JP2020164723A - Sealant composition - Google Patents

Abstract

To provide a sealant composition having excellent thixotropy, adhesiveness, and designability.SOLUTION: A sealant composition contains, based on 100 pts.mass of a polymer having a hydrolyzable silyl group (A), a silicone compound having a hydroxy group (B) 0.1-10 pts.mass, calcium carbonate (C) 200-300 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

When the present inventors prepared a sealing material composition with reference to Patent Document 1 and evaluated it, it became clear that such a composition may have low tixogenicity.
In addition, recent sealing materials are required to have a high level of adhesiveness.

When the sealing material is a two-component type, the two liquids 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 occurrence of avatars as described above is that when the two liquids are mixed as described above to obtain a sealing material, air bubbles are mixed in the sealing material and / or the air mixed in the sealing material is sealed. The reason for this is that the surface of the sealing material is dented by coming out of the surface of the material.
Therefore, it is an object of the present invention to provide a sealing material composition having excellent designability, in which avatars are inconspicuous in terms of ticking property, adhesiveness and avatar.

Regarding the problem of avatar of the sealing material, the present inventors can reduce the generation of avatar by containing a silicone compound having a hydroxyl group in the sealing material composition, and as a result, the avatar becomes less noticeable, or It has been found that even if avatars are generated on the surface of the sealing material, the silicone-based compound makes the surface of the sealing material matte, so that the avatars are visually inconspicuous.

It was also found that when the content of the silicone compound having a hydroxyl group is large, the avatar is inconspicuous, but the adhesiveness tends to decrease.

As described above, as a result of diligent research to solve the above problems, the present inventors have made a silicone compound (B) having a hydroxyl group with respect to 100 parts by mass of the polymer (A) having a hydrolyzable silyl group. According to the sealant composition containing 0.1 to 10 parts by mass, 200 to 300 parts by mass of calcium carbonate (C), and 0.1 to 10 parts by mass of silicon dioxide (D), the desired effect can be obtained. And came to the present invention.
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
Silicone compound (B) having a hydroxyl group 0.1 to 10 parts by mass,
A sealing material composition containing 200 to 300 parts by mass of calcium carbonate (C) and 0.1 to 10 parts by mass of silicon dioxide (D).
[2] The sealant composition according to [1], wherein the silicone compound (B) contains a polyether-modified polydimethylsiloxane having a hydroxyl group.
[3] The calcium carbonate (C) contains untreated calcium carbonate (c-1) and / or surface-treated calcium carbonate (c-2).
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 calcium carbonate (C) contains untreated calcium carbonate (c-1) and surface-treated calcium carbonate (c-2).
The mass ratio (c-1 / c-2) of the untreated calcium carbonate (c-1) to the surface-treated calcium carbonate (c-2) is 150/100 to 100/150. 1] The sealant composition according to any one of [3].
[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 ticking property, adhesiveness, avatar inconspicuous and designable.

The present invention will be described in detail below.
In the present specification, (meth) acrylate represents acrylate or methacrylate, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acrylic represents acrylic or methacrylic.
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, the fact that the avatar is inconspicuous and has excellent designability may be simply referred to as "excellent in designability". In addition, "the effect of the present invention is more excellent" means that at least one of the thixo property, the adhesive property and the design property 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 silicone-based compound (B) having a hydroxyl group may be simply referred to as "compound (B)" or "component (B)".
Calcium carbonate (C) may be simply referred to as "component (C)". The same applies to 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
Silicone compound (B) having a hydroxyl group 0.1 to 10 parts by mass,
It is a sealant composition containing 200 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 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.
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.
a is preferably 2 to 3.

(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 further 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), commercially available products of (meth) acrylic acid ester-based polymers having a hydrolyzable silyl group include, for example, SA100S, SA310S, XX009S (trade name, manufactured by Kaneka Corporation) and the like.

<< Compound (B) >>
The composition of the present invention contains a silicone-based compound (B) having a hydroxyl group.
Compound (B) can reduce avatars and / or function as a surface conditioner for the sealant to matte the surface of the sealant.

Compound (B) is a compound having a hydroxyl group (hydroxy group) and having a main chain having a silicone skeleton.

<Hydroxy group>
The hydroxyl group of compound (B) can be bonded to the main chain via an organic group. The organic group is not particularly limited. For example, a polyether group can be mentioned.
The hydroxyl group is preferably bonded to the carbon of the organic group from the viewpoint of being superior to the effect of the present invention.

(Main chain)
Examples of the main chain (silicone) contained in compound (B) include polyorganosiloxane.
The hydrocarbon group of the organopolysiloxane in the silicon atom is not particularly limited. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof. The hydrocarbon group 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. It is more preferable to have a methyl group or an ethyl group.

(Metamorphism)
Compound (B) may be modified with an organic group such as a polyether.
The compound (B) is preferably modified with a polyether (for example, a polyether-modified silicone compound having a hydroxyl group) from the viewpoint of being more excellent in the effects of the present invention.

From the viewpoint of being more excellent in the effects of the present invention, the compound (B) preferably contains a polyorganosiloxane having an organic group and the hydroxyl group bonded to the organic group, and the polyether modified silicone having a hydroxyl group (for example, poly). It is more preferable to contain a polyorganosiloxane having an ether group and the hydroxyl group bonded to the polyether group, and the polyether-modified polydialkylsiloxane having a hydroxyl group (having a polyether group and having the hydroxyl group attached to the polyether group) is more preferable. It is more preferable to contain a polydialkylsiloxane () to be bonded, and it is particularly preferable to contain a polyether-modified polydimethylsiloxane having a hydroxyl group (a polydimethylsiloxane having a polyether group and the hydroxyl group bonded to the polyether group).

When the hydroxyl group is bonded to the main chain as a side chain, the terminal of the compound (B) as described above may be sealed with, for example, a silyl group having three hydrocarbon groups. The hydrocarbon group is not particularly limited. Examples of the silyl group having three hydrocarbon groups include a trialkylsilyl group.

(Weight average molecular weight of compound (B))
The weight average molecular weight of compound (B) is preferably 500 to 10,000, more preferably 1,000 to 5,000, from the viewpoint of being more excellent in the effects of the present invention.
In the present invention, the weight average molecular weight of the compound (B) is a standard polystyrene-equivalent value measured by a gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

<Content of compound (B)>
In the present invention, the content of the compound (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 compound (B) is in the above range, the present invention is excellent in design and adhesiveness.
The content of the compound (B) is 1.0 to 5.0 mass by mass with respect to 100 parts by mass of the polymer (A) from the viewpoint that the effect of the present invention is excellent and the balance between design and adhesiveness is excellent. Part is preferable.

<< Calcium carbonate (C) >>
The composition of the present invention contains calcium carbonate (C) [component (C)].
The composition of the present invention is excellent in thixophilicity by containing 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 from the viewpoint of being excellent in the effects of the present invention and excellent in mixing of compositions.

(Average particle size of calcium carbonate (C))
The average particle size of calcium carbonate (C) is preferably 0.01 to 5.00 μm, preferably 0.05 to 3.0 μm, from the viewpoint of excellent effect of the present invention and excellent mixability of the composition. More preferably, it exceeds 0.05 μm and more preferably 3.0 μm or less.
The average particle size of calcium carbonate (C) refers to the average value of the primary particle size observed by an electron microscope, or the average particle size based on the specific surface area (calculated value from the specific surface area).

- specific surface area of the averaged particle size generally by calcium carbonate (C), the relationship of the specific surface area S _w and the particle size of the powder is given by the following equation.
_{S w = (k s / ρ} ) · (ΣnD 2 / ΣnD 3)
_Sw (cm ² / g): Total surface area (specific surface area) of a unit mass of powder (calcium carbonate in this case). The specific surface area can be obtained by using an air permeation method according to the JIS K8511: 2014 5.4 specific surface area test method.
k _s : Particle shape coefficient (of calcium carbonate) ρ: Powder density (calcium carbonate density is 2.7 g / cm ³ )
n: Number of particles (of calcium carbonate) of diameter D

In general, the powder assuming that (calcium carbonate) is made of a uniform particle shape particle (k _s = 6), the average particle size by specific surface area of calcium carbonate can be obtained, for example, from the following formula obtained by the Dm ..
S _w = 6 / (ρD _m )
D _m : Specific surface area diameter (average particle size based on the specific surface area of calcium carbonate). D _m corresponds to D ₃ (= ΣnD ³ / ΣnD ² ), which is the average diameter of the body area of the number distribution.

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 superior to the effect of the present invention, and the mixture of the compositions is improved. From the viewpoint of superiority, it is preferably 0.01 to 5.00 μm, more preferably more than 0.05 μm and less than 0.5 μm.

<Content of calcium carbonate (C)>
In the present invention, the content of calcium carbonate (C) is 200 to 300 parts by mass with respect to 100 parts by mass of the polymer (A).
When the content of the component (C) is in the above range, the present invention is excellent in thixo property, design property, and workability.
When a plurality of types of calcium carbonate are used as the calcium carbonate (C), the content of the calcium carbonate (C) means the total amount of calcium carbonate used.
The content of the component (C) is preferably 200 to 250 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 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 preferably untreated. It is more preferable to contain calcium carbonate (c-1) and surface-treated calcium carbonate (c-2).

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 the content of 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 (c-1) The mass ratio (c-1 / c-2) to c-2) is more preferably 150/100 to 100/150 from the viewpoint of being superior to the effect of the present invention.

<< Silicon Dioxide (D) >>
The composition of the present invention contains silicon dioxide (D) [component (D)].
The composition of the present invention is excellent in ticking property by containing 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 superior to 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.
Here, 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 thixo property and workability.
The content of the component (D) is preferably 0.1 to 20 parts by mass and more preferably 5 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.

(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 catalysts, titanium catalysts, zirconium catalysts, aluminum catalysts and amine catalysts.
Of these, a tin catalyst is 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.

(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 plasticizers such as epoxy hexahydrophthalic acid dialkyl esters such as epoxy hexahydrophthalate di2-ethylhexyl;
Examples include polyoxyalkylene polyols such as polyoxypropylene diol.
From the viewpoint of being more excellent in the effects of the present invention, it is preferable to use an aromatic carboxylic acid ester-based plasticizer, an epoxy-based 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, it 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 compound (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 room temperature conditions or by heating.
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.

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

<< Production 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 Nihon 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.
(Creativity)
-Evaluation method Each composition produced as described above is cast into joints (width: 40 mm, depth: 20 mm, length: 1,000 mm) so as to fully fill the joints, and after casting, gold is used. The surface of the composition cast with a spatula was leveled, and each composition was cured by leaving it under the conditions of 23 ° C. and 55% RH for 7 days to obtain a sealing material.
After 7 days, the state of avatar on the surface of the sealant and the state of gloss on the surface were visually confirmed.

-Evaluation criteria Scarring occurred on the surface of each sealing material after curing. Among them, the avatar on the surface of the sealing material after 7 days of Comparative Example 1 was the most.
When the surface of each sealing material after curing is not glossy and the amount of avatar is less than that of Comparative Example 1 and the avatar is hardly noticeable, it is evaluated that the design is very excellent, and this is evaluated as "◎". Was displayed.
The amount of avatar was almost the same as that of Comparative Example 1, but when the surface of each sealing material after curing was not glossy and the avatar was not so noticeable, or
The surface of each sealing material after curing is slightly glossy (at this time, it is not necessary to consider the amount of avatars), but when the avatars are not so noticeable, it is evaluated that the design is slightly excellent, and this is evaluated as " 〇 ”was displayed.
If the surface of each sealing material after curing is slightly glossy (at this time, it is not necessary to consider the amount of avatars) and the avatars are slightly conspicuous, it is evaluated that the design is slightly inferior. Was displayed.
When the surface gloss of each sealing material after curing is very strong (at this time, it is not necessary to consider the amount of avatars) and the avatars are very conspicuous, it is evaluated that the design is very inferior. Was displayed as "x".

(Chixo)
-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 6.0 or more, it is evaluated that the tincture property is very excellent, and this is indicated as "◎".
When the TI value was 5.0 or more and less than 6.0, it was evaluated that the thixo property was slightly excellent, and this was indicated as "○".
When the TI value was less than 5.0, it was evaluated that the thixo property was inferior, and this was indicated as "x".

(Adhesiveness)
The tensile adhesiveness test was carried out according to the tensile adhesiveness test of JIS A1439: 2010 "Test method for building sealant".
First, using each composition produced as described above and two aluminum plates (adhesive bodies), 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 curing / curing conditions shown below to obtain a test piece.
-Curing / curing conditions After curing at 23 ° C. and 50% RH for 7 days, it was cured at 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 temperature 23 ± 2 ° C. and humidity 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 was CF (cohesive fracture of sealing material) 100%, it was evaluated that the adhesiveness was very excellent, and this was indicated as "◎".
When the above fracture condition includes CF and TCF (thin layer cohesive fracture of the sealant in which the sealant remains thin on the surface of the adherend), it is evaluated that the adhesiveness is slightly excellent, and this is evaluated as "○". displayed.
If the above-mentioned fracture state does not include CF and is TCF, AF (interfacial peeling) or MF (adhesion fracture (base material fracture)), it is evaluated that the adhesiveness is inferior, and this is indicated as "x". did.

The details of each component shown in Table 1 are as follows.
-Polymer (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

-Compound (B) 1: Polyether-modified silicone having a hydroxyl group. A polydimethylsiloxane having both ends of the main chain sealed with a trimethylsilyl group and having a polyoxyalkylene group having a hydroxyl group (hydroxy group) at the end (of the side chain) as a side chain. The hydroxyl group is bonded to the carbon of the polyoxyalkylene group. Hydroxy group value is about 45 mgKOH / g. Product name BYK-377, manufactured by Big Chemie Japan. Weight average molecular weight 3,000

-Compound (B) 2: Polyether-modified silicone having a hydroxyl group. The hydroxyl group is bonded to the carbon of the polyether moiety. Silicone as the main chain is polydimethylsiloxane. Product name KL-404, manufactured by Kyoeisha Chemical Co., Ltd. Weight average molecular weight 3,000

-Comparative compound 1: Silicone compound having no hydroxyl group. Product name BYK-333, manufactured by Big Chemie Japan.
-Comparative compound 2: A silicone compound having no hydroxyl group. Product name KL-401, manufactured by Kyoeisha Chemical Co., Ltd.

-Calcium carbonate (C) 1: Colloidal calcium carbonate surface-treated with fatty acids. Product name Shiroishi Technical High School, manufactured by Shiroishi Kogyo. Average (primary) particle size approx. 0.08 μm (electron microscope observation value)
-Calcium carbonate (C) 2: Heavy calcium carbonate that has not been surface-treated. Product name Super SS, manufactured by Maruo Calcium Co., Ltd. Average particle size 2.2 μm (calculated from specific surface area)
-Calcium carbonate (C) 3: Calcium carbonate surface-treated with fatty acids. Product name Calfine N-40, manufactured by Maruo Calcium. Average particle size 0.04 μm (electron microscope observation value)

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

-Plasticizer 1: Diisononyl phthalate. Product name "DINP", manufactured by J-PLUS Co., Ltd. Plasticizer 2: Epoxy plasticizer. Di2-ethylhexyl epoxyhexahydrophthalate. Product name "Sun Sizar E-PS", manufactured by New Japan Chemical 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 compound (B) was extremely inferior in design.
Comparative Example 2 containing the comparative compound 1 which does not contain the compound (B) and instead has a hydroxyl group was slightly inferior in design.
Comparative Example 3 containing the comparative compound 2 which does not contain the compound (B) and instead has a hydroxyl group was slightly inferior in design.
Comparative Example 4 in which the content of the silicone compound (B) exceeds a predetermined range was inferior in designability and adhesiveness.
Comparative Example 5, which does not contain compound (B) and has a higher content of calcium carbonate (C) than Comparative Example 1, was very inferior in design and inferior in thixo property.
Comparative Examples 6 to 9 in which the content of calcium carbonate (C) was less than the predetermined range were inferior in design and thixo property.

On the other hand, the composition of the present invention was excellent in designability, ticking property and adhesiveness.

Claims (5)

With respect to 100 parts by mass of the polymer (A) having a hydrolyzable silyl group
Silicone compound (B) having a hydroxyl group 0.1 to 10 parts by mass,
A sealing material composition containing 200 to 300 parts by mass of calcium carbonate (C) and 0.1 to 10 parts by mass of silicon dioxide (D). The sealant composition according to claim 1, wherein the silicone compound (B) contains a polyether-modified polydimethylsiloxane having a hydroxyl group. The calcium carbonate (C) contains untreated calcium carbonate (c-1) and / or surface-treated calcium carbonate (c-2).
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 calcium carbonate (C) contains untreated calcium carbonate (c-1) and surface-treated calcium carbonate (c-2).
Claimed that the mass ratio (c-1 / c-2) of the untreated calcium carbonate (c-1) to the surface-treated calcium carbonate (c-2) is 150/100 to 100/150. Item 3. The sealing material composition according to any one of Items 1 to 3. 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.