JP6668903B2 - Composition for sealing material - Google Patents

Description

  The present invention relates to a composition for a sealing material.

Conventionally, a so-called modified silicone-based curable resin composition is known as a one-component moisture-curable resin composition.
The modified silicone-based moisture-curable resin composition usually contains a modified silicone polymer.
The modified silicone polymer is a polymer having a polyether or (meth) acrylic polymer as a main chain and further having a crosslinkable crosslinkable silyl group. The modified silicone polymer can be used in combination with a curing catalyst, in which case it is stable under seal for a long period of time, but can rapidly cure to a rubbery material when exposed to moisture. Therefore, the modified silicone-based moisture-curable resin composition can be a one-part composition.

The modified silicone-based moisture-curable resin composition can be used, for example, as a sealing material.
For example, Patent Document 1 is proposed as a modified silicone-based curable resin composition that can be used as a sealing material or the like.
Patent Literature 1 discloses that 100 parts by mass of a (meth) acrylic polymer (A) having at least one crosslinkable silyl group at a terminal and a monovalent or divalent C 8 or more carbon atom which may be branched. 0.1 to 100 parts by mass of a diamine compound (B) having an aliphatic or alicyclic hydrocarbon group and having at least one primary amino group, and a monovalent having 8 or more carbon atoms which may be branched Curable resin composition containing 0.1 to 100 parts by mass of an aliphatic or alicyclic hydrocarbon group, and 0.1 to 100 parts by mass of a diamine compound (C) having a crosslinkable silyl group and / or a (meth) acryloyl group. Has been described.

JP 2011-6535 A

Under such circumstances, it is assumed that the present inventor prepares a composition for a sealing material containing a modified silicone polymer and an amine compound based on Patent Document 1 and applies such a composition to joints between members. As a result of the evaluation, it was clarified that the obtained sealing material might be stained.
Then, an object of this invention is to provide the composition for sealing materials which is excellent in stain resistance.

The present inventor has conducted intensive studies to solve the above-described problems, and as a result, the modified silicone polymer, an amine compound having an alkyl group and an amino group having a prime number of 20 or more, and a silane coupling agent having an amino group are contained. It has been found that the effect of (1) can be obtained, and the present invention has been achieved.
The present invention is based on the above findings and the like, and specifically solves the above problems by the following constitutions.

1. A modified polymer having at least one crosslinkable silyl group, wherein the crosslinkable silyl group is bonded to a terminal;
An amine compound having an alkyl group having 20 or more carbon atoms and an amino group 1,
A silane coupling agent having an amino group 2,
A filler,
A composition for a sealing material, comprising a curing catalyst.
2. 2. The composition for a sealing material according to the above 1, wherein the carbon number is 22 to 30.
3. 3. The composition for a sealing material according to 1 or 2 above, wherein the melting point of the amine compound is 50 ° C. or higher.
4. The composition for a sealing material according to any one of the above items 1 to 3, wherein the amine compound has one amino group 1 in one molecule and has no imino group.
5. The sealing material composition according to any one of the above items 1 to 4, wherein the content of the amine compound is 0.5 to 10 parts by mass with respect to 100 parts by mass of the modified polymer.
6. The composition for a sealing material according to any one of the above items 1 to 5, wherein the silane coupling agent has one amino group 2 in one molecule and has no imino group.
7. The sealing material composition according to any one of the above items 1 to 6, wherein the content of the silane coupling agent is 0.5 to 3.0 parts by mass based on 100 parts by mass of the modified polymer.
8. The composition for a sealing material according to any one of the above 1 to 7, wherein the curing catalyst contains a tin catalyst.

  ADVANTAGE OF THE INVENTION According to the composition for sealing materials of this invention, the sealing material excellent in stain resistance can be obtained.

The present invention will be described in detail below.
In this specification, (meth) acrylate represents acrylate or methacrylate, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acryl represents acryl or methacryl.
Further, in this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the present specification, when a component contains two or more types of substances, the content of the above components means the total content of the two or more types of substances.
In the present invention, the amino group refers to "-NH _2", imino refers to "-NH- or = NH".

[Composition for sealing material]
The sealing material composition of the present invention (the composition of the present invention)
A modified polymer having at least one crosslinkable silyl group, wherein the crosslinkable silyl group is bonded to a terminal;
An amine compound having an alkyl group having 20 or more carbon atoms and an amino group 1,
A silane coupling agent having an amino group 2,
A filler,
A composition for a sealing material, comprising a curing catalyst.

Since the composition of the present invention has such a constitution, it is considered that a desired effect can be obtained. The reason is not clear, but is presumed to be as follows.
A conventional composition for a sealing material contains a diamine compound having two nitrogen-containing functional groups (for example, an amino group or -NH-). The above diamine compound is used for the purpose of suppressing tackiness of the sealing material and the like. When the diamine compound is a low molecular compound, its melting point is about 35 ° C. In such a case, since the diamine compound in the sealing material is often a liquid in a low-temperature environment such as winter, it tends to bleed out to the surface of the sealing material. Then, the amino group of the diamine compound reacts with carbon dioxide in the air to form a carbonate on the surface of the sealing material, whereby tackiness can be suppressed. By suppressing the tack in this way, it is possible to prevent dirt such as dust from adhering to the surface of the sealing material.
When the rain falls and the carbonate flows from the surface of the sealing material, the effect of suppressing tack and the like is once weakened, but the effect of suppressing tack can be regenerated by bleeding out the diamine compound again.
However, when the diamine compound easily bleeds out, the sealing material is exposed to rain or the like many times, so that the diamine compound in the sealing material decreases or disappears, and the diamine compound bleeds out again. It becomes difficult. As a result, the sealing material cannot maintain the above-described stain resistance for a long time.

On the other hand, in the composition of the present invention, since the alkyl group of the amine compound has a long carbon number of 20 or more, it is easily entangled with the modified polymer and hardly bleeds out. The melting point of the amine compound is relatively high, and bleed-out hardly occurs not only in winter but also in high-temperature conditions such as summer. In addition, since the silane coupling agent can react with the crosslinkable silyl group of the modified polymer by a condensation reaction, it does not easily bleed out.
As described above, the composition of the present invention makes it difficult for the amine compound and the silane coupling agent to bleed out from the sealing material, so that the amine compound and the silane coupling agent can bleed out for a long period of time and have excellent stain resistance. it is conceivable that.
Hereinafter, each component contained in the composition of the present invention will be described in detail.

<Modified polymer>
The modified polymer contained in the composition of the present invention is a polymer having at least one crosslinkable silyl group, and the crosslinkable silyl group is bonded to the terminal.

(Main chain of modified polymer)
Examples of the main chain of the modified polymer include a polymer having a hydrocarbon skeleton such as a (meth) acrylic polymer; and a polyether. Among them, one preferred embodiment is that the main chain of the modified polymer is a (meth) acrylic polymer.
The (meth) acrylic polymer as the main chain is not particularly limited as long as it is a polymer having a repeating unit of a (meth) acrylate monomer.

(Crosslinkable silyl group)
In the present invention, the crosslinkable silyl group means a group capable of causing a condensation reaction by using a curing catalyst or the like in the presence of moisture or the like.
Examples of the crosslinkable silyl group include a silicon-containing group having a hydrolyzable group bonded to a silicon atom and a silanol group. More specifically, for example, a group represented by the following general formula (1) can be mentioned.

In the formula, R ⁶ and R ⁷ are each independently represented by an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ⁸ ) ₃ SiO—. And when two or more R ⁶ or R ⁷ are present, they may be the same or different.
Here, R ⁸ is a monovalent hydrocarbon group having 1 to 20 carbon atoms and the three R ⁸ may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2.
Further, b in the t groups represented by the following general formula (2) may be different. t shows the integer of 0-19. However, it is assumed that a + t × b ≧ 1 is satisfied.

The hydrolyzable group represented by Y is not particularly limited, and may be any conventionally known hydrolyzable group. Specific examples include a hydrogen atom, 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. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferred, and methoxy is preferred because of its mild hydrolyzability and easy handling. Alkoxy groups such as groups are particularly preferred.
Among the crosslinkable silyl groups, a crosslinkable silyl group represented by the following general formula (3) is preferable from the viewpoint of easy availability. In the following general formula (3), R ⁷ , Y and a have the same meanings as R ⁷ , Y and a described above.

Specific examples of R ⁶ and R ⁷ in the general formula (1) include, for example, an alkyl group such as a methyl group and an ethyl group; an alicyclic hydrocarbon group such as a cyclohexyl group; an aryl group such as a phenyl group; And an aralkyl group such as a triorganosiloxy group represented by (R ⁸ ) ₃ SiO—, wherein R ⁸ is a methyl group or a phenyl group. As R ⁶ , R ⁷ and R ⁸ , a methyl group is particularly preferred.

On the other hand, examples of the (meth) acrylate monomer capable of forming the main chain of the (meth) acrylic polymer include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, Isobutyl acrylate, tertiary butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, lauryl Acrylates such as acrylate, tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, and behenyl acrylate Acrylic acid alkyl ester or methacrylic acid alkyl esters corresponding thereto;
Acrylic esters having aromatic hydrocarbons such as phenyl acrylate, toluyl acrylate, benzyl acrylate, biphenyl acrylate or the corresponding methacrylates;
Acrylic acid ester having an alkoxy group such as 2-methoxyethyl acrylate, 3-methoxybutyl acrylate or a corresponding methacrylic acid ester;
Acrylic acid ester having a hydroxy group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate or a corresponding methacrylic acid ester;
Acrylic acid esters having epoxy groups such as glycidyl acrylate;
Acrylic acid ester having an amino group and / or imino group such as 2-aminoethyl acrylate or a corresponding methacrylic acid ester;
Acrylates or corresponding methacrylates with tertiary amines such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate;
Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethyl Acrylic ester having a halogen such as methyl acrylate, 2-perfluoromethyl-2-perfluoroethylethyl acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate And methacrylic esters corresponding thereto.
These may be used alone or in combination of two or more.

  In addition, the amount of the repeating unit of the (meth) acrylate monomer in the main chain of the (meth) acrylic polymer depends on availability and weather resistance of the obtained cured product and flexibility at low temperatures. Therefore, it is preferable that the amount exceeds 50% by mass, more preferably 70% by mass or more of the total amount of the repeating units constituting the main chain.

Further, the main chain of the (meth) acrylic polymer may contain, in addition to the above-mentioned repeating unit, a monomer unit copolymerizable therewith. For example, a monomer unit containing a carboxy group such as acrylic acid and methacrylic acid; a monomer unit containing an amide group such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide; aminoethyl vinyl ether; Compounds having an ether bond such as polyoxyethylene acrylate and polyoxyethylene methacrylate can be expected to have a copolymerization effect in terms of moisture curability and internal curability.
Other examples include monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, and the like.

  The monomer composition of the (meth) acrylic polymer can be appropriately selected depending on the use, purpose, and the like.

  The synthesis of the modified polymer is not particularly limited, and can be synthesized by a known method.

  The molecular weight of the modified polymer is not particularly limited, but those having a number average molecular weight in terms of polystyrene of 500 to 100,000 in gel permeation chromatography (GPC) are difficult, compatible, and difficult to handle during polymerization. It is preferable in terms of viscosity. Among them, those having a number average molecular weight of 1,000 to 50,000 are preferred in terms of balance between strength and viscosity, and those having a number average molecular weight of 2,000 to 30,000 are preferred in terms of workability such as workability, adhesion and the like. Is more preferable.

  Examples of the modified polymer include a modified (meth) acrylic polymer such as Kaneka Telechelic Polyacrylate-SA100S, SA110S, SA120S, SA310S, SB802S manufactured by Kaneka Corporation.

  The above-mentioned modified polymers can be used alone or in combination of two or more.

<Amine compound>
The amine compound contained in the composition of the present invention is a compound having an alkyl group and an amino group having 20 or more carbon atoms. The amine compound has an amino group as amino group 1.
The amine compound bleeds out to the surface of the sealing material after the composition of the present invention is cured to form a sealing material, and can function as a stain-resistant agent for the sealing material.

(Alkyl group)
The alkyl group of the amine compound may be linear, branched or cyclic. It is mentioned as one of the preferable aspects that it is linear.

  The carbon number of the alkyl group is preferably from 22 to 30 in that the effect (stain resistance) of the present invention is more excellent.

As the alkyl group, e.g., C ₂₀ H ₄₁ - (eicosyl _{group), C 21 H 43 -,} C 22 H 45 - and the like. Among them, C ₂₂ H ₄₅ − is preferable in that the effects of the present invention are more excellent and the melting point is more excellent.

(Amino group 1)
The amine compound can have one or more amino groups 1 (—NH ₂ ) in one molecule, and is excellent in the effect of the present invention and excellent in tackiness (the composition of the present invention is cured (for example, 24 hours). Thereafter, it is preferable that the number is one in terms of low tack (residual tack) on the surface of the composition.

Amino group 1 can be bonded to an alkyl group directly or via an organic group. The organic group is not particularly limited. For example, a group represented by the formula (4) can be mentioned.
-NH-R ⁴¹ - (4)
In the formula (4), R ⁴¹ is preferably a hydrocarbon group having 1 to 19 carbon atoms. The hydrocarbon group having 1 to 19 carbon atoms is not particularly limited. -NH- is a so-called imino group.

  An amine compound is one of the preferable embodiments that does not have an imino group in that the effect of the present invention is more excellent and tackiness is excellent.

The amine compound is preferably a compound represented by the following formula (5) in that the effects of the present invention are more excellent and the tackiness is excellent.
^{R 52 - (NH-R 51} ) m5 -NH 2 (5)
In the formula (5), R ⁵² is an alkyl group having 20 or more carbon atoms, R ⁵¹ is a hydrocarbon group having 1 to 19 carbon atoms, and m5 is 0 or 1.
The alkyl group having 20 or more carbon atoms is the same as described above.
R ⁵¹ is the same as R ^{41 in the} formula (4).
m5 is preferably 0 in that the effect of the present invention is more excellent. When m5 is 0, the amine compound is a monoamine.

Amine compound, the effect of the present invention is more excellent, in terms of excellent tack out, preferably C ₂₂ H ₄₅ -NH _2.

  The melting point or freezing point of the amine compound is preferably 50 ° C or more, more preferably 50 to 80 ° C, from the viewpoint that the effect of the present invention is more excellent and the tackiness in summer is excellent. The freezing point can be measured according to JIS K 0065.

The method for producing the amine compound is not particularly limited. For example, a conventionally well-known thing is mentioned.
The amine compounds can be used alone or in combination of two or more.

  The content of the amine compound is more excellent in the effect of the present invention, the surface of the sealing material has no irregularities, the appearance of the sealing material is excellent, and the tackiness is excellent. It is preferably from 10 to 10 parts by mass, more preferably from 1 to 3 parts by mass.

<Silane coupling agent>
The silane coupling agent contained in the composition of the present invention is a compound having a hydrolyzable silyl group and an amino group. The silane coupling agent has an amino group as amino group 2.
The silane coupling agent can react with the modified polymer by having a hydrolyzable silyl group. This makes it difficult for the silane coupling agent to bleed out of the sealing material in the present invention.

(Hydrolyzable silyl group)
A hydrolyzable silyl group is a group in which a hydrolyzable group is bonded to a silicon atom. In the present invention, the hydrolyzable silyl group includes a hydroxy group generated by hydrolysis of the hydrolyzable group. The hydrolyzable silyl group is, for example, the same as the above-mentioned crosslinkable silyl group. Specific examples of the hydrolyzable group include an alkoxy group. Examples of the alkoxy group include a methoxy group and an ethoxy group.

Examples of the hydrolyzable silyl group include those in which 1 to 3 hydrolyzable groups are bonded to a silicon atom.
When one or two hydrolyzable groups are bonded to a silicon atom, the remaining groups are not particularly limited. For example, an alkyl group is mentioned. Examples of the alkyl group include a methyl group and an ethyl group.

The amino group and the hydrolyzable silyl group can be bonded via an organic group. The organic group is not particularly limited. For example, a group represented by the formula (6) can be mentioned.
^{-R 62 - (NH-R 61} ) m61 - (6)
In the formula (6), R ⁶¹ and R ⁶² are each independently a hydrocarbon group. The hydrocarbon group is not particularly limited. For example, an aliphatic hydrocarbon group (chain or branched) and an aromatic hydrocarbon group are exemplified. Examples of the aliphatic hydrocarbon group include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, and a trimethylene group.
m61 is 0 or 1.

Examples of the silane coupling agent include a compound represented by the following formula (7).
In the formula (7), OR ⁷¹ is a hydrolyzable group, and OR ⁷¹ may be a hydroxy group.
R ⁷² is the same as defined above for the remaining groups,
m71 is 1-3.
R ⁷³ is a hydrocarbon group as in R ⁶¹ .
m72 is 0 or 1.
R ⁷⁴ is a hydrocarbon group as in R ⁶² .

It is preferable that the silane coupling agent has one amino group 2 in one molecule, since the effect of the present invention is more excellent and the tackiness is excellent.
The silane coupling agent is mentioned as one of the preferable embodiments not having an imino group, in that the effect of the present invention is more excellent and the tackiness is excellent.

Examples of the silane coupling agent include an amino group and an imino group such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane. A compound having:
A compound having an amino group (monoamine) such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane;
Compounds having C = N, such as 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine;
Examples include compounds having -NH-, such as N-phenyl-3-aminopropyltrimethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane.

The method for producing the silane coupling agent is not particularly limited. For example, a conventionally well-known thing is mentioned.
The silane coupling agents can be used alone or in combination of two or more.

  The content of the silane coupling agent is preferably from 0.1 to 5 parts by mass, based on 100 parts by mass of the modified polymer, from the viewpoint that the effects of the present invention are more excellent, workability and reduction of residual tack are excellent. The amount is more preferably from 0.5 to 3.0 parts by mass, even more preferably from 1 to 2 parts by mass.

<Filler>
The filler contained in the composition of the present invention is not particularly limited as long as it can be contained in the composition for a sealing material. For example, calcium carbonate, talc, silica, carbon black and the like can be mentioned.
Among them, calcium carbonate is preferred. Calcium carbonate is not particularly limited.
The fillers can be used alone or in combination of two or more.

  The content of the filler is preferably from 100 to 300 parts by mass, more preferably from 150 to 200 parts by mass, based on 100 parts by mass of the modified polymer, in that the effect of the present invention is more excellent and the workability is excellent. preferable.

<Curing catalyst>
The curing catalyst contained in the composition of the present invention is not particularly limited as long as it is a compound capable of hydrolyzing and / or condensing a crosslinkable silyl group or a hydrolyzable silyl group.

  One of the preferable embodiments is that the curing catalyst contains a tin catalyst.

  The tin catalyst is not particularly limited. For example, metal carboxylate such as tin octoate, tin butanoate, tin caprylate, tin oleate; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dioctyltin dilaurate, diphenyltin diacetate , Dibutyltin oxide, a reaction product of dibutyltin oxide and a phthalate, an organic tin compound such as dibutyltin dimethoxide, dibutyltin (triethoxysiloxy), and a tin chelate compound such as dibutyltin diacetylacetonate. .

Above all, dibutyltin such as dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dioctyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin (triethoxysiloxy), dibutyltin such as dibutyltin diacetylacetonate (A compound in which two butyl groups are bonded to a tin atom) is preferable.
The curing catalysts can be used alone or in combination of two or more.

  The content of the curing catalyst is preferably from 0.1 to 2.0 parts by mass, and more preferably from 0.1 to 1.0 part by mass, based on 100 parts by mass of the modified polymer, in that the effect of the present invention is more excellent. Parts are more preferred.

  The composition of the present invention may further contain additives in addition to the above components. As the additive, for example, a polymer other than a predetermined modified polymer, a nitrogen-containing compound other than a predetermined amine compound, a silane coupling agent other than a predetermined silane coupling agent, a plasticizer, a thixotropic agent, a dehydrating agent, And thickeners.

The method for producing the composition of the present invention is not particularly limited. For example, it can be produced by mixing the above-mentioned predetermined components and additives that can be contained as necessary.
The composition of the present invention can be manufactured as a one-part composition.

The composition of the present invention can be used as a composition for a sealing material.
The substrate to which the composition of the present invention can be applied is not particularly limited. Examples include glass, plastic, rubber, wood, metal, asphalt, stone, and porous members.
The method for applying the composition of the present invention to a substrate is not particularly limited.

The composition of the present invention can be cured by, for example, moisture in the air. The temperature at the time of curing can be, for example, 5 to 35 ° C.
An adhesive can be applied to the sealant formed by the composition of the present invention. The adhesive is not particularly limited. For example, a conventionally well-known thing is mentioned.

Hereinafter, the present invention will be described specifically with reference to examples. However, the present invention is not limited to these.
<Production of composition>
The components shown in Table 1 below were used in the compositions (parts by mass) shown in the same table, and were mixed with a stirrer to produce a composition.

<Evaluation>
The following evaluation was performed using the composition manufactured as described above. The results are shown in Table 1.
(Residual tack)
The composition produced as described above is applied on a substrate in a thickness of 10 mm, and cured at 23 ° C. and 50% RH for 24 hours. Then, the residual tack on the surface of the obtained sealing material is tack-checked. (Product name Tackiness checker HTC-1, manufactured by Toyo Seiki Co., Ltd.) was used to measure the strength of residual tack.

When the strength of the residual tack was 0.2 N or less, it was evaluated that the reduction of the residual tack was very excellent, and this was indicated as “◎”.
When the strength of the residual tack was more than 0.2 N and 0.5 N or less, it was evaluated that the reduction of the residual tack was excellent, and this was indicated by “〇”.
When the strength of the residual tack exceeded 0.5 N, it was evaluated that the reduction of the residual tack was inferior, and this was indicated as "x".

(Stain resistance)
-Initial The composition produced as described above was applied on a substrate in a thickness of 10 mm and cured at 50 ° C and 50% RH for 24 hours, and then at 23 ° C and 50% RH for 3 hours. After curing, the surface resistance of the obtained sealing material was examined for stain resistance according to Japan Sealing Material Manufacturers Association Standard JSIA 003: 2011.
As a result of the above evaluation, when there was no stain on the surface of the sealing material, it was evaluated that the initial contamination resistance was excellent, and this was indicated by “Δ”.
As a result of the above evaluation, if there was a stain on the surface of the sealing material, it was evaluated that the initial stain resistance was poor, and this was indicated as "x".

-After outdoor exposure The composition produced as described above is applied on a substrate in a thickness of 10 mm, cured at 50 ° C and 50% RH for 24 hours, and then cured at 23 ° C and 50% RH for 3 hours. After allowing to cure for a period of time and being left outdoors for 3 months, the surface resistance of the obtained sealing material was examined according to the Japan Sealing Material Manufacturers Association Standard JSIA 003: 2011.
As a result of the above evaluation, when there was no stain on the surface of the sealing material, it was evaluated as having extremely excellent stain resistance after outdoor exposure, and this was indicated as “◎”.
When silica sand adhered to less than 10% of the surface of the sealing material, it was evaluated as having excellent stain resistance after outdoor exposure, and this was indicated by “〇”.
When silica sand adhered to 10% or more and less than 20% of the surface of the sealing material, it was evaluated as poor in stain resistance after outdoor exposure, and this was indicated by “Δ”.
When silica sand adhered to 20% or more of the surface of the sealing material, it was evaluated as extremely poor in stain resistance after outdoor exposure, and this was indicated as "x".

(Workability)
The composition produced as described above is applied to a substrate in a thickness of 10 mm, cured at 23 ° C. and 50% RH, and the tack of the surface of the obtained sealing material is touched with a finger to obtain a surface tack. Was checked, and the time from the start of curing until the surface tack disappeared was measured.
When the time until the surface tack disappeared was 1 hour or more from the start of curing, the workability was evaluated to be excellent, and this was indicated by “〇”.
When the time until the surface tack disappeared was less than 1 hour from the start of curing, the workability was evaluated as poor, and this was indicated by "x".

Details of each component shown in Table 1 are as follows.
Modified polymer: (meth) acrylic acid ester polymer having a trimethoxysilyl group at a terminal. Product name SB802S (manufactured by Kaneka Corporation)

Amine compound 1 (monoamine): Nissan amine VB-S (trade name), manufactured by NOF Corporation. Freezing point 55-65 ° C
Comparative amine compound _{1 (C 17 H 33 -)} : hardened beef tallow propylenediamine _{(Structure: C 17 H 33 -NH- (C} 3 H 6) -NH 2), trade name Asufazoru 10, manufactured by NOF CORPORATION and compare Amine compound 2 (hexylene group): 1,6-hexanediamine, manufactured by Tokyo Chemical Industry ・ Comparative amine compound 3 (dodecylene group): 1,12-dodecanediamine, manufactured by Tokyo Chemical Industry

Silane coupling agent 1 (monoamine): 3-aminopropyltrimethoxysilane _{(Structure: (CH 3 O) 3 SiC} 3 H 6 NH 2), trade name KBM-903, Shin-Etsu Chemical Co., Ltd. Silane coupling agent 2 (amino group + imino group): N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, trade name KBM-602 (structure below), manufactured by Shin-Etsu Chemical Co., Ltd.
-Epoxy silane: KBM-403 (structure below), manufactured by Shin-Etsu Chemical Co., Ltd.

Filler 1: Colloidal calcium carbonate, Calfine 200M (manufactured by Maruo Calcium Co., Ltd.)
-Filler 2: heavy calcium carbonate, snow light S (manufactured by Maruo Calcium Co., Ltd.)
・ Curing catalyst: dibutyltin (U-202H, manufactured by Nitto Kasei)

・ Thixotropic agent: Disparon # 6500, manufactured by Kusumoto Chemicals ・ Dehydrating agent: vinyltrimethoxysilane (trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Plasticizer: polyoxypropylene diol (trade name: Exenol 3020, manufactured by Asahi Glass Co., Ltd.)
・ Thickener: trade name mineral spirit, manufactured by Nippon Oil Corporation

  As is evident from the results shown in Table 1, Comparative Examples 1 to 4 which do not contain a predetermined amine compound but instead contain an amine compound having an alkyl group or an alkylene group having less than 20 carbon atoms have stain resistance Was low.

On the other hand, it was confirmed that the sealing material obtained from the composition of the present invention had the desired effects.
Comparing Examples 1 and 2, Example 1 containing a silane coupling agent 1 having one amino group and no imino group contains a silane coupling agent 2 having an amino group and an imino group. It was superior to Example 2 in stain resistance after outdoor exposure.
When Examples 1 and 3 are compared, Example 1 in which the content of the silane coupling agent exceeds 0.2 parts by mass is higher than that in Example 3 in which the content is 0.2 parts by mass after the outdoor exposure. Excellent in stain resistance and excellent in reducing residual tack.
Comparing Examples 1 and 4, Example 1 in which the content of the silane coupling agent is less than 4 parts by mass is more resistant to contamination after outdoor exposure than Example 4 in which the content is 4 parts by mass. More excellent, reduced residual tack and excellent workability.

Claims (8)

A modified polymer having at least one crosslinkable silyl group, wherein the crosslinkable silyl group is bonded to a terminal;
An amine compound having an alkyl group having 20 or more carbon atoms and an amino group 1,
A silane coupling agent having an amino group 2,
A filler,
A composition for a sealing material, comprising a curing catalyst.   The composition for a sealing material according to claim 1, wherein the carbon number is 22 to 30.   The sealing material composition according to claim 1, wherein the amine compound has a melting point of 50 ° C. or higher.   The composition for a sealing material according to any one of claims 1 to 3, wherein the amine compound has one amino group 1 in one molecule and does not have an imino group.   The sealing material composition according to any one of claims 1 to 4, wherein the content of the amine compound is 0.5 to 10 parts by mass with respect to 100 parts by mass of the modified polymer.   The composition for a sealing material according to any one of claims 1 to 5, wherein the silane coupling agent has one amino group 2 in one molecule and does not have an imino group.   The composition for a sealing material according to any one of claims 1 to 6, wherein the content of the silane coupling agent is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the modified polymer. object.   The composition for a sealing material according to any one of claims 1 to 7, wherein the curing catalyst includes a tin catalyst.