the present invention are construction materials mainly composed of inorganic materials such as row-based, brick-based, cement-based, calcium silicate-based, gypsum-based, asbestos-based, etc. There are no particular restrictions, and examples include Oya stone, brick, light concrete,
Precast concrete, lightweight aerated concrete (A
LC), mortar, asbestos cement board, wood wool cement board,
Includes gypsum board, hardboard, plaster, gypsum plaster, dolomite plaster, hard plaster, etc.

In order to apply the surface treatment agent for inorganic building materials of the present invention to the surface of inorganic building materials, conventionally known coating methods such as brush coating, spraying, roller coating, and dipping can be employed. Also,
Drying may be carried out at room temperature, or may be carried out under heating conditions if necessary.

(Effects of the Invention) The inorganic building materials treated with the surface treatment agent of the present invention obtained in this way have excellent water repellency, waterproofness, efflorescence resistance, etc., and these properties are maintained over a long period of time. Because it is maintained, it has extremely high utility value as an industrial material.

The reason why the surface treatment agent of the present invention exhibits such excellent performance is not clear, but it is thought to be approximately as follows.

That is, by polymerizing the polymerizable monomer component containing the polymerizable silane compound (B) in the presence of the terminal hydroxyl group-containing organopolysiloxane (A), the polymer chains produced by the polymerization of the monomer component are The reactive group contained in the silane compound unit and the terminal hydroxyl group contained in the organopolysiloxane (A) react, and a polymer grafted with the organopolysiloxane component is obtained. When the surface treatment agent of the present invention containing such a polymer is applied to an inorganic building material, the organopolysiloxane component is present at the air-side interface, while the polymer chain component generated by polymerization of the polymerizable monomer component is is oriented at the interface on the base material side, and as a result, the a! ! This is thought to be due to the formation of a coating film that exhibits both high adhesion and adhesion. However, this reason does not limit the present invention in any way.

(Examples) The present invention will be specifically described below with reference to Examples, but the present invention is not limited in any way by these. In addition, all parts in the examples indicate parts by weight.

Reference Example 1 In a four-eye flask equipped with a thermometer, reflux condenser, dropping funnel, nitrogen inlet tube, and stirrer, prepare 2〇H3 as an organopolysiloxane containing a terminal hydroxyl group (where n is 1500 on average). 30 of dihydroxydimethylpolysiloxane
10 parts of a wt% toluene solution and 100 parts of toluene were charged, and 8 parts were heated to 4° C. under a nitrogen atmosphere. To this, 64.4 parts of methyl methacrylate, 20 parts of butyl acrylate, 5 parts of acrylic acid, 5.6 parts of hydroxyethyl acrylate,
20% by weight of a homogeneous monomer solution consisting of 5 parts of γ-methacryloxypropyltrimethoxysilane and 2 parts of azobisisobutyronitrile was added, and the mixture was heated at 80'C for 3 portions.
Initial polymerization was performed. Next, the remaining monomer homogeneous solution was added dropwise over 2 hours at the same temperature, and when the polymerization was continued for 20 minutes after the addition was completed, 1.0 parts of isopropyl alcohol was added to dilute the solution. Continue to maintain the temperature at 80°C for 3 hours at 40°C.
After stirring for several minutes to continue the polymerization reaction, the solution of the polymer for surface treatment agent of the present invention (hereinafter referred to as polymer solution (1
). ) was obtained. The viscosity of the obtained polymer solution (1) was 5Qcps (25°C, B type viscometer, 60 rpm),
The solid content was 33.3% by weight.

Reference Example 2 Add Reference Example 1 to a four-bottle flask similar to that used in Reference Example 1.
33.3 parts of a 30% by weight toluene solution of the same terminal hydroxyl group-containing organopolysiloxane as used in 1.
The temperature rose to . To this was added a homogeneous monomer solution consisting of 50 parts of methyl methacrylate, 20 parts of butyl acrylate, 20 parts of acrylonitrile, 5 parts of acrylic acid, 5 parts of γ-methacryloxypropyltrimethoxysilane, and 2 parts of azobisisobutyronitrile. The initial polymerization operation and the dropping operation of a homogeneous monomer solution were carried out in the same manner as in Reference Example 1. When the polymerization was continued for 30 minutes after the dropwise addition of the monomer homogeneous solution, 100 parts of ethyl alcohol was added to dilute the solution. Further at 80℃ 3
The reaction was continued for 30 minutes and then cooled to obtain a solution of the polymer for surface treatment agent of the present invention (hereinafter referred to as polymer solution (2)). The viscosity of the obtained polymer solution (2) is 7
The solid content was 33.0% by weight at 0 cps (25° C., B-type viscometer, 60 ppm).

Reference Example 3 Into a fourth flask similar to that used in Reference Example 1, 3 parts of dihydroxydimethylpolysiloxane represented by the formula (however, n is 650 on average) as an organopolysiloxane containing terminal hydroxyl groups and 100 parts of toluene were charged. , under nitrogen atmosphere, 80℃
The temperature rose to . To this was added a homogeneous monomer solution consisting of 30 parts of methyl methacrylate, 30 parts of styrene, 30 parts of vinyl acetate, 5 parts of acrylic acid, 5 parts of 2-sdyryldyltrimethoxysilane, and 2 parts of azobisisobutyronitrile. Using this, the same initial polymerization operation and dropping operation of a monomer homogeneous solution as in Reference Example 1 were performed. 15 after the completion of dropping monomer homogeneous solution
When polymerization was continued for minutes, isopropyl alcohol 100
diluted by adding 1 part. The polymerization reaction was further continued at 80° C. for 3 hours and 45 minutes, and then cooled to obtain a solution of the polymer for surface treatment agent of the present invention (hereinafter referred to as polymer solution (3)).

The viscosity of the obtained polymer solution (3) was 55 cps (25°C
, type B viscosity, 60 ml), and solid content was 33.9%.

Reference Example 4 The same procedure as Reference Example 1 was performed except that the terminal hydroxyl group-containing organopolysiloxane in Reference Example 1 was not used, and the viscosity (25°C, B-type viscometer, 60 ppm) was 4.
A comparative polymer solution with a solid content of 33.2% at 0 cps (hereinafter referred to as comparative polymer solution (1)).

).

Reference Example 5 In Reference Example 1, the viscosity (25°C, B-type viscometer, 60 rpm) 2
A comparative polymer solution having a solid content of 33.2% at 5 cps (hereinafter referred to as comparative polymer solution (2)).

)　　ml　.

Example 1 The polymer solution (1) obtained in Reference Example 1 was diluted with toluene to a solid content concentration of 4w%. This diluted polymer solution (
A surface treating agent (1) of the present invention was prepared by adding 0.5 part of dibdeltin dilaurate as a curing catalyst to 11,100 parts. This surface treatment agent was applied with a brush to a mortar (based on LIISR5201) at a rate of 40 to 70 g/TrL2, and dried at room temperature for 24 hours to obtain a test piece for performance evaluation.

The performance evaluation results of the obtained test pieces are shown in Table 2. Note that performance evaluation was performed according to the following method.

(1) Water permeability: Water permeability was measured after 24 hours in accordance with JrSA6910.

(2) Water repellency: The contact angle of the coating film with water was measured by the droplet method using a contact angle measuring device (manufactured by Kyowa Interface Science ■, CA-Hemata).

(3) Effluorescence prevention property: The test piece was placed in a constant temperature and humidity chamber (Tabai (manufactured by +M, PR-2GM) as shown in Figure 1, and the occurrence of efflorescence on the coating surface was observed after 14 days. The temperature inside the tank during the test was set at near °C and humidity: 50% Rl-(.

Examples 2 to 3 and Comparative Examples 1 to 2 In Example 1, surface treatment agents (2) to (3) and comparative surface treatment agents (1) to (2) having the formulations shown in Table 1 were used as surface treatment agents. ), and a test piece for performance evaluation was obtained in exactly the same manner as in Example 1, except that the substrate and coating method were as shown in Table 2. The performance evaluation results of the obtained test pieces were as shown in Table 2. As reference data, Table 2 also shows the performance evaluation results conducted in the same manner using a base material not coated with a surface treatment agent.

Example 4 and Comparative Example 3 The test pieces obtained in Example 1 and Comparative Example 2 were exposed outdoors for 4 months under a south facing condition of 45 degrees, and then their water repellency performance was evaluated. The contact angle of the test piece obtained in Example 1 with water was 112 degrees, and the initial water repellency was maintained at a high retention rate. On the other hand, the contact angle of the test piece obtained in Comparative Example 2 with water was 78 degrees, indicating that the water repellency was significantly reduced.

Chapter 1 Table Table 2 ― *Evaluation) ○: No effusion occurred △: Partial efflorescence ×: Efro occurs on the entire surface

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing the outline of the eflo-prevention test. 1: Coating film 2: Test piece base material (sides sealed with paraffin) 3. Pure water 4. Transparent acrylic board 5. Stand to place the test piece Patent applicant: Nippon Shokubai Chemical Co., Ltd. Figure 81

Claims (1)

[Claims] 1. Organopolysiloxane containing terminal hydroxyl groups (
A) In the presence of 1 to 80% by weight, a polymerizable silane compound (B
) 0.05-10% by weight, unsaturated organic acid (C) 0.5-10% by weight
10% by weight and other polymerizable monomers (D) copolymerizable with these 0 to 98.45% by weight (However, (A), (B),
The total of components (C) and (D) is 100% by weight. )
A surface treatment agent for inorganic building materials comprising a polymer obtained by polymerizing.