JPH07305018A - Sealing material composition having high weather resistance - Google Patents

Abstract

PURPOSE:To provide a sealing material composition having high weather resistance, containing a specific fluorine-containing copolymer, a curing agent, etc., and a filler as main components, curable at normal temperature, exhibiting excellent flexibility and stain resistance and suitable as an outdoor sealant, etc. CONSTITUTION:This sealing material composition having high weather resistance is composed mainly of (A) 100 pts.wt. of a fluorine-containing copolymer having a glass-transition temperature of <=10 deg.C and a number-average molecular weight of 10,000-1,000,000 (in terms of PS) and composed of (i) 5-60mol% of a fluoroolefin, (ii) 30-95mol% of an alkyl (meth)acrylate of formula CH2=CXCOOR (R is a 1-20C alkyl, a cycloalkyl or a halogen-containing alkyl; X is H or methyl) and (iii) 0.5-10mol% of a monomer having reactive group such as hydroxyethyl vinyl ether, (B) preferably 10ppm to 5 pts.wt. of a curing agent such as a polyvalent isocyanate compound and/or a cure accelerator such as dibutyltin diacetate and (C) preferably 1-200 pts.wt. of a filler such as silica.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealant composition excellent in weather resistance, which comprises a fluorine-containing copolymer that can be cured at room temperature as an essential component.

[0002]

2. Description of the Related Art Fluorine-based resins have been known to possess excellent heat resistance, chemical resistance, weather resistance, water repellency, lubricity and electrical characteristics, and these characteristics have been utilized in recent years. Is widely used in the building exterior field such as high weather resistance paints and overlay films. On the other hand, in the field of sealing materials, resins such as polysulfide-based, polyurethane-based, silicone-based, and modified silicone-based resins are used, but polysulfide-based and polyurethane-based sealing materials lack flexibility and weather resistance, and The system suffers from bleeding contamination of low molecular weight compounds, and the modified silicone system suffers from poor weatherability.

As a room temperature curable composition and a sealant, which has a stretchable property and gives a cured product excellent in both weather resistance and stain resistance, in order to solve such problems, (a) the repeating unit is from 10 to 10. A number average molecular weight of 1,000 to 5 containing a polymerized unit having 50 polyether side chains and a polymerized unit based on fluoroolefin, and having a curable site.
A composition containing, as an active ingredient, 50,000 fluorocopolymers and (b) a copolymer having a functional group and a polyfluoroalkyl group capable of co-crosslinking with the fluorocopolymer of (a) above. Has been proposed (JP-A-3-122152).

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of multifaceted research on a high weather resistance sealant material having a fluorine-containing copolymer composition different from the above-mentioned prior art,
A fluorocopolymer mainly composed of a fluoroolefin and a specific (meth) acrylic acid alkyl ester and a monomer having a reactive group is capable of being cured at room temperature and has excellent weather resistance and flexibility for a long period of time. The present invention has been completed by discovering that the material exhibits high resistance and stain resistance.

Therefore, an object of the present invention is to provide a highly weather resistant sealant composition which contains a fluorine-containing copolymer curable at room temperature as an essential component and exhibits excellent weather resistance, flexibility and stain resistance. Especially.

[0006]

The highly weather-resistant sealant composition according to the present invention for achieving the above object comprises (a)
Fluoroolefin 5-60 mol%, general formula CH ₂ ═C
XCOOR (where R is an alkyl group having 1 to 20 carbon atoms,
(Meth) acrylic acid alkyl ester represented by a cycloalkyl group or a halogen-containing alkyl group, and X represents hydrogen or a methyl group, from 30 to 95 mol%, and a monomer having a reactive group from 0.5 to 10 mol% A constitutional feature is that a fluorine-containing copolymer having a glass transition temperature of 10 ° C. or lower, (b) a curing agent and / or a curing accelerator, and (c) a filler are main components.

Examples of the fluoroolefin constituting the (a) fluorine-containing copolymer of the present invention include tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, dichlorodifluoroethylene, trifluoroethylene, vinylidene fluoride and vinyl fluoride. , Perfluoro (alkyl vinyl ether), etc., but tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene are preferable from the viewpoint of polymerizability,
Chlorotrifluoroethylene is more preferred.

An alkyl (meth) acrylate represented by the general formula CH ₂ ═CXCOOR (wherein R represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or a halogen-containing alkyl group, and X represents hydrogen or a methyl group). The ester includes an ester chain containing an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, and a halogen-containing alkyl group, but the ester chain may contain atoms such as oxygen, nitrogen, and sulfur as long as the physical properties are not impaired. . However, when the ratio of the above-mentioned atoms increases, weather resistance, stain resistance, etc. decrease, so that it is preferable that the number of atoms in the ester chain be 5 or less.

Specific examples of these acrylic acid alkyl ester compounds include acrylic acid methyl ester,
Acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid butyl ester, acrylic acid isobutyl ester, acrylic acid tertiary butyl ester, acrylic acid neopentyl ester, acrylic acid ethylhexyl ester, acrylic acid isodecyl ester, acrylic acid lauryl ester, acrylic Acid tridecyl ester,
Acrylic acid stearyl ester, acrylic acid cyclohexyl ester, acrylic acid isobornyl ester, acrylic acid tricyclodecynyl ester, acrylic acid tetrahydrofurfuryl ester, acrylic acid methoxyethyl ester, acrylic acid dimethylaminoethyl ester,
Acrylic acid chloroethyl ester, acrylic acid trifluoroethyl ester and other acrylic acid alkyl esters, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, methacrylic acid butyl ester, methacrylic acid isobutyl ester,
Methacrylic acid tert-butyl ester, methacrylic acid neopentyl ester, methacrylic acid ethylhexyl ester, methacrylic acid isodecyl ester, methacrylic acid lauryl ester, methacrylic acid tridecyl ester, methacrylic acid stearyl ester, methacrylic acid cyclohexyl ester, methacrylic acid isobornyl ester Methacrylic acid alkyl esters such as ester, methacrylic acid tricyclodecynyl ester, methacrylic acid tetrahydrofurfuryl ester, methacrylic acid methoxyethyl ester, methacrylic acid dimethylaminoethyl ester, methacrylic acid chloroethyl ester, methacrylic acid trifluoroethyl ester, etc. These may be used alone or in admixture of several types. Of these, application of alkyl acrylates is particularly preferable in view of the polymerizability with fluoroolefins, the flexibility of the copolymer, and the like.

As the monomer having a reactive group, a monomer containing a hydroxyl group, a carboxylic acid group, an epoxy group or an alkoxysilyl group is used, but a hydroxyl group-containing monomer or an alkoxy group capable of imparting room temperature curability is used. It is preferable to select a silyl group-containing monomer. Of these, the hydroxyl group-containing monomer includes, for example, hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, and hydroxypropyl vinyl ether,
Hydroxy group-containing allyl ethers such as hydroxyethyl allyl ether and hydroxybutyl allyl ether, hydroxyalkyl crotonates such as hydroxyethyl crotonate and hydroxypropyl crotonate, hydroxyalkyl acrylates such as hydroxyethyl acrylate, hydroxybutyl acrylate and hydroxypropyl methacrylate. Although there are (meth) acrylates, it is preferable to use hydroxyalkyl (meth) acrylate from the viewpoint of copolymerizability with fluoroolefin and (meth) acrylic acid alkyl ester and flexibility of the copolymer. On the other hand, the alkoxysilyl group-containing monomers include vinylsilanes such as trimethoxyvinylsilane and methyltriethoxyvinylsilane, silyl group-containing monomers such as trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, and dimethyldimethoxysilylpropyl acrylate ( Examples of the (meth) acrylates include silyl group-containing (meth) acrylates.

The fluorinated copolymer (a) of the present invention may be copolymerized with other monomers as long as the physical properties are not impaired. Such copolymers include ethylene, propylene,
Α-olefins such as isobutylene, vinyl chloride, chloroethylenes such as vinylidene chloride, ethyl vinyl ether, alkyl vinyl ethers such as butyl vinyl ether, vinyl acetate, vinyl propionate, vinyl esters such as vinyl caproate are exemplified.
It is not limited to these.

However, the glass transition temperature of the fluorocopolymer must be 10 ° C or lower, preferably -10 ° C or lower. When the glass transition point exceeds 10 ° C, the functionality as a sealing material is lost.

The composition range of each monomer in the fluorine-containing copolymer is as described above. When the content of fluoroolefin is less than 5 mol%, the weather resistance is lowered, and when it exceeds 60 mol%, the crystalline copolymer is contained. Becomes less flexible. When the content of the (meth) acrylic acid alkyl ester is less than 30 mol%, the flexibility is lowered, and when it exceeds 95 mol%, the stain resistance of the resin cannot be maintained. Further, when the amount of the monomer having a reactive group is less than 0.5 mol%, the strength is impaired, and 10
When the amount is more than mol%, the crosslinking density of the copolymer becomes high and the flexibility decreases. Other monomers have the effect of lowering the cost of the copolymer, but if they exceed 30 mol%, the weather resistance will decrease. The preferred composition range of each monomer is 15 to 50 mol% of fluoroolefin, 40 to 80 mol% of (meth) acrylic acid alkyl ester, and 1 to 7 mol% of a monomer having a reactive group. The copolymerizable monomer is in the range of 0 to 30 mol%. However,
These composition ranges are values when all the monomers are 100 mol%.

The (a) fluorine-containing copolymer of the present invention is produced by a method of copolymerizing in the presence of a radical-generating polymerization initiator. As the polymerization method, a usual method such as suspension polymerization or emulsion polymerization in an aqueous medium, solution polymerization in an organic solvent can be employed. As the organic solvent in this case, organic hydrocarbon compounds or fluorine-based organic solvents are suitable, for example, tetrahydrofuran, cyclic ethers such as dioxane, benzene, toluene, aromatic hydrocarbon compounds such as xylene, ethyl acetate, One or more of esters such as butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and freons such as 1,1,2-trichloro-1,2,2-trifluoroethylene can be used. .

As the radical-generating type polymerization initiator, peroxides such as diisopropyl peroxydicarbonate, tertiary butyl peroxypivalate, benzoyl peroxide, lauroyl peroxide, or azobisisobutyronitrile, azobisiso Azo compounds such as valeronitrile and inorganic peroxides such as ammonium persulfate and potassium persulfate can be used. Examples of the emulsifier for emulsion polymerization include perfluorooctanoic acid potassium salt, ammonium salt, perfluorooctanesulfonic acid ammonium salt, higher alcohol sulfate sodium salt, and polyethylene glycol ether.

Polymerization can be carried out in a pressure autoclave under the conditions of a polymerization temperature of 20 to 100 ° C., a pressure of 1 to 200 kg / cm ² , and a reaction time of 3 to 40 hours. Upon polymerization, all monomers may be batch-charged at the initial stage,
A part of the monomers may be sequentially added as the polymerization proceeds.
Further, if necessary, a pH adjusting agent such as potassium carbonate, sodium hydrogen carbonate, hydrotalcite, anion exchange resin may be added.

The molecular weight of the fluorine-containing copolymer is 2000 to 200 in terms of number average molecular weight (in terms of polystyrene) by gel permeation chromatography (GPC).
The range of 10,000 to 1,000,000 is more preferable.
If the molecular weight is too high, the workability will deteriorate, and if it is too low, the mechanical properties will deteriorate.

The above-mentioned (a) fluorine-containing copolymer is blended with the following (b) curing agent and / or curing accelerator depending on the type of reactive group it has, and (c) filling A sealant composition is prepared by blending the agent.

The curing agent (b) is required to be a compound capable of reacting with a reactive group in the fluorine-containing copolymer to form crosslinks. For example, a polyvalent isocyanate compound, a polyvalent blocked isocyanate compound, Examples thereof include aminoplast resins, polycarboxylic acids, acid anhydrides and diglycidyl compounds. As the curing accelerator, tin compounds such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate and dibutyltin dimalate, acidic compounds such as p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid and dodecylbenzenesulfonic acid, Examples thereof include basic compounds such as dibutylamine, triethylamine, diethanolamine, and DBU (diazabicycloundecene).

As described above, it is preferable to select a hydroxyl group or an alkoxysilyl group as the reactive group in the fluorocopolymer from the viewpoint of imparting room temperature curability, and when a hydroxyl group is used as the reactive group, for example, It is preferable that a curing agent is blended with and a curing accelerator is used in combination. As the curing agent at this time, an isocyanate compound such as isocyanurate type, biuret type, trimethylolpropane modified type is preferably used, and the compounding amount thereof is a ratio of the NCO group of the isocyanate compound and the OH group in the fluorine-containing copolymer. It is desirable to set the amount such that is 0.5 to 2 molar equivalents. The curing accelerator used in combination is preferably a tin compound from the viewpoint of curing speed, and the compounding amount is preferably set to 10 ppm to 5% by weight based on the weight of the fluorocopolymer. On the other hand, when an alkoxysilyl group is used as the reactive group, a curing accelerator that accelerates the hydrolysis and condensation reaction of the alkoxysilyl group is used. In this case, the curing accelerator is preferably a tin-based compound from the viewpoint of the curing rate, and the compounding amount is preferably set within the range of 10 ppm to 5% by weight based on the weight of the fluorocopolymer.

As the filler of (c), silica, silicic acid, diatomaceous earth, calcium carbonate, magnesium carbonate, carbon black, clay, talc, bentonite, titanium oxide, iron oxide, zinc oxide, zinc white, shirasu balloon , Glass fiber and the like. Of these, silica, silicic acids, clay, talc, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide and the like are preferably used because they have the function of improving the strength or elongation of the sealing material. The preferred amount of the filler used is 1 to 200 parts by weight per 100 parts by weight of the copolymer.

In addition to the above-mentioned components, the sealing material composition of the present invention contains an ultraviolet absorber such as a benzophenone compound, a benzotriazole compound, an oxalic acid anilide compound, a light stabilizer such as a hindered amine compound, a plasticizer or a solvent. You may mix | blend.

[0023]

According to the sealant composition of the present invention, a fluoroolefin blended in a specific ratio constituting a fluorine-containing copolymer, and having the general formula CH ₂ = CXCOOR (where R is an alkyl group having 1 to 20 carbon atoms). , A cycloalkyl group or a halogen-containing alkyl group, and X represents hydrogen or a methyl group), and each component of the (meth) acrylic acid alkyl ester represented by the formula (3) and a monomer having a reactive group has excellent room temperature curability and excellent weather resistance. It exerts the effect of imparting the property, flexibility and stain resistance, and effectively functions to exert the various performances required for the sealing material, and the curing agent and / or the curing accelerator and the filler are mixed therein. As a result, it exhibits high and stable sealing performance over a long period of time.

[0024]

EXAMPLES Hereinafter, examples of the present invention will be specifically described in comparison with comparative examples. In each example, the fluorine-containing copolymer prepared in the following Synthesis Examples 1 to 6 was used.

[Synthesis Example 1] In a 1.75 liter autoclave equipped with a stirrer, 350 g of ethyl acetate, 130 g of butyl acrylate (hereinafter referred to as "BA"),
12 g of hydroxybutyl acrylate (hereinafter referred to as "HBA") was charged, and deaeration and nitrogen substitution were repeated 3 times, followed by deaeration, and chlorotrifluoroethylene (hereinafter referred to as "CT").
300g was charged. After the temperature was raised to 70 ° C, a polymerization initiator solution prepared by dissolving 1.5 g of azobisisobutyronitrile (hereinafter referred to as "AIBN") in 50 g of ethyl acetate was pressed into an autoclave to start polymerization. Polymerization was carried out for 24 hours, unreacted CTFE was purged, and the autoclave was opened to obtain a copolymer solution. The obtained solution is poured into methanol, washed and dried, and 190
Fluorine-containing copolymer (g) was obtained. GP of the obtained copolymer
The polystyrene equivalent number average molecular weight measured by C is 350.
The glass transition temperature (hereinafter referred to as "Tg") was -35 ° C. When the fluorine analysis of the obtained fluorine-containing copolymer was performed, it was 13.5% by weight, and the hydroxyl value was 24 (mg-KOH / g-resin). ¹ H
The composition of the copolymer by -NMR and ¹³ C-NMR is CT
The FE / BA / HBA was 29.7 / 64.9 / 5.4 (mol%).

[Synthesis Example 2] The monomer composition of Synthesis Example 1 was changed to
Change to CTFE 300g, 2 ethylhexyl acrylate (hereinafter referred to as "HA") 130g, HBA 10g,
The solvent was changed to xylene. Other than that, polymerization was performed under the same conditions as in Synthesis Example 1, and 190 g of a fluorinated copolymer was obtained after drying. The number average molecular weight of the obtained copolymer was 2400.
0 and Tg was -48 ° C. Further, the fluorine analysis value of the copolymer was 11.9%, and the hydroxyl value was 18. When analyzed in the same manner as in Synthesis Example 1, CTFE / HA /
It was confirmed that HBA = 33.3 / 61.6 / 5.1 (mol%).

[Synthesis Example 3] The monomer composition of Synthesis Example 1 was changed to
250 g of CTFE, ethyl acrylate (hereinafter “EA”)
), Methoxyethyl methacrylate (hereinafter referred to as “MEMA”) 25 g, and hydroxyethyl acrylate (hereinafter referred to as “MEA”) 20 g.
Other than that, polymerization was carried out under the same conditions as in Synthesis Example 1, and after drying, 250 g of a fluorinated copolymer was obtained. The number average molecular weight of the obtained copolymer was 14,000 and Tg was -15 ° C. The fluorine analysis value of the copolymer was 8.9%,
The hydroxyl value was 34. When analyzed in the same manner as in Synthesis Example 1, CTFE / EA / MEMA / HEA = 16.5 / 7
It was confirmed to be 2.8 / 4.3 / 6.4 (mol%).

[Synthesis Example 4] The monomer composition of Synthesis Example 1 was changed to
CTFE 200 g, BA 195 g, trimethoxysilylpropyl acrylate (hereinafter referred to as "TRIMSPA") 6 g were changed, and the solvent was changed to ethyl acetate 370 g and isopropanol 30 g. Other than that, the polymerization was performed under the same conditions as in Synthesis Example 1, and 220 g of a fluorine-containing copolymer was obtained after drying. The number average molecular weight of the obtained copolymer was 340.
At 00, the Tg was -39 ° C. The fluorine analysis value of the copolymer was 8.7% and the silicon analysis value was 0.3%. When analyzed in the same manner as in Synthesis Example 1, CTFE / BA
It was confirmed that /TRIMSPA=19.4/79.3/1.2 (mol%).

[Synthesis Example 5] The monomer composition of Synthesis Example 1 was changed to
CTFE 540g, HA 130g, triethoxyvinylsilane (hereinafter referred to as "TRIEVS") 10g, solvent 350g ethyl acetate, isopropanol 50
changed to g. Other than that, polymerization was carried out under the same conditions as in Synthesis Example 1, and after drying, 150 g of a fluorinated copolymer was obtained. The number average molecular weight of the obtained copolymer was 11,000, and T
g was -41 ° C. In addition, the fluorine analysis value of the copolymer was 14.7%, and the silicon analysis value was 0.9%. When analyzed in the same manner as in Synthesis Example 1, CTFE / HA / TRI
It was confirmed that EVS = 40.6 / 54.6 / 4.8 (mol%).

Synthesis Example 6 The monomer composition of Synthesis Example 1 is
Hexafluoropropylene (hereinafter referred to as "HFP") 2
It was changed to 80 g, BA 130 g, and HBA 15 g. Otherwise, polymerization was carried out under the same conditions as in Synthesis Example 1, and after drying, 14
0 g of a fluorine-containing copolymer was obtained. The number average molecular weight of the obtained copolymer was 34,000 and Tg was -38 ° C. Further, the fluorine analysis value of the copolymer was 4.6%, and the hydroxyl value was 39. When analyzed in the same manner as in Synthesis Example 1, it was confirmed that HFP / BA / HBA = 5.3 / 85.7 / 9.1 (mol%).

Examples 1 to 6 100 parts by weight of the fluorine-containing copolymers of Synthesis Examples 1 to 6 were mixed with a curing agent [Dainippon Ink & Chemicals Co., Ltd. "Bernock 95".
5 ″], a curing accelerator (dibutyltin dilaurate reagent),
Calcium carbonate [“CCR” manufactured by Shiraishi Industry Co., Ltd.] and titanium oxide [“R820” manufactured by Ishihara Industry Co., Ltd.] were blended in a weight ratio shown in Table 1.

Then, after curing treatment (at room temperature for 2 weeks), various evaluation tests were carried out, and the results are shown in Table 3.
In addition, each test was based on the following method. (1) The tack-free test, the tensile adhesion test (the adherend is aluminum) and the durability test were in accordance with JIS A5758 (sealing material for construction) and classification code 9030. (2) In the water resistance test, a test body was prepared in accordance with JIS A5758, and the presence or absence of turbidity in warm water after standing in warm water at 50 ° C for one month was observed. (3) For the accelerated weather resistance test, the sample was attached to the holder described in JIS A5758, and a fluorescent ultraviolet weather meter (Q
The surface condition and elongation retention rate after 2000 hours were observed by a panel company, QUV tester. The criteria for the surface condition and the calculation of the elongation retention rate were as follows. Surface condition determination criteria ○: No change Δ: Discoloration ×: Crack occurrence Elongation retention rate = (elongation after accelerated weathering test / initial elongation)
In the x 100 (4) outdoor pollution test, a test plate having a thickness of 1 mm was prepared by applying a sample to the upper half of a 7 cm x 15 cm glass plate with a spatula to prevent bubbles from entering. Outdoor exposure was carried out for 6 months in Funami-cho, Nagoya City, and the degree of contamination was visually evaluated according to the following criteria. ◯: Almost no dust adhered Δ: A little dust adhered ×: Dust adhered considerably

[0033]

[Table 1]

Comparative Example 1 Polypropylene oxide having methoxysilyl groups at both ends [“MS Polymer 20A” manufactured by Kaneka] was blended in a composition shown in Table 2 to prepare a modified silicone sealant. After curing, the same evaluation test as in the example was performed, and the results are also shown in Table 3.

Comparative Example 2 Urethane-modified polysulfide ["Permapol P965" manufactured by Nippon Shokubai Co., Ltd.] was blended in a composition shown in Table 2 to prepare a polysulfide-based sealant. After curing, the same evaluation test as in the example was performed, and the results are also shown in Table 3.

[0036]

[Table 2]

Comparative Example 3 A commercially available one-component silicone-based sealing material [TOSSEAL 381] manufactured by Toshiba Silicone Co., Ltd. was used, and Example 1 was used.
Evaluation tests similar to those in Examples 1 to 6 were performed and compared. The results are also shown in Table 3.

Comparative Example 4 The monomer used in Synthesis Example 1 was 300 g of CTFE / methyl methacrylate (hereinafter referred to as “MMA”) / HBA.
/ 130 g / 10 g, and the solvent was changed to xylene. Others are polymerized by the same method,
After drying, 160 g of a copolymer was obtained. The number average molecular weight of the obtained copolymer was 9,000 and Tg was 93 ° C. The fluorine analysis value of this copolymer was 6.1%, and the hydroxyl value was 22. When analyzed in the same manner as in Synthesis Example 1, CTFE / MMA / HBA = 11.2 / 84.7 /
It was found to be 4.2 (mol%). Obtained Tg9
A composition was prepared in the same manner as in Example 1 except that 100 parts by weight of the copolymer at 3 ° C. was used and the amount of the curing agent was 27 parts by weight, and various evaluation tests were conducted. The results are also shown in Table 3.

[0039]

[Table 3]

From the results of Table 3, the sealing material compositions according to Examples 1 to 6 using the fluorine-containing copolymer of the present invention are excellent in weather resistance and stain resistance, and have sufficient durability and flexibility. It was recognized to have. On the other hand, the modified silicone-based (Comparative Example 1) and polysulfide-based (Comparative Example 2) sealants have reduced weather resistance due to the polyoxyethylene chains and sulfur atoms present in the molecule, and also have a one-component silicone-based sealant. The sealant (Comparative Example 3) has low stain resistance because of its low molecular weight silicone.

[0041]

As described above, according to the present invention, a fluorine-containing copolymer having a novel composition that can be cured at room temperature is used as an essential component,
It is possible to provide a sealing material composition that exhibits effects such as excellent weather resistance, flexibility, and stain resistance. Therefore, it is expected to be useful as a high-quality outdoor sealant.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Ryusei Nishio 1 1 Funami-cho, Minato-ku, Nagoya-shi, Aichi Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute (72) Inventor Akito Iida Nagoya, Aichi 1 Toago Synthetic Chemical Industry Co., Ltd., Nagoya Research Institute, Minami-ku, Toagosei Chemical Industry Co., Ltd. (72) Inventor Hiroshi Inukai 1 Touna Synthetic Chemical Industry Co., Ltd. Nagoya Research Laboratories, 1 Funami-cho, Minato-ku, Aichi Within

Claims (1)

[Claims] 1. (a) 5 to 60 mol% of fluoroolefin, general formula CH ₂ = CXCOOR (where R is 1 carbon atom)
~ 20 alkyl group, cycloalkyl group or halogen-containing alkyl group, X represents hydrogen or methyl group) (meth) acrylic acid alkyl ester 30-95
A fluorine-containing copolymer having a glass transition temperature of 10 ° C. or lower, comprising (b) a curing agent and / or a curing accelerator, and (c) ) A high weather-resistant sealant composition comprising a filler as a main component.