JP2023156581A - modified silicone composition - Google Patents

Abstract

To provide a modified silicone composition for bonding a surface material such as a floor material or a wall material to a substrate material, such as the substrate material of a floor or the substrate material of a wall, wherein the modified silicone composition does not cause misalignment or peeling after the substrate material of the floor and the floor material, and the substrate material of the wall and the wall material are bonded, even under normal use; and when they are demolished, the surface material such as the floor material and the wall material can be readily peeled, and there is no need of replacing the substrate by damaging it.SOLUTION: A modified silicone composition comprises, relative to 100 pts.mass of modified silicone (A), 70 to 150 pts.mass of plasticizer (B), 50 to 350 pts.mass of Kansuiseki (C) having a dry sieving test average particle size based on JIS-Z-8815 of 0.1 to 0.6 mm, and 50 to 400 pts.mass of an additional filler (D).SELECTED DRAWING: None

Description

The present invention relates to a modified silicone composition for adhering a surface material such as a floor material or wall material to a base material such as a floor material or a wall material.

BACKGROUND OF THE INVENTION In buildings such as general houses, apartment complexes, offices, commercial facilities, medical facilities, welfare facilities, etc., surface materials such as flooring materials and wall materials are generally interior finished. In the case of floors in general homes, a plywood base is installed on top of the flooring, and composite flooring materials may be laminated on top of that.
Plywood, gypsum board, and the like are used as base materials for flooring and wall materials, but in both cases interior finishing is performed on surface materials such as flooring and wall materials.
In the case of apartment buildings, offices, commercial facilities, medical facilities, and welfare facilities, the base material may be concrete, in which case a decorative resin sheet with foam may be pasted, or on top of the concrete. In some cases, a cushioning base material such as wood or gypsum board is provided, and flooring materials, wall materials, etc. are installed on top of this.
In this way, various materials are used for base materials such as floor materials and wall materials, and various materials are also used for surface materials such as floor materials and wall materials. Modified silicone compositions are often used for adhesion of such a wide variety of materials.

When interior finishing is done by adhering surface materials such as flooring or wall materials to the underlying materials such as flooring materials or wall materials, they may shift or shift while people are living there. It is required that it does not peel off.

As people live there, flooring and wall materials deteriorate and will eventually need to be replaced. This is often seen in rental stores and rental housing, and surface materials such as flooring and wall materials may be replaced when the lessee changes.
In this case, there is a need for a modified silicone composition that can be easily removed from surface materials such as flooring and wall materials and that does not damage the underlying material and eliminate the need to replace the underlying material.

JP2009-024095 JP2006-096859 JP2007-016129 JP2020-029473

Patent Document 1 relates to an easily peelable one-component moisture-curing adhesive used when bonding a surface material such as a flooring material or wall material to a base material such as a flooring material or a wall material, and particularly relates to an easily peelable one-component moisture-curing adhesive used when adhering a surface material such as a floor material or wall material to a base material such as a floor material or a wall material. It is an easy-to-peel one-component moisture-curing adhesive that can easily peel off the surface material and streamline the work of replacing surface materials such as flooring materials in residential buildings, etc., and the purpose is almost the same as the present application. However, there was room for improvement in releasability.

Patent Document 2 discloses a sealing material composition that, when used for a sand-like ceramic siding board joint, has an appearance that harmonizes with the external wall, and has the physical properties of low modulus and high elongation required for the ceramic siding board joint. There are things. Patent Document 3 discloses a sealing material composition for balloons that is difficult to break during compounding, is lightweight, and has good workability, and the cured product has physical properties of low modulus and high elongation, and has a rough texture on the surface. There is a sealant composition that can be suitably used as a sealant. Patent Document 2 and Patent Document 3, which compositions are used as modified silicone compositions for adhering surface materials such as floor materials and wall materials to foundation materials such as floor materials and wall materials. There was room for improvement in releasability.

In Patent Document 4, the resin composition does not flow out even when applied on a substantially vertical surface, and after being thinly stretched using a comb-shaped trowel, there is no stringiness when the comb-shaped trowel is removed from the liquid resin composition. Patent Document 1, Patent Document 2, and Patent Document 1 disclose that a composition can be obtained that exhibits good adhesion after tile bonding without contaminating the surrounding area, and in which unreacted components of the resin composition do not bleed out from the cured product. Similar to Document 3, there was room for improvement in releasability.

The problem to be solved by the present invention is to obtain a modified silicone composition for adhering a surface material such as a floor material or wall material to a base material such as a floor material or a wall material, The modified silicone composition can be used to bond a floor base material and a wall base material, or a wall base material and a wall material, without causing them to shift or peel off even during normal life, and when they are disassembled. The object of the present invention is to obtain a modified silicone composition that can be easily removed from surface materials such as flooring materials and wall materials, and does not damage the underlying material and eliminate the need to replace the underlying material.

100 parts by mass of modified silicone (A), 70 to 150 parts by mass of plasticizer (B), dry sieving test based on JIS-Z-8815, and ankansuite (C) with an average particle diameter of 0.1 to 0.6 mm. This is a modified silicone composition containing 50 to 350 parts by mass of filler (D) and 50 to 400 parts by mass of filler (D).

The purpose of the modified silicone composition according to the present invention is to obtain a modified silicone composition for adhering a surface material such as a floor material or wall material to a base material such as a floor material or a wall material, The modified silicone composition can be used to bond a floor base material and a wall base material, or a wall base material and a wall material, without causing them to shift or peel off even during normal life, and when they are disassembled. is a modified silicone composition that can be easily removed from surface materials such as flooring and wall materials, and there is no need to damage or replace the underlying material, so it is safe for people to live in. You can live there, and surface materials such as flooring and wall materials can be easily replaced.
Note that various materials are used for base materials such as floor base materials and wall base materials, and various materials are used for surface materials such as floor materials and wall materials, but the modified silicone composition of the present application is a modified silicone composition that can be used in any combination.

An example of a modified silicone composition for adhering a surface material such as a floor material or a wall material to a base material such as a floor material or a wall material is shown below.

The modified silicone (A) used in this application has a structure such as polyether polyol, polyester polyol, acrylic polyol, polycarbonate polyol, etc. in the main skeleton, and has a hydrolyzable silyl group in either the main chain or side chain. It is a compound. The alkoxy group of the hydrolyzable silyl group is hydrolyzed by moisture in the air, and the resulting silanol group is condensed, thereby progressing the polymerization.
Modified silicone (A) is commercially available, and specific product names include: Kaneka, product name: Cyryl EST-250, product name: Cyryl EST-280, product name: Cyryl OR110S, product name: Cyryl MA440, Product Name: Cyryl MA480, Product Name: Cyryl MA451, Product Name: Cyryl MA904, Product Name: Cyryl MAX602, Product Name: Cyryl MAX923, Product Name: Cyryl MAX951, Product Name: Cyryl S203H, Product Name: Cyryl S227, Product Name: Cyryl S303H, Product Name: Cyryl S327, Product Name: Cyryl SA100S, Product Name: Cyryl SA310S, Product Name: Cyryl SA410S, Product Name: Cyryl SAT010, Product Name: Cyryl SAT-200, Product Name: Cyryl SAT145, Product name: Cyryl SAX015, Product name: Cyryl SAX260, Product name: Cyryl SAX350, Product name: Cyryl SAX400 are sold by Wacker Chemie Aktiengesellschaft, Product name: STP-E10, Product name: STP-E15, Product Name: STP-E30, product name: STP-E35, etc. are on sale.
Wacker Chemie Aktiengesellschaft products are sometimes referred to as silylated urethanes because the main skeleton and hydrolyzable silyl groups are connected via urethane bonds. Note that these can be used in combination.

As the plasticizer (B), any compound can be added as long as it is compatible with the modified silicone composition and does not react with the modified silicone (A). Examples of such compounds include polyether polyols, acrylic polyols, polyester polyols, and hydroxyl group-containing liquid rubbers.

Polyether polyols are commercially available, and specific product names include AGC's product name: EXCENOL420, product name: EXCENOL720, product name: EXCENOL1020, product name: EXCENOL2020, product name: EXCENOL3020, and product name: Examples include EXCENOL430, product name: EXCENOL1030, product name: EXCENOL3030, product name: EXCENOL4030, and product name: EXCENOL5030.
Acrylic polyols are commercially available, and specific product names include Toagosei's product name: ARUFON UP-1000, product name: ARUFON UP-1021, product name: ARUFON UP-1061, and product name: ARUFON. Examples include UP-1110, product name: ARUFON UH-2000, product name: ARUFON UH-2041, product name: ARUFON UH-2170, and product name: ARUFON UH-2190.
The amount of plasticizer (B) added is 70 to 150 parts by mass, more preferably 85 to 135 parts by mass, per 100 parts by mass of modified silicone (A). Note that these can be used in combination.

Kansuite is a granular marble whose main component is calcium carbonate. The average particle size is a dry sieving test average particle size based on JIS-Z-8815, and a preferable average particle size is 0.1 to 0.6 mm.
A specific product name of Kansuiseki (C) having an average particle diameter of 0.1 to 0.6 mm is Hakuryu Kaiseki Ichirin manufactured by Asahi Kosuesha.
The amount of agarite (C) with an average particle diameter of 0.1 to 0.6 mm is 50 to 350 parts by mass, more preferably 60 to 340 parts by mass, per 100 parts by mass of modified silicone resin (A). It is. In addition, various types of akansuite with different average particle sizes can be used in combination within the range that satisfies the required performance.

Other fillers (D) may be inorganic or organic materials. Inorganic materials include calcium carbonate, talc, silica, calcium oxide, kaolin, calcined kaolin, clay, calcium silicate, calcium sulfate, and aluminum oxide. (alumina), aluminum hydroxide, aluminum silicate, titanium oxide, zinc oxide, magnesium carbonate, magnesium silicate, zeolite, glass beads, and shirasu balloons.
Organic materials include polyethylene, polypropylene, polymethyl methacrylate, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-vinyl acetate copolymer, nylon, polyethylene terephthalate, Examples include polybutylene terephthalate, polystyrene, ABS resin, acrylonitrile-styrene copolymer, polycarbonate, and the like.

Specifically, the product names of calcium carbonate are manufactured by Shiraishi Calcium Co., Ltd., product name: Softon SB, product name: Softon 2200, product name: Softon 3200, product name: Softon SB, Hakuenka CCR-B, product name: White. Examples include Whiten SB and product name: Whiten SSB. Specific talc product names include Nippon Talc's product name: Micro Ace MS, product name: Micro Ace MS-P, product name: Micro Ace P-2, product name: Micro Ace K-1, etc. can be mentioned. Note that these can be used in combination.
In addition, hollow fillers such as fly ash balloons, shirasu balloons, and glass balloons may float out of the composition and separate, or after bonding the base material of the floor and the base material of the wall, and the base material of the wall and the wall material. It is better not to use it as it may slip or peel off.

A silane coupling agent can be added to the modified silicone composition of the present application in order to improve adhesion. Specifically, the product names are: Shin-Etsu Chemical Co., Ltd., product name: KBM-1003 (vinyltrimethoxysilane), product name: KBM-603 (N-2-(aminoethyl)-3-aminopropyltrimethoxy) Silane), Product name: KBM-403 (3-glycidoxypropyltrimethoxysilane), Product name: KBM-503 (3-methacryloxypropyltrimethoxysilane), Product name: KBM-903 (3-aminopropyltrimethoxysilane). methoxysilane). The amount added is 0 to 15 parts by weight, more preferably 1 to 12 parts by weight, per 100 parts by weight of the modified silicone (A). Note that these can be used in combination.

A reaction catalyst can be added to the modified silicone composition of the present application in order to promote the hydrolysis reaction of the alkoxy group of the hydrolyzable silyl group of the modified silicone (A).
As the reaction catalyst, tin-based, bismuth-based, or amine-based catalysts can also be used.
To give specific product names, the tin catalyst is manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-100, product name: Neostan U-130, product name: Neostan U-200, product name: Neostan U-220H. , trade name: Neostan U-303, etc.
As the bismuth catalyst, Nitto Kasei Co., Ltd. sells product name: Neostan U-600, and Matsuo Sangyo Co., Ltd. sells product names such as Borchi Kat24 and Borchi Kat315.
As amine catalysts, products such as U-CAT SA-1, U-CAT SA-102, U-CAT SA-106, U-CAT SA-112, U-CAT SA-506, etc. manufactured by Sun-Apro Co., Ltd. are sold. has been done.
The amount added is 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, per 100 parts by weight of the modified silicone (A). Note that these can be used in combination.

An antioxidant can be added to the modified silicone composition of the present application. Examples of the antioxidant include phosphorus-based, hydroquinone-based, bis-tris-polyphenol-based, thiobisphenol-based, and hindered phenol-based antioxidants.
The amount added is 0 to 5 parts by weight, more preferably 0 to 3 parts by weight, per 100 parts by weight of the modified silicone (A). Note that these can be used in combination.

In addition, an index of not shifting or peeling after bonding a floor base material and a floor material, or a wall base material and a wall material, can be evaluated by the planar tensile strength described below. In addition, an index of ease of peeling between a floor base material and a flooring material, and between a wall base material and a wall material can be evaluated by the splitting strength described below.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but these are intended to be specific examples and are not particularly limited to these.

Preparation of modified silicone composition of Example 1 In a pot of a planetary mixer manufactured by Inoue Seisakusho Co., Ltd. (trade name: PLM-2), 100 g of Cyryl EST-280, 100 g of EXCENOL 3020, 70 g of Hakuryu crushed stone, and Whiten 230 g of SB, 50 g of Hakuenka CCR-B, 6 g of KBM-1003, 4 g of KBM-603, and 1.5 g of Neostan U-220H were stirred and mixed at 23° C. under reduced pressure to obtain the modified silicone composition of Example 1. The fabrication was obtained.

Preparation of modified silicone compositions of Examples 2 to 10 and Comparative Examples 1 to 15 Examples 2 to 10 were prepared in the same manner as in the preparation of the modified silicone composition of Example 1 using the blending ratios shown in Tables 1 and 2. 10. Modified silicone compositions of Comparative Examples 1 to 15 were prepared.
In addition, Hakuryu Kaiseki Nirin has an average particle size of 0.7 mm, and Hakuryu Kaiseki Sanrin has an average particle diameter of 1 mm. is a bisphenol A type diglycidylate manufactured by Mitsubishi Chemical Corporation, which is an epoxy compound, and Eponit K100 is a ketimine compound manufactured by Nitto Kasei Co., Ltd., which is an epoxy curing agent.

The plane tensile strength test was conducted in accordance with JIS K 6849. A 70 mm x 70 mm x 12 mm thick plywood and a 40 mm x 40 mm x 12 mm thick plywood were prepared.
500 to 600 g/m ² of the modified silicone composition was applied onto a plywood board of 70 mm x 70 mm x 12 mm thickness, and the modified silicone composition was rolled out using a comb-shaped trowel in accordance with JIS A5536 (adhesives for floor finishing materials). Then, a 40 mm x 40 mm x 12 mm thick plywood was placed on top of it, and a 1 kg weight was placed on top of the plywood, followed by compression for 5 seconds. After removing the weight, the protruding modified silicone composition was removed, and the modified silicone composition was left to stand for 168 hours at 23° C. to cure the modified silicone composition.
Adhesive strength was measured using an autograph universal testing machine AG-Xplus manufactured by Shimadzu Corporation at a tensile speed of 3 mm/min. n=5 average. The results are shown in Tables 3 and 4.
The criteria for judgment is that if it is 0.84N/mm2 ^or more, there will be no misalignment between the base material such as floor base material or wall base material and the surface material such as floor material or wall material even during normal life. It was determined that it would not peel off, so it passed the test. Less than 0.84 N/mm ² is a failure.

Splitting strength The test was conducted in accordance with JIS K 6853. A 70 mm x 40 mm x 12 mm thick plywood, a 50 mm x 25 mm x 12 mm thick plywood, and two spacers 5 mm wide and 0.3 mm thick were prepared.
Spacers with a width of 5 mm and a thickness of 0.3 mm were arranged at both ends of the long sides of a 70 mm x 40 mm x 12 mm thick plywood, so that the contact volume was 30 mm x 25 mm x 0.3 mm thick. 1.5 to 2 g of modified silicone composition is applied thereto, and one long side of a 70 mm x 40 mm x 12 mm thick plywood and one short side of a 50 mm x 25 mm x 12 mm thick plywood are coated on top of it. A piece of plywood 50 mm x 25 mm x 12 mm thick was placed so that it was evenly aligned, and it was crushed by hand for 5 seconds. The protruding modified silicone composition was removed, and the modified silicone composition was left to stand for 168 hours at 23° C. to cure the modified silicone composition.
A 50mm x 25mm x 12mm thick plywood has an area of about 10mm x 25mm and there is a part that does not overlap with another plywood, but by hooking an L-shaped jig to that part, the autograph universal test made by Shimadzu Corporation was carried out. The adhesive strength was measured using a machine AG-Xplus at a tensile speed of 50 mm/min. n=5 average. The results are shown in Tables 3 and 4.
As a criterion, if it is 270N/25mm or less, it is judged that the surface material such as flooring material or wall material can be easily removed without damaging the base material, and it is passed. Exceeding 270N/25mm is a failure.

100 parts by mass of modified silicone (A), 70 to 150 parts by mass of plasticizer (B), dry sieving test based on JIS-Z-8815, and ankansuite (C) with an average particle diameter of 0.1 to 0.6 mm. Examples 1 to 9, which are modified silicone compositions containing 50 to 350 parts by mass of filler (D) and 50 to 400 parts by mass of filler (D), passed both plane tensile strength and splitting strength.

Dry sieving test based on JIS-Z-8815 Examples 1 to 4 in which no agarite (C) with an average particle size of 0.1 to 0.6 mm were added, and Example 5 in which the amount added was small, showed that the splitting strength was It was found to be rejected and could not be easily peeled off.
Dry sieving test based on JIS-Z-8815 Comparative examples 6 and 7 using akansuite (C) with a larger average particle size than akansuite (C) with an average particle size of 0.1 to 0.6 mm are It was found that the strength was rejected, and there was a risk that the base materials such as floor base materials and wall base materials and the surface materials such as floor materials and wall materials could become misaligned or peel off.
Comparative Example 8, in which no other filler (D) was added, failed in plane tensile strength.

Comparative Example 9, in which the added amount of plasticizer (B) was small, was rejected for splitting strength, and Comparative Examples 10 and 11, in which the added amount was large, were failed in plane tensile strength. A large amount of plasticizer (B) is added, no agarite (C) with an average particle diameter of 0.1 to 0.6 mm in dry sieving test based on JIS-Z-8815 is added, and a large amount of other filler (D) is added. Comparative Example 12 failed in plane tensile strength.

Other fillers among modified silicone (A), plasticizer (B), dry sieving test based on JIS-Z-8815 with an average particle size of 0.1 to 0.6 mm agarite (C), and other fillers (D) Comparative Example 13, in which Senolite SA of the fly ash balloon, which is a hollow filler, was used as (D), the planar tensile strength was rejected. Dry sieving test based on JIS-Z-8815 Comparative Example 14, in which Senolite SA was used instead of Kansuiite (C) with an average particle diameter of 0.1 to 0.6 mm, failed in terms of splitting strength.
Comparative Example 15, which used 828, which is a bisphenol A type diglycidylate and is an epoxy compound, and Eponite K100, which is a ketimine compound that is a curing agent thereof, failed in terms of splitting strength.

Claims (3)

100 parts by mass of modified silicone (A), 70 to 150 parts by mass of plasticizer (B), dry sieving test based on JIS-Z-8815, and ankansuite (C) with an average particle diameter of 0.1 to 0.6 mm. A modified silicone composition containing 50 to 350 parts by mass of filler (D) and 50 to 400 parts by mass of filler (D). The modified silicone composition according to claim 1, which does not contain a hollow filler such as a fly ash balloon or an epoxy compound. The modified silicone composition according to claim 1 or 2, wherein the modified silicone composition is used for adhering a surface material such as a flooring material or a wall material to a base material such as a floor material or a wall material. thing.