JP4889354B2 - Joint material composition and joint formation method - Google Patents

Description

  The present invention relates to a joint material composition filled in a joint gap formed between building materials such as tiles and stones, a joint formation method using the joint material composition, and a joint structure. A joint material composition having good wiping workability with water and excellent in elasticity, adhesiveness and water resistance, a method of forming joints by a joint joint method using the joint material composition, and Concerning joint structure.

  Conventionally, inorganic joint materials mainly composed of cement have been used for filling the joints between the tiles and stones. As a joint filling method for such joint materials, a joint joint method with high construction efficiency is widely adopted. This joint joint method is a method in which paste joint material is applied to one surface of a floor or wall tile or stone, the joint material is filled in the joint gap, and then the excess joint material on the surface of the tile or stone is wiped off. Therefore, joint filling can be performed very efficiently (see, for example, Patent Documents 1 and 2).

  Since the inorganic joint material is water-based, excess joint material adhering to the tile surface during joint filling can be easily wiped off with a sponge moistened with water. However, since the inorganic joint material is poor in elasticity, there is a problem that when it is applied to a base where bending occurs, it tends to crack or chip, and it cannot follow the movement of the base and causes tile cracks.

In recent years, in order to solve the above problems, there is a tendency to use an organic joint material having elasticity instead of an inorganic joint material. However, since the organic joint material is non-aqueous, the joint is filled with a joint joint. If this is done, it is necessary to use an organic solvent after wiping off the excess joint material adhering to the tile surface, and then using an organic solvent to wipe off stains remaining on the tile surface. It was complicated. Examples of construction methods other than the fill joint method include, for example, a single joint where the joint material is filled only in the joint portion, a method of masking the tile surface, filling the joint material, and then removing the masking coating film. Although there is (patent document 3), all have the problem that workability | operativity is inferior compared with an inorganic type joint material.
Japanese Patent Laid-Open No. 5-156781 JP 2001-49240 A JP-A 63-295207

  The present invention solves the problems associated with the prior art described above, and its purpose is that wiping with water is possible, and by following the movement of the foundation, cracking and chipping of joints are less likely to occur. And a joint material composition excellent in workability, elasticity, adhesion and water resistance, a joint formation method using the joint material composition, and joint structure can be provided. Is.

The present inventors can wipe off with water by blending 5 to 50 parts by weight of (b) a silicone surfactant with 100 parts by weight of a polymer having hydrolyzable silicon groups. The present invention has been found.
That is, the joint material composition of the present invention is a joint material composition used for a joint formation method in which joint materials are filled into joint spaces formed between tiles or stones by a joint joint method, and (a) hydrolysis A polymer having a functional silicon group and (b) a silicone-based surfactant, and (b) 15 to 50 parts by weight, more preferably 15 to 100 parts by weight of the polymer (a). It is characterized by comprising ~ 35 parts by weight. The joint material composition of the present invention preferably has a viscosity at 23 ° C. of 50 to 700 Pa · s.

  The joint material composition of the present invention preferably further contains (c) a silane coupling agent, and the amount of the (c) silane coupling agent is 0.5 to 100 parts by weight of the polymer (a). It is more preferable to blend 10 parts by weight. The (c) silane coupling agent is preferably aminosilane.

The joint forming method of the present invention is a method of forming joints by filling joint materials into tile joints formed between tiles or stones by a paint joint method , wherein the joint material is the joint material composition of the present invention. It is characterized by that.

  The joint structure is a joint structure in which joint materials are filled in joint joints, and the joint material is the joint material composition of the present invention.

  According to the present invention, it is possible to wipe off with water, and it is possible to efficiently perform construction by the joint joint method, and it is difficult to cause cracks and chipping of joints by following the movement of the foundation, and prevents cracking of tiles or stones The effect can be achieved.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

The joint material composition of the present invention contains (a) a polymer having a hydrolyzable silicon group, and (b) a silicone-based surfactant.
Component (a) Polymer having a hydrolyzable silicon group of the joint material composition of the present invention is a silicon having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. An organic polymer having a containing group, that is, a hydrolyzable silicon group is used.

  The hydrolyzable silicon group is not particularly limited, but generally 1 to 6 hydrolyzable silicon groups are contained in the molecule. The position of the hydrolyzable silicon group is not particularly limited and may be at the end or inside of the organic polymer molecular chain, or may be at both, but it is preferably at the end of the molecular chain. Furthermore, the hydrolyzable silicon group is preferably one represented by the following general formula (1) which is easy to crosslink and easy to produce.

[In Formula (1), R is a C1-C20 substituted or unsubstituted monovalent organic group, a C1-C20 alkyl group, a C6-C20 aryl group, or C7-C7 Twenty aralkyl groups are preferred, and a methyl group is most preferred. When a plurality of R are present, they may be the same or different. X is a hydroxyl group or a hydrolyzable group, and is a group selected from a halogen atom, hydrogen atom, hydroxyl group, alkoxy group, acyloxy group, ketoximate group, amide group, acid amide group, mercapto group, alkenyloxy group and aminooxy group Are preferred, alkoxy groups are more preferred, and methoxy groups are most preferred. When a plurality of X are present, they may be the same or different. n is 1, 2 or 3, and 2 is most preferable. ]

  In the polymer (a) having the hydrolyzable silicon group, when a plurality of hydrolyzable silicon groups are present, these may be the same or different, and further, n in the formula (1) The numbers may be the same or different. Two or more kinds of organic polymers having different hydrolyzable silicon groups may be used.

  The polymer in the polymer (a) having a hydrolyzable silicon group is not particularly limited. For example, a polyoxyalkylene polymer, a vinyl-modified polyoxy, each having a main chain that may contain an organosiloxane. Alkylene polymer, (meth) acryl-modified polyoxyalkylene polymer, (meth) acrylic polymer, vinyl polymer, polyester polymer, (meth) acrylic ester polymer, polyisobutylene polymer, and These copolymers (for example, JP-A No. 2003-238895, JP-A No. 2000-169544, JP-A No. 2004-059882, JP-A No. 2004-51830, JP-A No. 2003-138151 and JP-A No. 2003-138151 are disclosed. 2001-40037 publication etc.) can be mentioned as a suitable example. These polymers (a) may be used alone or in combination of two or more. In the present invention, acryl and methacryl are collectively referred to as (meth) acryl.

Specifically, the polymer (a) includes a polyoxyalkylene polymer having a hydrolyzable silicon group, a (meth) acrylic polymer having a hydrolyzable silicon group, and a hydrolyzable silicon group ( Suitable examples include (meth) acryl-modified polyoxyalkylene polymers and mixtures thereof.
The (meth) acrylic polymer having a hydrolyzable silicon group is more preferably a (meth) acrylic organic polymer having a hydrolyzable silicon group at the molecular chain terminal. The method for producing the (meth) acrylic polymer having a hydrolyzable silicon group at the end is not particularly limited, but a controlled radical polymerization method is preferable, a living radical polymerization method is more preferable, and an atom transfer radical polymerization method is further preferable. .

  The production method of the polymer (a) having a hydrolyzable silicon group is not particularly limited, and a known synthesis method can be used. When the hydrolyzable silicon group-containing organic polymer contains a hydrolyzable silicon group and the main chain is a vinyl polymer such as an acrylic polymer, a vinyl polymer synthesized by a radical polymerization method is used. It is desirable to use a polymer.

The radical polymerization method includes a general radical polymerization method in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound or a peroxide as a polymerization initiator, and a terminal or the like. A vinyl polymer synthesized by a controlled radical polymerization method in which a specific functional group can be introduced at a controlled position is more effective.
The controlled radical polymerization method further includes a chain transfer agent method in which a vinyl polymer having a functional group at the terminal is obtained by polymerization using a chain transfer agent having a specific functional group, and a polymerization growth terminal is terminated. It can be divided into the living radical polymerization method that grows without causing etc.

The living radical polymerization method has an arbitrary molecular weight, a molecular weight distribution is narrow, a polymer having a low viscosity can be obtained, and a monomer having a specific functional group can be introduced at an arbitrary position. Is particularly preferred. In the present invention, in addition to the polymerization in which the terminal always has activity and the molecular chain grows, the terminal inactivated and the activated one are grown while in equilibrium. Living polymerization is also included in living polymerization.
Living radical polymerization includes a method using a cobalt porphyrin complex, a method using a radical scavenger such as a nitroxide compound, an organic halogen compound, a sulfonyl halide compound, etc. as an initiator and a vinyl monomer as a catalyst using a transition metal complex as a catalyst. Atom transfer radical polymerization (ATRP) method and the like are mentioned. The living radical polymerization method is not particularly limited, but the atom transfer radical polymerization method is preferable. In the present invention, the reverse atom transfer radical polymerization method, that is, a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, Cu (II) when Cu (I) is used as a catalyst. In contrast to '), a general radical initiator such as a peroxide is allowed to act, and as a result, a method of producing parallelism similar to atom transfer radical polymerization is also included in the atom transfer radical polymerization method.

As the chain transfer agent method, a halogen-terminated polymer is obtained using a halogenated hydrocarbon as a chain transfer agent, or a hydroxyl-terminated polymer is obtained using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent. Methods and the like.
For example, it has a halogen at the terminal by radical polymerization of a vinyl monomer having an acrylic monomer as a main component using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. An acrylic polymer is produced. The (meth) acrylic polymer having a hydrolyzable silicon group at the molecular chain end used in the present invention is obtained by converting the halogen of the acrylic polymer having the halogen at the end to a hydrolyzable silicon group. Can do. The conversion method is not particularly limited, and a known method can be used.

  The number average molecular weight of the polymer (a) having a hydrolyzable silicon group is preferably 3,000 to 30,000, more preferably 5,000 to 20,000, and examples generally referred to as modified silicone resins. it can. Specific examples thereof include product names SAT200, MA903, and SA310S manufactured by Kaneka Corporation, product names Exester S3630 manufactured by Asahi Glass Co., Ltd., and the like.

  The component (b) silicone surfactant of the joint material composition of the present invention includes a nonionic surfactant in which the main chain is composed of, for example, dimethylsiloxane and polyalkylene oxide, methylsiloxane is a hydrophobic group, and alkylene oxide is a hydrophilic group. Examples of the agent include side chain-modified copolymers with Si-C bonds or terminal-modified polymers with Si-O-C bonds with respect to the dimethylsiloxane main chain. Various products are produced by adjusting the silicon concentration, the chain length of the dimethylsiloxane portion, the type of alkylene oxide, etc., and are also marketed as silicone surfactants, foam stabilizers for urethane foam, antifoaming agents, and the like. Specific examples thereof include Silwet L7604, FZ2162, and FZ2207 manufactured by Toray Dow Co., Ltd.

  The silicone surfactant (b) is preferably blended in an amount of 5 to 50 parts by weight with respect to 100 parts by weight of the polymer (a) having the hydrolyzable silicon group. If it is less than 5 parts by weight, it is difficult to wipe off the joint material adhering to the tile surface. If it exceeds 50 parts by weight, there is a problem in terms of water-resistant adhesion to the side surface of the tile after curing. Furthermore, blending 15 to 35 parts by weight of component (b) with respect to 100 parts by weight of component (a) is excellent in terms of wiping at the time of construction and adhesiveness to the tile side after curing, preferable.

  The joint material composition of this invention can improve adhesiveness more by mix | blending a silane coupling agent (c). Examples of the silane coupling agent (c) include aminosilanes represented by the following formula (2), epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. Acrylic silanes, vinylsilanes such as vinyltrimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate silanes such as γ-isocyanatopropyltrimethoxysilane, and the like, with aminosilanes being particularly preferred. These silane coupling agents may be used alone or in combination of two or more. In addition, alkoxysilanes that are copolymers of these silane coupling agents may be used.

[In Formula (2), Y is an alkyl group, an aryl group, an alkoxyalkyl group, or a cycloalkyl group that may contain a —NH ₂ group and / or a —NH— bond, and Z is a group having 1 to 6 carbon atoms. Represents an alkyl group. The three Zs may be the same or different. n is an integer of 1 to 3]

Specific examples of the aminosilanes include N-β- (aminoethyl) aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, and the like. Examples of commercially available products include “KBM603” and “KBM903” (manufactured by Shin-Etsu Chemical Co., Ltd.). These aminosilanes may be used alone or in combination of two or more. Moreover, you may use together aminosilanes and another silane coupling agent.
The aminosilanes may be blocked with a carbonyl compound, and examples of the carbonyl compound include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and aldehydes such as acetaldehyde, propionaldehyde, and benzaldehyde.

  The blending ratio of the silane coupling agent (c) is not particularly limited, but it is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight based on 100 parts by weight of the component (a). .

  The joint material composition of the present invention preferably has a viscosity at 23 ° C. of 50 to 700 Pa · s, more preferably 80 to 500 Pa · s. By using the joint material composition of this viscosity, the joints can be easily filled in the joint gap without dripping the joints even when the joints are applied to the vertical surface such as a wall. It can be significantly improved.

  An epoxy resin can be further added to the joint material composition of the present invention for the purpose of improving water-resistant adhesion. Conventionally known epoxy resins can be widely used. For example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated epoxy resins, novolac type epoxy resins, alcohol type epoxy resins, hydrogenated bisphenol A type epoxy resins. Glycidyl ether type epoxy resin such as bisphenol A propylene oxide addition epoxy resin, glycidyl ester type epoxy resin such as adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, diglycidyl aniline, p-aminophenol Examples thereof include glycidylamine type epoxy resins such as molds, various modified epoxy resins, alicyclic epoxy resins and the like, and these can be used alone or in combination.

  In addition, if necessary, a polymer having a hydrolyzable silicon group (a) as a compounding agent, a curing catalyst, a curing accelerator, a curing retarder, a plasticizer, a filler, an adhesion promoter, a diluent, a pigment, Dyes, dehydrating agents, ultraviolet absorbers, light stabilizers, antioxidants, fungicides and the like may be added.

  The joint formation method of the present invention uses the joint material composition of the present invention as the joint material in the method of forming joints by filling the joint material into joint spaces formed between building materials such as tiles and stones. Is. The construction method for filling the joint is not particularly limited, and a known method can be applied, but it is preferable to use the joint joint method. That is, the joint material composition of the present invention is applied to one surface of a building material such as a floor or wall tile or stone, and after filling the joint gap, the joint material adhered to the surface of the building material such as tile or stone is removed with water. The method is more preferred. The method for removing the joint material attached to the surface of the building material such as tile or stone is not particularly limited. For example, it is preferable to wipe off the joint material on the surface of the building material using a sponge soaked with water.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it cannot be overemphasized that these Examples are shown by illustration and should not be interpreted limitedly.

( Experimental Examples 1 and 2, Examples 1 to 4 and Comparative Examples 1 to 4)
According to the blending composition shown in Table 1, each blended substance was mixed at room temperature and reduced pressure using a high-viscosity mixing stirrer to obtain a joint material composition.

The compounding amounts of the compounding substances in Table 1 are shown in parts by weight, and * 1 to * 12 are as follows.
* 1: SA310S (manufactured by Kaneka Corporation)
* 2: SAT200 (manufactured by Kaneka Corporation)
* 3: Silwet FZ2162 (manufactured by Toray Dow Co., Ltd.)
* 4: Silwet L7604 (manufactured by Toray Dow Co., Ltd.)
* 5: KBM603 (Shin-Etsu Chemical Co., Ltd.)
* 6: KBM903 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 7: Whiten SB (Shiraishi Kogyo Co., Ltd., calcium carbonate)
* 8: White gloss flower CCR (Shiraishi Kogyo Co., Ltd., calcium carbonate)
* 9: Diisononyl phthalate * 10: Tetraethoxysilicate * 11: Neostan U-100 (manufactured by Nitto Kasei Co., Ltd.)
* 12: R820 (Ishihara Sangyo Co., Ltd.)

(Comparative Example 5)
Cement powder: 40 parts by weight, fine aggregate: 59 parts by weight, water retaining material (methylcellulose): 1 part by weight of water was added to a powder obtained by mixing water to obtain a cement joint material composition.

(Comparative Example 6)
A one-component modified silicone resin-based sealing material “POS seal” (manufactured by Cemedine Co., Ltd.) was used as a joint material composition.

The following test was done about the obtained joint material composition.
1) Viscosity The viscosity at 23 ° C. of the joint material composition obtained was measured using a B-type rotational viscometer. The results are shown in Table 2.

2) Workability Porcelain tiles were pasted on the walls, and joints with a width of about 5 mm were produced between the tiles. The obtained joint material composition was filled in joints between tiles while spreading with a paint joint method using a joint joint method, and evaluated for ease of application and prevention of joint dripping on a vertical surface. The results are shown in Table 2. The evaluation criteria for ease of application and sag prevention are as follows.
Ease of application: Five-stage evaluation was performed with 5 being the most easy to apply and good, and 3 or more were considered acceptable.
Sag prevention: A: No sagging, O: Slight sagging after 2 hours, x: Sagging immediately after application.

3) Wiping workability Porcelain tiles were pasted on the wall surface, and joints with a width of about 5 mm were produced between the tiles. The obtained joint material composition was filled in the joints between the tiles while spreading with a scissors by the joint joint method, and then the excess joint material was scraped off. Then, the joint material adhering to the tile surface was wiped and cleaned with a sponge moistened with water, and the wiping workability at that time was evaluated. The results are shown in Table 2.
Evaluation criteria: ◎: Wiping workability is good and no adhesion residue remains on the tile surface, ○: It takes a little work to wipe, but there is no adhesion residue remaining on the tile surface, △: Some joint material on the tile surface X: There is a large amount of joint material remaining on the tile surface.

4) Normal Adhesiveness FIG. 1 is a schematic explanatory view of a specimen for a normal adhesiveness test, (a) is a cross-sectional view, and (b) is a top view. In FIG. 1, 10 is a tile, and 12 is a joint material composition.
As shown in FIG. 1, two 50 mm square porcelain tiles 10 are arranged, a joint width of 5 mm is created between the tiles, and then the joint material composition 12 obtained is filled, and 7 days at 23 ° C. and 50% RH. Cured and used as test specimen 20a.
The prepared specimen was attached to a testing machine, a tensile test was performed at a speed of 50 mm / min, the stress until breaking was measured, and the breaking state was visually observed. The results are shown in Table 3. In Table 3, the fracture state was represented by cf: cohesive fracture of joint material, cf / af: interface fracture from a part of the tile side, af: interface fracture from the tile side.

5) Water-resistant adhesiveness A test body was obtained by the same method as the above-mentioned normal adhesiveness. The obtained specimen was immersed in water at 23 ° C. for 7 days, then attached to a testing machine, a tensile test was conducted at a speed of 50 mm / min, the stress until breaking was measured, and the breaking state was visually observed. The results are shown in Table 3. The fracture state was evaluated in the same manner as in the normal state adhesion test. Moreover, what peeled naturally after being immersed in water was shown by x.

6) Deflection followability test FIG. 2 is a schematic explanatory view of a test body for a deflection followability test, in which (a) is a cross-sectional view and (b) is a top view. FIG. 3 is a schematic explanatory view showing a method for testing the deflection followability.
As shown in FIG. 2, a 50 mm square porcelain tile 10 is attached to a 1 mm thick SUS plate 16 with an adhesive 14 (Tile Ace: Cemedine Co., Ltd.) with a joint spacing of 5 mm secured at 23 ° C. Curing was performed at% RH for 3 days. Thereafter, the obtained joint material composition 12 was filled and cured at 23 ° C. and 50% RH for 7 days to obtain a specimen 20b.
The prepared test body 20b was attached to the testing machine 30, and a displacement of 1 mm was applied from the SUS plate 16 as shown in FIG. 3, and the joint condition after the test was visually observed. In FIG. 3, the direction of the load is indicated by an arrow. The results are shown in Table 3.
Evaluation criteria: ◎: No abnormality, △: Cracks / cracks in some joint materials, x: Cracks / cracks in joints or peeling of tiles and joints.

  As shown in Table 2, the joint material composition of the present invention blended with a silicone surfactant was excellent in workability and could be wiped off with water. Furthermore, as shown in Table 3, the joint material composition of the present invention was excellent in normal-state adhesiveness, water-resistant adhesiveness, and deflection followability.

  The joint material composition of the present invention can be wiped off with water, and can be efficiently constructed by the joint joint method. Can be suitably used as a joint material for tiles and stones.

It is a schematic explanatory drawing of the normal adhesiveness test body produced in the Example, (a) is sectional drawing, (b) is a top view. It is a schematic explanatory drawing of the test body of deflection followability produced in the example, (a) is a sectional view and (b) is a top view. It is a schematic explanatory drawing which shows the test method of a deflection | trackability followability.

Explanation of symbols

10: tile, 12: joint material composition, 14: adhesive, 16: SUS plate, 20a, 20b: specimen, 30: testing machine.

Claims (5)

A joint material composition used in a joint formation method for filling joint materials between tiles or stones with joint materials by a joint joint method,
(A) a polymer having a hydrolyzable silicon group, and (b) a silicone-based surfactant, and 15 to 50 parts by weight of the (b) surfactant with respect to 100 parts by weight of the polymer (a). A joint material composition comprising:   The joint material composition according to claim 1, wherein 15 to 35 parts by weight of the surfactant (b) is blended with 100 parts by weight of the polymer (a).   The joint material composition according to claim 1 or 2, further comprising (c) a silane coupling agent.   The joint material composition according to any one of claims 1 to 3, wherein a viscosity at 23 ° C is 50 to 700 Pa · s. The joint material is a method of forming joints by filling joint materials into tile joints formed between tiles or stones, and the joint material is the joint material composition according to any one of claims 1 to 4. A joint formation method characterized by being.