JP2021127357A - Sealant composition - Google Patents

Abstract

To provide a sealant composition that has inconspicuous craters and excellent designability, and also has excellent workability and durability.SOLUTION: A sealant composition contains, based on 100 pts.mass of a polymer having a hydrolyzable silyl group (A), a resin hollow body (B) 0.1-10 pts.mass, calcium carbonate (C) 100-300 pts.mass, and silicon dioxide (D) 0.1-10 pts.mass.SELECTED DRAWING: None

Description

The present invention relates to a sealant composition.

Conventionally, a sealing material has been widely used for the purpose of filling joints and gaps between various members in buildings and the like to ensure watertightness or airtightness.

As a sealing material, Patent Document 1 states that it is hydrolyzed into a molecule for the purpose of providing a sealing material composition in which a slip phenomenon is less likely to occur during construction of the sealing material without deteriorating durability and adhesiveness after curing. With respect to 100 parts by weight of the polymer (A) having a silyl group and whose main chain skeleton is a polyalkylene ether or a (meth) acrylic acid ester-based polymer.
Silicone-based surfactant (B) containing a hydroxyl group in the molecule 0.1 to 5 parts by weight,
40 to 100 parts by weight of calcium carbonate (C) having an average particle size of 0.05 μm or less and 0.01 μm or more surface-treated with a fatty acid-based, resin acid-based, or fatty acid ester-based surface treatment agent.
Hydrophobic silica (D) 1-10 parts by weight,
A sealant composition containing 0.5 to 15 parts by weight of the curing catalyst (E) has been described.

Japanese Unexamined Patent Publication No. 2012-57002

The present inventors prepared a sealing material composition containing a plastic balloon (resin hollow body) with reference to Patent Document 1, and evaluated the composition. As a result, such a composition has low workability (for example, sagging). It became clear that there are cases where it is easy) or where durability is low.

When the sealing material is a two-component type, the two components are mixed to obtain a mixture (sealing material), the above sealing material is cured, and then avatar (partial on the surface of the sealing material) is applied to the surface of the sealing material. It refers to the state of unevenness. It is also called a crater.) May occur. The generation of avatars as described above is caused by the inclusion of air bubbles in the sealing material when the two components are mixed to obtain the sealing material as described above, and / or the air mixed in the sealing material seals. The reason for this is that the surface of the sealing material is dented by coming out of the surface of the material.

Therefore, an object of the present invention is to provide a sealing material composition in which avatars are inconspicuous, excellent in design, and excellent in workability and durability.

Regarding the problem of avatar of the sealing material, the present inventors have solved the problem of avataring of the sealing material even if avatar is generated on the surface of the sealing material by containing a resin balloon (resin hollow body) in a specific range amount in the sealing material composition. The present invention has been made by finding that avatars are less noticeable and that they are excellent in workability and durability.
The present invention is based on the above findings and the like, and specifically solves the above problems by the following configurations.

[1] With respect to 100 parts by mass of the polymer (A) having a hydrolyzable silyl group
Resin hollow body (B) 0.1 to 10 parts by mass,
A sealing material composition containing 100 to 300 parts by mass of calcium carbonate (C) and 0.1 to 10 parts by mass of silicon dioxide (D).
[2] The resin hollow body (B) contains a hollow body of an acrylonitrile-based copolymer coated with calcium carbonate.
The sealant composition according to [1], wherein the resin hollow body (B) has an average particle size of 80 to 150 μm.
[3] The sealant composition according to [1] or [2], wherein the average particle size of the calcium carbonate (C) is 0.01 to 5.00 μm.
[4] The sealant composition according to any one of [1] to [3], wherein the calcium carbonate (C) contains a surface-treated calcium carbonate (c-2).
[5] The silicon dioxide (D) is hydrophilic silicon dioxide.
The sealant composition according to any one of [1] to [4], wherein the silicon dioxide (D) has an average particle size of 10 to 20 μm.

The sealing material of the present invention is excellent in designability, workability and durability, as well as inconspicuous avatars.

The present invention will be described in detail below.
In addition, in this specification, (meth) acrylic represents acrylic or methacryl.
In addition, the numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present specification, unless otherwise specified, each component may use a substance corresponding to the component individually or in combination of two or more kinds. When a component contains two or more substances, the content of the component means the total content of the two or more substances.
In the present specification, unless otherwise specified, each component is not particularly limited in its production method. For example, a conventionally known method can be mentioned. In addition, commercially available products can be used as each component.
In the present specification, the fact that the avatar is inconspicuous and has excellent design may be simply referred to as "excellent in design". Further, when at least one of the above-mentioned design, workability, and durability is more excellent, it may be said that "the effect of the present invention is more excellent".
In the present specification, the polymer (A) having a hydrolyzable silyl group may be simply referred to as "polymer (A)" or "component (A)". The resin hollow body (B) may be simply referred to as "component (B)". The same applies to calcium carbonate (C) and silicon dioxide (D).

[Sealing material composition]
The sealant composition of the present invention (the composition of the present invention) is
With respect to 100 parts by mass of the polymer (A) having a hydrolyzable silyl group
Resin hollow body (B) 0.1 to 10 parts by mass,
A sealing material composition containing 100 to 300 parts by mass of calcium carbonate (C) and 0.1 to 10 parts by mass of silicon dioxide (D).
Hereinafter, each component contained in the composition of the present invention will be described in detail.

<< Polymer (A) >>
The composition of the present invention contains a polymer (A) having a hydrolyzable silyl group.
The polymer (A) can form, for example, a siloxane bond by hydrolyzing and condensing the hydrolyzable silyl group.

<Hydrolyzable silyl group>
The polymer (A) has a hydrolyzable silyl group in the molecule. The hydrolyzable silyl group has a hydrolyzable group bonded to a silicon atom. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group and an alkenyloxy group. Of these, an alkoxy group is preferable from the viewpoint of being more excellent in the effects of the present invention. A hydrolyzable silyl group having an alkoxy group as the hydrolyzable group may be referred to as an alkoxysilyl group.
In addition, a part of the hydrolyzable group may be hydrolyzed to become a silanol group.

Examples of the hydrolyzable silyl group include a group represented by the following formula (1).
−SiR ¹ _3-a (OR ² ) _a (1)
In formula (1), R ¹ _and R ² each independently represent a hydrocarbon group, and a represents 1-3.

The hydrocarbon groups as R ¹ _and R ² are not particularly limited. For example, aliphatic hydrocarbon groups (linear, branched or cyclic), aromatic hydrocarbon groups or combinations thereof can be mentioned.
R ¹ is preferably an aliphatic hydrocarbon group or a phenyl group, more preferably a methyl group, an ethyl group, a propyl group, a butyl group or a phenyl group, and is a methyl group, an ethyl group, a propyl group or a butyl group. Is more preferable, and a methyl group and an ethyl group are further preferable.
R ² is preferably an aliphatic hydrocarbon group. OR ² is preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group.
From the viewpoint that the effect of the present invention is more excellent, a is preferably 2 to 3 and more preferably 2.

(Main chain)
The main chain of the polymer (A) is preferably an organic polymer having a skeleton of at least carbon from the viewpoint of being superior to the effects of the present invention.
Examples of the main chain of the polymer (A) include a polyether polymer (for example, polyoxyalkylene), a (meth) acrylic acid ester polymer, an ether / ester copolymer, and a polymer of an ethylenically unsaturated compound. , Polymers of diene compounds.
The hydrolyzable silyl group can be attached to the terminal or side chain of the main chain. The hydrolyzable silyl group can be attached to the main chain directly or via an organic group. The organic group is not particularly limited.

The polymer (A) is a polyether polymer, a (meth) acrylic acid ester polymer, an ether / ester copolymer, or an ethylenic polymer having a hydrolyzable silyl group from the viewpoint of being superior to the effects of the present invention. A polymer of an unsaturated compound or a polymer of a diene compound is preferable, a polyether polymer having a hydrolyzable silyl group is more preferable, a polyoxypropylene polymer having a hydrolyzable silyl group is more preferable, and an alkoxy A polyoxypropylene-based polymer having a silyl group is particularly preferable.

As the polymer (A), a commercially available product may be used. Among the polymers (A), as a polyether having a hydrolyzable silyl group, a so-called "modified silicone" is commercially available. Examples of such commercially available products include MSP-S203, S303, S810 (trade name, manufactured by Kaneka Corporation), ES-S2410, ES-S2420, ES-S3430, ES-S3630, ES-S2730C (trade name, manufactured by Asahi Glass Co., Ltd.). ) Etc. can be mentioned.
Among the polymers (A), examples of commercially available (meth) acrylic acid ester-based polymers having a hydrolyzable silyl group include SA100S, SA310S, and XX009S (trade name, manufactured by Kaneka Corporation).

<< Resin hollow body (B) >>
The composition of the present invention contains a resin hollow body (B).
The composition of the present invention is excellent in the above-mentioned design property by containing the resin hollow body (B).
As a resin hollow body (B), it is preferable that the outer shell is made of resin and the inside is hollow.

Examples of the material of the outer shell of the resin hollow body (B) include phenol resin; urea resin; polystyrene resin; polyvinylidene chloride; acrylonitrile-based copolymer (for example, a copolymer of acrylonitrile and methacrylonitrile, acrylonitrile). And thermoplastic resins such as (copolymers of vinyl-based monomers such as butadiene and styrene) that can be copolymerized with acrylonitrile.

The resin hollow body (B) preferably contains a hollow body of an acrylonitrile-based copolymer from the viewpoint of being excellent in the effects of the present invention and excellent in weather resistance.

The surface of the resin hollow body (B) may be coated with a filler. Examples of the filler include calcium carbonate, talc, and titanium oxide.
The resin hollow body (B) is preferably coated with the above filler, more preferably with calcium carbonate, and calcium carbonate from the viewpoint of being excellent in the effect of the present invention and excellent in weather resistance. It is more preferable to contain a coated hollow body of an acrylonitrile-based copolymer.
When the resin hollow body (B) is a resin hollow body coated with calcium carbonate, the calcium carbonate that coats the resin hollow body is not included in the calcium carbonate (C) described later.
Further, the filler capable of coating the resin hollow body (B) does not contain silicon dioxide (D) described later.

(Average particle size of resin hollow body (B))
The average particle size of the resin hollow body (B) is preferably 80 to 150 μm, more preferably 100 to 140 μm, from the viewpoint of being more excellent in the effects of the present invention.
In the present invention, the average particle size of the resin hollow body (B) can be measured by a laser diffraction method.

In the present invention, when the average particle size of the resin hollow body (B) is displayed in the numerical range (for example, A to B μm), the average of the resin hollow body (B) is displayed. The median value of the numerical range of the particle size (that is, (A + B) / 2) can be treated as the average particle size of the resin hollow body (B).
When the average particle size of the resin hollow body (B) is displayed in a numerical range, the average particle size (median value) of the resin hollow body (B) is more excellent than the effect of the present invention. Therefore, it is preferably 80 to 150 μm, more preferably 100 to 140 μm, and even more preferably 115 to 130 μm.

(True density of resin hollow body (B))
True specific gravity of the resin hollow body (B), from the viewpoint of obtaining superior effects of the present invention, preferably ^{0.05~0.35g / cm 3, 0.07~0.12g / cm} 3 is more preferable.
In the present invention, the true specific gravity of the resin hollow body (B) refers to the specific gravity obtained only from the outer shell of the resin hollow body obtained by finely pulverizing the resin hollow body.
The true specific gravity of the resin hollow body (B) can be measured by, for example, a gas substitution type pycnometer method (constant volume expansion method) using a dry automatic density meter Accupic 1330 (trade name) manufactured by Shimadzu Corporation. Is.

In the present invention, when the true specific gravity of the resin hollow body (B) is displayed in the numerical range ^{(for example, C to Dg / cm 3), the resin hollow body (B)} The median value of the numerical range of the true specific density of (that is, (C + D) / 2) can be treated as the true specific gravity of the resin hollow body (B).
When the true specific gravity of the resin hollow body (B) is displayed in the numerical range, the true specific gravity (the above median value) of the resin hollow body (B) is 0 from the viewpoint of being superior to the effect of the present invention. .05 to 0.35 g / cm ³ is preferable, 0.07 to 0.12 g / cm ³ is more preferable, and 0.10 to 0.12 g / cm ³ is further preferable.

<Content of resin hollow body (B)>
In the present invention, the content of the resin hollow body (B) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (A).
When the content of the component (B) is within the above range, the present invention is excellent in design, workability, and durability.
The content of the component (B) is preferably 5 to 10 parts by mass, more preferably 8 to 10 parts by mass with respect to 100 parts by mass of the polymer (A) from the viewpoint of being more excellent in the effect of the present invention.
When the resin hollow body (B) is coated with the filler, the content of the component (B) refers to the amount containing the filler.

<< Calcium carbonate (C) >>
The composition of the present invention contains calcium carbonate (C) (component (C)).
The composition of the present invention is excellent in workability because it contains the component (C).

The component (C) is not particularly limited. For example, untreated calcium carbonate (c-1) or surface-treated calcium carbonate (c-2) can be mentioned.
The untreated calcium carbonate refers to calcium carbonate that has not been surface-treated.
The surface treatment agent used for surface treatment of calcium carbonate is not particularly limited. The surface treatment agent is preferably at least one selected from the group consisting of fatty acids, resin acids and fatty acid esters, and more preferably contains fatty acids, from the viewpoint of being superior in the effects of the present invention and excellent in mixing of compositions. ..
The above fatty acids are not particularly limited. For example, saturated fatty acids such as caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid; unsaturated fatty acids such as oleic acid, elaidic acid, linolic acid, ricinolic acid can be mentioned.

(Average particle size of calcium carbonate (C))
The average particle size of calcium carbonate (C) is preferably 0.01 to 5.00 μm, preferably 0.01 to 1.00 μm, from the viewpoint of excellent effect of the present invention and excellent mixability of the composition. More preferably, 0.01 to 0.1 μm is further preferable.
In the present invention, the average particle size of calcium carbonate (C) refers to the average value of the primary particle size observed by an electron microscope.

When the component (C) contains untreated calcium carbonate (c-1), the average particle size of the untreated calcium carbonate (c-1) is said to be excellent due to the effect of the present invention and excellent in mixing of the composition. From the viewpoint, it is preferably 0.01 to 5.00 μm, more preferably 0.05 to 3.0 μm, and even more preferably 0.5 to 3.0 μm.

When the component (C) contains surface-treated calcium carbonate (c-2), the average particle size of the surface-treated calcium carbonate (c-2) is more excellent due to the effect of the present invention, and the mixing property of the composition is improved. From the viewpoint of superiority, it is preferably 0.01 to 5.00 μm, more preferably 0.01 to 1.00 μm, and even more preferably 0.01 to 0.1 μm.

<Content of calcium carbonate (C)>
In the present invention, the content of calcium carbonate (C) is 100 to 300 parts by mass with respect to 100 parts by mass of the polymer (A).
When the content of the component (C) is within the above range, the present invention is excellent in workability, designability, and workability.
The content of the component (C) is preferably 100 to 200 parts by mass, more preferably 100 to 180 parts by mass, and 120 to 120 parts by mass with respect to 100 parts by mass of the polymer (A) from the viewpoint of being more excellent in the effect of the present invention. 150 parts by mass is more preferable.

The calcium carbonate (C) preferably contains untreated calcium carbonate (c-1) and / or surface-treated calcium carbonate (c-2) from the viewpoint of being superior to the effects of the present invention, and is surface-treated. It is more preferable to contain calcium carbonate (c-2), and it is further preferable to contain untreated calcium carbonate (c-1) and surface-treated calcium carbonate (c-2).

When the calcium carbonate (C) contains the surface-treated calcium carbonate (c-2), the calcium carbonate (C) is surface-treated and has an average particle size of 0. Calcium carbonate (c-2-1) which is 05 to 1.0 μm and / or calcium carbonate (c-2-2) which is surface-treated and has an average particle size of 0.01 μm or more and less than 0.05 μm. It is preferable, and it is more preferable to contain the above-mentioned calcium carbonate (c-2-1) and calcium carbonate (c-2-2).
The average particle size of the calcium carbonate (c-2-1) is preferably 0.07 to 1.0 μm from the viewpoint of being superior to the effect of the present invention.
The average particle size of the calcium carbonate (c-2-2) is preferably 0.01 to 0.04 μm from the viewpoint of being superior to the effect of the present invention.

When the calcium carbonate (C) contains the calcium carbonate (c-2-1) and the calcium carbonate (c-2-2), the calcium carbonate (c-2) with respect to the calcium carbonate (c-2-2) The mass ratio of -1) (calcium carbonate (c-2-1) / calcium carbonate (c-2-2)) is preferably 1.0 to 4.0 from the viewpoint of being superior to the effect of the present invention. .5-3.0 is more preferable.

When the calcium carbonate (C) contains untreated calcium carbonate (c-1) and surface-treated calcium carbonate (c-2), the content of the surface-treated calcium carbonate (c-2) is determined by the present invention. From the viewpoint of being more excellent in the effect of the above, 100 parts by mass or more is preferable, 100 to 200 parts by mass is more preferable, and 100 to 150 parts by mass is further preferable with respect to 100 parts by mass of the polymer (A).

When calcium carbonate (C) contains untreated calcium carbonate (c-1) and surface-treated calcium carbonate (c-2), the content of untreated calcium carbonate (c-1) is determined by the present invention. From the viewpoint of being more excellent in effect, 100 parts by mass or more is preferable, 100 to 200 parts by mass is more preferable, and 100 to 150 parts by mass is further preferable with respect to 100 parts by mass of the polymer (A).

When calcium carbonate (C) contains untreated calcium carbonate (c-1) and surface-treated calcium carbonate (c-2), untreated calcium carbonate (c-1) and surface-treated calcium carbonate ( The mass ratio (c-1 / c-2) to c-2) is preferably 150/100 to 100/150 from the viewpoint of being superior to the effect of the present invention.

(Mass ratio of calcium carbonate (C) / resin hollow body (B))
The mass ratio of the content of calcium carbonate (C) to the content of the resin hollow body (B) (calcium carbonate (C) / resin hollow body (B)) is 10 from the viewpoint of being superior to the effect of the present invention. ~ 110 is preferable, 15 to 80 is more preferable, 15 to 50 is further preferable, and 15 to 18 is particularly preferable.

<< Silicon Dioxide (D) >>
The composition of the present invention contains silicon dioxide (D) (component (D)).
The composition of the present invention is excellent in workability because it contains the component (D).

The component (D) is not particularly limited.
For example, hydrophilic silica and hydrophobic silica can be mentioned. As the component (D), hydrophilic silica is preferable from the viewpoint of being more excellent in the effect of the present invention.

(Average particle size of silicon dioxide (D))
The average particle size of silicon dioxide (D) is preferably 10 to 20 μm from the viewpoint of being excellent in the effect of the present invention and excellent in mixing of the composition.
In the present invention, the average particle size of silicon dioxide (D) refers to the 50% volume cumulative diameter (D50) measured using a laser diffraction type particle size distribution measuring device. The particle size that is the basis for calculating the average value is the average value obtained by dividing the total value of the major axis and the minor axis by 2 when the cross section of the component (D) is elliptical, and when it is a perfect circle. Refers to its diameter.

The method for producing silicon dioxide (D) is not particularly limited, but a method for producing silicon dioxide by a wet method is one of the preferred embodiments.

<Content of silicon dioxide (D)>
In the present invention, the content of silicon dioxide (D) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (A).
When the content of silicon dioxide (D) is in the above range, the present invention is excellent in workability.
The content of the component (D) is preferably 1 to 9 parts by mass, more preferably 5 to 8 parts by mass with respect to 100 parts by mass of the polymer (A) from the viewpoint of being more excellent in the effect of the present invention.

(Mass ratio of silicon dioxide (D) / resin hollow body (B))
The mass ratio of the content of the silicon dioxide (D) to the content of the resin hollow body (B) (silicon dioxide (D) / resin hollow body (B)) is 0 from the viewpoint of being superior to the effect of the present invention. .1 to 7.0 is preferable, 0.5 to 2.0 is more preferable, and 0.5 to 1.0 is further preferable.

(Curing catalyst)
The composition of the present invention can further contain a curing catalyst.
The curing catalyst is not particularly limited as long as it is a compound capable of curing the polymer (A). Examples thereof include tin-based catalysts, titanium-based catalysts, zirconium-based catalysts, aluminum-based catalysts, and amine-based catalysts.
Of these, tin-based catalysts are preferable from the viewpoint of excellent curability.

Examples of the tin-based catalyst include tin carboxylates such as tin butanoate, tin octylate, tin caprylate, and tin oleate (excluding alkyltin carboxylates described below);
Alkyltin carboxylates such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diolaate, dioctyltin dilaurate;
Alkyl oxide tin such as dibutyltin oxide;
Examples include alkyltin alkoxides such as dibutyltin dimethoxyde.

The tin-based catalyst is preferably tin carboxylate, more preferably tin octylate.
Examples of the tin octylate include stannous 2-ethylhexylate.

The content of the curing catalyst is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (A) from the viewpoint of being excellent in the effect of the present invention and excellent in curability.

(Additive)
The composition of the present invention may further contain additives, if necessary, as long as the purpose or effect is not impaired.
Examples of the additive include a plasticizer, an organic solvent, an antiaging agent, a thixo-imparting agent other than calcium carbonate (C) and silicon dioxide (D), and a filler other than calcium carbonate (C) and silicon dioxide (D). Can be mentioned.
Each of the above additives is not particularly limited. It can be selected as appropriate.

Examples of the plasticizer include aromatic carboxylic acid ester-based plasticizers such as diisononyl phthalate;
Aliphatic carboxylic acid ester plasticizer;
Epoxy-based plasticizers such as epoxy hexahydrophthalate dialkyl esters such as epoxy hexahydrophthalate di2-ethylhexyl;
Examples include polyoxyalkylene polyols such as polyoxypropylene diols.
From the viewpoint that the plasticizer is more excellent in the effect of the present invention, it is preferable to use an aromatic carboxylic acid ester plasticizer, an epoxy plasticizer and a polyoxyalkylene polyol in combination.
The content of the plasticizer is preferably 10 to 200 parts by mass and preferably 50 to 100 parts by mass with respect to 100 parts by mass of the polymer (A) from the viewpoint of being more excellent in the effect of the present invention.

The composition of the present invention may be either a one-component type or a two-component type.
When the composition of the present invention is a two-component type, the composition of the present invention can have a base and a curing agent.
When the composition of the present invention is a two-component type, the base can contain a polymer (A), a resin hollow body (B), calcium carbonate (C), and silicon dioxide (D).
On the other hand, the above-mentioned curing agent means a curing agent in a broad sense. The curing agent can include the curing catalyst as a curing agent in a narrow sense (a component capable of curing the polymer (A)).
The above additives can be contained in the base and / or the curing agent.

The method for producing the composition of the present invention is not particularly limited. For example, a method of sufficiently mixing each of the above components under reduced pressure or in an atmosphere of an inert gas such as nitrogen using a stirrer such as a roll, a kneader, an extruder, a ball mill, a universal stirrer, or a mixing mixer can be mentioned.

When the composition of the present invention is a two-component type, the base and the curing agent may be separately stored in a container, and the base and the curing agent may be mixed and used when used.

The composition of the present invention can be cured, for example, by moisture such as humidity in the air, or by heating under room temperature conditions.
When the composition of the present invention further contains a curing catalyst, it can be cured by the above-mentioned curing catalyst.

The composition of the present invention can be used as a composition for a sealing material.

Examples of the base material to which the composition of the present invention can be applied include concrete, wood, metal, glass, plastic, ceramic, and stone.
The method of applying the composition of the present invention to a substrate is not particularly limited. For example, a conventionally known method can be mentioned.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples.

<< Manufacture of composition >>
Each component in Table 1 below was used in the composition (part by mass) shown in the same table, and these were mixed with a stirrer to prepare a base for a two-component sealant composition.
A tin catalyst (2-ethylhexylate tin, trade name Nikkaoctix tin, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was used as a curing agent for the two-component sealant composition.
The total amount of each base obtained as described above and 5 parts by mass of the curing agent are sufficiently mixed with a stirrer (Nippon Sosei Kogyo Co., Ltd., a container rotary stirrer for sealing materials (product name: Carmaze)). Mixing was performed to produce each composition.

<< Evaluation >>
The following evaluations were carried out for each composition produced as described above. The results are shown in Table 1.
(Preparation of sealing material)
Each composition produced as described above is cast and driven so as to fill the joints (width: 40 mm, depth (depth): 20 mm, length: 1,000 mm) (completely fill the joints). After the setting, the surface of the composition cast with a gold spatula was leveled, and each composition was cured by leaving it under the conditions of 23 ° C. and 50% RH (relative humidity) for 7 days to prepare a sealing material.
Abata was generated in almost the same manner on the surface of each sealing material after curing.

(Presence / absence of surface roughness)
The surface roughness of each sealing material prepared as described above was visually observed.
When the entire surface of the sealing material (including the avatar part) had surface roughness (unevenness other than avatar and smaller than avatar), this was indicated as "yes".
When there was avatar on the surface of the sealant but the entire surface including that part was relatively smooth, this was indicated as "none".

(Creativity)
The state of avatar on the surface of each sealant produced as described above was visually confirmed.
-Evaluation criteria When the avatar was hardly noticeable on the surface of each sealing material after curing, it was evaluated as having the best design, and this was labeled as "AAA".
When the avatar was not so conspicuous on the surface of each sealing material after curing, it was evaluated that the design was very excellent, and this was labeled as "AA".
When the avatar appeared to be slightly present on the surface of each sealing material after curing, it was evaluated that the design was slightly excellent, and this was indicated as "A".
When the avatar was slightly conspicuous on the surface of each sealing material after curing, it was evaluated as having excellent design, and this was indicated as "B".
In each sealing material after curing, when the avatar was very conspicuous, it was evaluated as inferior in designability, and this was indicated as "C".

(Workability)
-Evaluation method The viscosity (Pa · s) of each composition manufactured as described above immediately after production was measured at 20 ° C. using a BS type viscometer (No. 7 rotor) at rotation speeds of 1 rpm and 10 rpm. I measured it.
The viscosity obtained as described above was applied to the following formula to calculate the chixo index (hereinafter, simply abbreviated as "TI") value.
TI value = (viscosity at 1 rpm) / (viscosity at 10 rpm)

-Evaluation Criteria When the TI value calculated as described above is 7.0 or more, it is evaluated that the workability is very excellent, and this is indicated as "◎".
When the TI value was 6.0 or more and less than 7.0, it was evaluated that the workability was slightly excellent, and this was indicated as "○".
When the TI value was 5.0 or more and less than 6.0, it was evaluated that the workability was excellent, and this was indicated as “Δ”.
When the TI value was less than 5.0, it was evaluated that the workability was inferior, and this was indicated as "x".

(durability)
The tensile adhesiveness test was carried out according to the tensile adhesiveness test of JIS A1439: 2016 “Test method for building sealant”.
First, each composition produced as described above and two aluminum plates (adhesive bodies) are used, and each composition is arranged between the two aluminum plates to be referred to as an H-type tensile test body (hereinafter referred to as a test body). ) Was prepared, and each composition was cured under the following curing / curing conditions to obtain a test piece.
-Curing / curing conditions After curing under the conditions of 23 ° C. and 50% RH for 7 days, the cells were further cured under the conditions of 50 ° C. for 7 days.

-Tensile test Each test piece obtained as described above was subjected to a tensile shear test under the conditions of a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% RH according to JIS A1439: 2016, and the test piece after the tensile shear test was performed. The state of destruction was visually observed.

-Evaluation criteria When the above-mentioned fracture condition is CF (aggregation fracture of sealing material) 100%, or CF and TCF (thin layer aggregation fracture of sealing material in which the sealing material remains thinly on the surface of the adherend) When it was included, it was evaluated as having excellent durability, and this was indicated as "○".
When the above-mentioned destruction situation was other than the above, it was evaluated that the durability was inferior, and this was indicated as "x".

The details of each component shown in Table 1 are as follows.
<Ingredient (A)>
-Combination having a hydrolyzable silyl group (A): A polymer having a dimethoxysilyl group as a hydrolyzable silyl group at both ends and having a main chain of polyoxypropylene. Product name "MSP-S810", manufactured by Kaneka Corporation

<Ingredient (B)>
The resin hollow body (B) 1 and the resin hollow body (B) 2 correspond to the component (B) in the present invention.
-Resin hollow body (B) 1: A hollow body of an acrylonitrile-based copolymer coated with calcium carbonate. Product name MFL-110CAL, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd. True specific gravity: 0.07 to 0.09 g / cm ³ , average particle size: 90 to 120 μm. The median true specific gravity of the resin hollow body (B) 1 is 0.08 g / cm ³ , and the median average particle size is 105 μm.

-Resin hollow body (B) 2: A hollow body of an acrylonitrile-based copolymer coated with calcium carbonate. Product name EMC-120 (α), manufactured by Nippon Phillite. True specific gravity 0.08 to ^{0.12 g / cm 3} , average particle size: 100 to 140 μm. The median true specific gravity of the resin hollow body (B) 2 is 0.10 g / cm ³ , and the median average particle size is 120 μm.

<Component (C)>
-Calcium carbonate (C) 1: Colloidal calcium carbonate surface-treated with fatty acids. Product name Shiro Gloss Flower CCR, manufactured by Shiraishi Kogyo Co., Ltd. The average particle size is about 0.08 μm. The calcium carbonate (C) 1 used in this example corresponds to the above-mentioned calcium carbonate (c-2-1) which has been surface-treated and has an average particle size of 0.05 to 1.0 μm in the present specification. do.

-Calcium carbonate (C) 2: Colloidal calcium carbonate surface-treated with fatty acids. Product name Viscoexcel-30, manufactured by Shiraishi Kogyo Co., Ltd. Average particle size 0.03 μm. The calcium carbonate (C) 2 used in this example is surface-treated to the calcium carbonate (c-2-2) having an average particle size of 0.01 μm or more and less than 0.05 μm in the present specification. Applicable.

<Component (D)>
-Silicon dioxide (D): Hydrophilic silica produced by a wet method. Product name Carplex # 80, DSL. Made by Japan. Average particle size about 15 μm

-Plasticizer 1: Diisononyl phthalate. Product name "DINP", manufactured by J-PLUS Co., Ltd. Plasticizer 2: Epoxy-based plasticizer. Di2-ethylhexyl epoxyhexahydrophthalate. Product name "Sun Sizar E-PS", manufactured by Shin Nihon Rika Co., Ltd. Plasticizer 3: Polyoxypropylene diol (PPG). Product name "PREMINOL S4012", manufactured by AGC Inc.

As is clear from the results shown in Table 1, Comparative Example 1 containing no resin hollow body (B) was extremely inferior in design.
Comparative Example 2 in which the content of the resin hollow body (B) was larger than the predetermined range was inferior in workability and durability.

On the other hand, the composition of the present invention was excellent in design, workability, and durability.

Claims (5)

With respect to 100 parts by mass of the polymer (A) having a hydrolyzable silyl group
Resin hollow body (B) 0.1 to 10 parts by mass,
A sealing material composition containing 100 to 300 parts by mass of calcium carbonate (C) and 0.1 to 10 parts by mass of silicon dioxide (D). The resin hollow body (B) contains a hollow body of an acrylonitrile-based copolymer coated with calcium carbonate.
The sealant composition according to claim 1, wherein the resin hollow body (B) has an average particle size of 80 to 150 μm. The sealant composition according to claim 1 or 2, wherein the average particle size of the calcium carbonate (C) is 0.01 to 5.00 μm. The sealant composition according to any one of claims 1 to 3, wherein the calcium carbonate (C) contains a surface-treated calcium carbonate (c-2). The silicon dioxide (D) is hydrophilic silicon dioxide, and the silicon dioxide (D) is hydrophilic.
The sealant composition according to any one of claims 1 to 4, wherein the silicon dioxide (D) has an average particle size of 10 to 20 μm.