JPH1112423A - Highly weatherable sealing material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-pack sealing material composition which is curable at ordinary temperature and improved in extensibility, weatherability and durability by blending a specified fluoro-copolymer and a polymer obtained through the reaction of a hydroxylated polymer with an isocyanate having hydrolyzable silyl groups. SOLUTION: This composition consists of 99-10 wt.% fluoro-copolymer obtained by copolymerizing 10-70 mol.% fluoroolefin monomer, 10-70 mol.% alkyl (meth)acrylate monomer of formula I (wherein R is a 1-20C alkyl, cycloalkyl, or halogenated alkyl; and X is H or methyl), 3-40 mol.% vinyl ester monomer of formula II (wherein R<1> is a 1-20C alkyl, cycloalyl, or phenyl which may be substituted) and 0.5-30 mol.% olefin monomer having hydrolyzable silyl groups; and 1-90 wt.% polymer obtained by reacting a polymer having at least two hydroxyl groups with an isocyanate having hydrolyzable silyl groups in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealant composition which is excellent in weather resistance and can be cured at room temperature in a one-pack type.

[0002]

2. Description of the Related Art Fluororesins are known to be excellent in heat resistance, chemical resistance, weather resistance, water repellency, lubricity and electrical properties. It has become widely used in architectural exterior applications such as paints and overlay films. On the other hand, in the field of sealing materials, polysulfide-based, polyurethane-based, silicone-based and modified silicone-based compositions are known, but polysulfide-based and polyurethane-based compositions lack flexibility and weather resistance, and silicone-based The composition is problematic in that it is contaminated by low molecular weight bleed, and the modified silicone composition has insufficient weather resistance, and no satisfactory material has been found as a sealing material in all aspects. The present inventors have previously proposed a solution of the above problem as a fluoroolefin, a specific alkyl (meth) acrylate, a specific vinyl ester and a fluorine-containing copolymer comprising a monomer having an alkoxysilyl group, and both terminals. (Japanese Patent Application No. 8-313100) has proposed a sealing material composition containing a polyoxyalkylene having an alkoxysilyl group as an essential component. However, it has been found that there is still room for improvement in durability in this method.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high weather-resistant sealing material which can be cured at room temperature in a one-pack type and has excellent elongation and durability.

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a fluorine-containing copolymer having a hydrolyzable silyl group and a polymer having two or more hydroxyl groups have been combined with an intramolecular compound. A sealing material made of a polymer obtained by reacting an isocyanate having a hydrolyzable silyl group into not only has excellent weather resistance and high elongation,
The inventor has found that it has excellent durability that cannot be predicted from the prior art, and has completed the present invention. That is, the present invention provides a fluoroolefin monomer unit:
70 mol%, (meth) acrylic acid alkyl ester monomer unit represented by the following formula (1): 10 to 70 mol%, vinyl ester monomer unit represented by the following formula (2): 3 to
A fluorine-containing copolymer (A) comprising 40 mol% and 0.5 to 30 mol% of an olefinic monomer unit having a hydrolyzable silyl group, and a polymer having two or more hydroxyl groups and hydrolyzing in a molecule It is a highly weather-resistant sealing material composition containing a polymer (B) obtained by reaction with an isocyanate having a hydrophilic silyl group as an essential component. CH ₂ ＣCXCOOR (1) (wherein, R represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or a halogen-containing alkyl group, and X represents a hydrogen atom or a methyl group.) R ¹ COOCHＣＨCH ₂ (2) (wherein, R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or a phenyl group which may have a substituent.)

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The fluoroolefin in the present invention includes tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, dichlorodifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride and perfluoro (alkyl vinyl ether). Among them, among these,
Tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and trifluoroethylene are preferred from the viewpoint of polymerizability, and more preferred are tetrafluoroethylene, chlorotrifluoroethylene and trifluoroethylene.

The alkyl (meth) acrylate in the present invention is a compound represented by the above formula (1),
The ester chain represented by R in the formula (1) is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or a halogen-containing alkyl group, and atoms such as oxygen, nitrogen and sulfur are added to the ester chain within a range not to impair the physical properties. May be included. However, when the proportion of these atoms is increased, the weather resistance and stain resistance are reduced, so that it is preferable that the number of these atoms be 5 or less in the ester chain.

The above compounds include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, neopentyl acrylate, and ethylhexyl acrylate. , Acrylic acid isodecyl ester,
Lauryl acrylate, tridecyl acrylate, stearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, tricyclodecinyl acrylate, tetrahydrofurfuryl acrylate, methoxyethyl acrylate, acrylate Alkyl acrylates such as dimethylaminoethyl acrylate, chloroethyl acrylate and trifluoroethyl acrylate, and methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and isobutyl methacrylate Ester, tertiary butyl methacrylate, neopentyl methacrylate, ethylhexyl methacrylate Esters, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, tricyclodecynyl methacrylate, tetrahydrofurfuryl methacrylate And methacrylic acid alkyl esters such as methacrylic acid methoxyethyl ester, methacrylic acid dimethylaminoethyl ester, methacrylic acid chloroethyl ester and methacrylic acid trifluoroethyl ester. They are used alone or in combination of several kinds. Among these, alkyl acrylates are preferred from the viewpoints of copolymerizability with fluoroolefin and flexibility of the obtained fluorine-containing copolymer.

[0008] vinyl esters of the present invention, the a compound represented by formula (2), R ¹ in formula (2)
The alkyl chain represented by is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group or a phenyl group which may have a substituent. Further, oxygen, nitrogen, sulfur, etc. may be added to the ester chain as long as the physical properties are not impaired. May be included. Specific examples of the above compounds include vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, and vinyl pivalate. And vinyl versatate, vinyl cyclohexanecarboxylate, vinyl chloroacetate, vinyl benzoate and vinyl para-tert-butyl benzoate. Among them, R ¹ represents an alkyl group having 3 to 18 carbon atoms or a cycloalkyl group. Is preferred.

The olefinic monomer having a hydrolyzable silyl group in the present invention is a compound represented by the following formula (3). These compounds include, for example, a hydroxyl-containing monomer having an olefinically unsaturated bond. It can be synthesized by reacting the monomer with an isocyanate having a hydrolyzable silyl group in the molecule. R ² SiR ³ _n Y _3-n (3) (wherein, R ² is a group having an olefinically unsaturated bond;
³ represents an alkyl group having 1 to 20 carbon atoms, Y represents a hydrolyzable group, and when there are a plurality of groups, Y may be the same or different;
Represents an integer of 0 to 2) In the formula (3), R ² is a vinyl group, an allyl group, a butenyl group, a vinyloxy group, an allyloxy group, an acryloyl group, a metallyloyl group, CH ₂ ＣＨCHO (CH ₂ )
_{3 -, CH 2 = CHCOO (} CH 2) 3 -, CH 2 = C
_{HOCO (CH 2) 3 -,} CH 2 = C (CH 3) COO
(CH ₂ ) ₃ — or CH ₂ ＣC (CH ₃ ) COO (C
H ₂ ) ₂ —O— (CH ₂ ) ₃ — and the like. Among them, a vinyl group and CH ₂ ＣＨCHCOO (CH ₂ )
_3- is preferred. R ³ in the above formula (3) includes a methyl group, an ethyl group, a propyl group, an octyl group, an octadecyl group and the like. Y represents an alkoxy group, a chlorine atom, a bromine atom, an amino group, an acyloxy group,
Examples thereof include a phenoxy group, a mercapto group, and an iminooxy group. Among them, an alkoxy group is particularly preferable. Further, a methoxy group as a specific example of the alkoxy group,
Examples thereof include an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group. Among them, a methoxy group and an ethoxy group are particularly preferable.

Further, instead of copolymerizing the olefinic monomer having a hydrolyzable silyl group, a hydroxyl group-containing monomer having an olefinically unsaturated bond is copolymerized with the fluoroolefin monomer and the like. A method in which the obtained copolymer is reacted with an isocyanate having a hydrolyzable silyl group to replace a hydroxyl group in the copolymer with a hydrolyzable silyl group is also applicable. In the case of the above method, the hydroxyl group-containing monomer having an olefinically unsaturated bond includes hydroxyl group-containing ethers such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether and hydroxydecyl vinyl ether, hydroxyethyl crotonate and hydroxyoctyl crotonate. Examples include hydroxyalkyl (meth) acrylates such as hydroxyalkyl crotonates, hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate and hydroxy (caprolactam-containing alkyl) acrylate. The isocyanate having a hydrolyzable silyl group in the molecule used for substituting the hydroxyl group of the hydroxyl group-containing monomer having an olefinically unsaturated bond with a hydrolyzable silyl group is represented by the following formula (4). Compound. R ⁴ _(3-a) SiY ² _a R ⁵ NCO (4) (wherein, R ⁴ is an alkyl group having 1 to 20 carbon atoms, Y ² is a hydrolyzable group, and R ⁵ is an alkylene having 1 to 17 carbon atoms) A represents an integer of 1 to 3) Examples of the isocyanate having a hydrolyzable silyl group in the molecule include (C ₂ H ₅
O) ₃ Si (CH ₂ ) ₃ NCO, (CH ₃ O) ₃ Si
(CH ₂ ) ₃ NCO and (CH ₃ O) ₃ SiNCO are exemplified.

The fluorinated copolymer (A) in the present invention
May be copolymerized with a monomer other than the above monomers as long as the physical properties are not impaired. Such monomers include α-olefins such as ethylene, propylene and isobutylene; chloroethylenes such as vinyl chloride and vinylidene chloride; alkyl vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; vinyl acetate, vinyl caproate, caprylic acid Examples include vinyl esters such as vinyl and vinyl laurate,
It is not limited to these.

The ratio of each monomer unit in the above-mentioned fluorinated copolymer is as follows: fluoroolefin monomer unit: 10 to 7
0 mol%, (meth) acrylic acid alkyl ester monomer unit: 10 to 70 mol%, vinyl ester monomer unit:
3 to 40 mol% and an olefinic monomer unit having a hydrolyzable silyl group: 0.5 to 30 mol%, preferably a fluoroolefin monomer unit: 20 to 60 mol%, (meth) acrylic Acid alkyl ester monomer unit: 20 to 60 mol%, vinyl ester monomer unit: 5
３０30 mol% and an olefinic monomer unit having a hydrolyzable silyl group: 2-20 mol%.

When the amount of the fluoroolefin monomer unit exceeds 70 mol%, the copolymer becomes a crystalline copolymer, and the flexibility may be lowered. When it is less than 10 mol%, the weather resistance may be lowered. If the amount of the (meth) acrylic acid alkyl ester monomer unit exceeds 70 mol%, the stain resistance may decrease, and if it is less than 10 mol%, the flexibility may decrease. Further, if the vinyl ester monomer unit exceeds 40 mol%, the weather resistance may decrease, and if it is less than 3 mol%, the water resistance may decrease. Further, when the olefinic monomer unit having a hydrolyzable silyl group has 3
If it exceeds 0 mol%, the crosslink density of the copolymer may increase and the flexibility may decrease. If it is less than 0.5 mol%, the crosslinking may be insufficient and the strength may decrease. Other monomers have the effect of reducing the cost of the copolymer, but if it exceeds 40 mol%, the weather resistance may be reduced.

The molecular weight of the fluorinated copolymer is preferably from 2,000 to 200,000, more preferably from 3,000 to 20,000, as the number average molecular weight (in terms of polystyrene) determined by gel permeation chromatography (GPC). If the molecular weight is too high, the workability deteriorates, and if it is too low, the mechanical strength decreases.

The fluorinated copolymer is produced by a method of copolymerizing the monomers in the presence of a radical-generating polymerization initiator. Examples of the polymerization method include ordinary methods such as suspension polymerization and emulsion polymerization in an aqueous medium and solution polymerization in an organic solvent.

The radical-generating polymerization initiator includes:
Diisopropyl peroxydicarbonate, di-2-ethoxyethyloxydicarbonate, tert-butyl peroxypivalate, peroxides such as benzoyl peroxide and lauroyl peroxide, azobisisobutyronitrile and azobisisovaleronitrile, etc. Azo compounds and inorganic peroxides such as ammonium persulfate and potassium persulfate can be used.

Examples of the emulsifier in the emulsion polymerization include potassium or ammonium perfluorooctanoate, ammonium perfluorooctanesulfonate, sodium salt of higher alcohol sulfate and polyethylene glycol ether.

As the organic solvent in the solution polymerization, an organic hydrocarbon compound or a fluorine organic solvent is suitable, and cyclic ethers such as tetrahydrofuran and dioxane; and aromatic hydrocarbon compounds such as benzene, toluene and xylene. Esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and cyclohexanone; freons such as 1,1,2-trichloro-1,2,2-trifluoroethylene;
Examples thereof include alcohols such as methanol, ethanol and isopropanol, and one or more of these can be used.

In the polymerization, a pressure-resistant autoclave is used,
The polymerization is preferably carried out at 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. In the polymerization, all the monomers may be initially charged in a batch, or a part of the monomers may be sequentially added as the polymerization proceeds. If necessary, potassium carbonate, sodium hydrogen carbonate, hydrotalcite, an anion exchange resin and the like may be added as a pH adjuster.

The highly weather-resistant sealing material composition of the present invention is obtained by reacting the fluorine-containing copolymer (A) with a polymer having two or more hydroxyl groups and an isocyanate having a hydrolyzable silyl group in the molecule. (B). Examples of the polymer having two or more hydroxyl groups include polyether polyols and polyester polyols, and examples of the polyether polyols include polyethylene glycol and polypropylene glycol. These compounds are commercially available, for example, desmophen 1900U as a commercial product,
1915U (trade names: all manufactured by Sumitomo Bayer Urethane Co., Ltd.) and the like are preferably used. On the other hand, as polyester polyols, FLEXOREZ-188 and 148 [trade names: both KING INDUSTO]
Commercially available products such as RIES Co., Ltd.) and desmophen 1652, 1200 [trade names: all manufactured by Sumitomo Bayer Urethane Co., Ltd.], but not limited thereto, for example, a hydroxyl group-containing acrylic ester, a hydroxyl group-containing vinyl ether and A copolymer containing a hydroxyl group-containing vinyl ester or the like in a monomer unit may be used.

It is necessary that the number of hydroxyl groups present in one molecule of the polymer is two or more, but the number of hydroxyl groups is preferably within ten, more preferably within five. When the number of hydroxyl groups is one, crosslinking is insufficient, and when the number is more than 10, the crosslinking density is increased, so that flexibility may be reduced. The number average molecular weight (in terms of polystyrene) of the polymer by GPC is 100 to 5000.
0 is preferable, and 200 to 10,000 is more preferable. If the molecular weight is too high, the workability becomes insufficient, and if it is too low, the flexibility may decrease.

The isocyanate having a hydrolyzable silyl group in the molecule to be reacted with the polymer having two or more hydroxyl groups may be a compound represented by the formula (4). The reaction between the polymer having two or more hydroxyl groups and the isocyanate having a hydrolyzable silyl group in the molecule is represented by, for example, the following formula (5). HO- (R ⁶ ) -OH + R ⁴ _(3-a) SiY ² _a R ⁵ NCO → R ⁴ _(3-a) SiY ² _a R ⁵ NHCOO- (R ⁶ ) -OCONHR ⁵ SiY ² _a R ⁴ _{( 3-a)} (5) (wherein, R ⁴ represents an alkyl group having 1 to 20 carbon atoms, Y ² represents a hydrolyzable group, R ⁵ represents an alkylene group having 1 to 17 carbon atoms, and a represents 1 to 3 And R ⁶ represents a polyether group or a polyester group.)

The above-mentioned reaction may be carried out in an organic solvent. As the organic solvent, an organic hydrocarbon compound containing no hydroxyl group is suitable. For example, cyclic ethers such as tetrahydrofuran and dioxane, benzene, toluene and xylene And aromatic ketones such as ethyl acetate and butyl acetate, and ketones such as acetone, methyl ethyl ketone and cyclohexanone. One or more of these can be used. The reaction is preferably carried out at a ratio of 0.5 to 3 mol of isocyanate to 1 mol of hydroxyl group of the polymer, more preferably 0.8 to 1.5 mol. The reaction is carried out under a nitrogen atmosphere at a reaction temperature of 20 to 10.
The reaction is preferably performed at 0 ° C. and a reaction time of 1 to 48 hours.

The mixing ratio of the polymer (B) obtained by reacting the fluorocopolymer (A) with the isocyanate in the present invention is (A) :( B) = 99: 1 to 1 by weight.
0:90 is preferred, and more preferably (A):
(B) = 90: 10 to 30:70. If the ratio of (A) is higher than 99: 1, sufficient flexibility cannot be obtained, and if the ratio of (B) is higher than 10:90, the weather resistance may decrease. The mixing method of the above (A) and (B) is not particularly limited, and the mixing method used in the field of ordinary paints is applied as it is.

The sealing material composition of the present invention includes:
It is desirable to mix a curing accelerator and a filler in addition to the essential components of the fluorinated copolymer (A) and the polymer (B). Examples of the curing accelerator include tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin diacetate, organic acid compounds such as p-toluenesulfonic acid, and amines such as DBU (diazabicycloundecene). Among them, tin-based is preferable from the viewpoint of curing speed. The use amount of these is preferably 100 ppm to 15% (weight ratio) based on the total weight of the polymer.

The fillers include silica, silicates, diatomaceous earth, calcium carbonate, magnesium carbonate,
Examples thereof include carbon black, clay, talc, bentonite, titanium oxide, iron oxide, zinc oxide, zinc white, shirasu balloon, and glass fiber. Among these, silica, silicic acid, clay, talc, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide and the like are preferable because they improve the strength or elongation of the sealing material. The amount of these used is preferably 10 to 400 parts by weight per 100 parts by weight of the total weight of the polymer.

The sealing agent in the present invention may further include, if necessary, an ultraviolet absorber such as a benzophenone compound, a benzotriazole compound and an oxalic anilide compound, a light stabilizer such as a hindered amine compound,
Antioxidants such as hindered phenols, plasticizers such as DOP, paraffin oil and polypropylene glycol compounds, adhesion enhancers, dehydrating agents and organic solvents may be blended. Hereinafter, specific examples will be described.

[0028]

【Example】

[Synthesis of Fluorinated Copolymer] Synthesis Example 1 In a 2-liter autoclave equipped with a stirrer, 135 g of butyl acetate and 75 g of ethanol were used as organic solvents.
Acrylic acid butyl ester (hereinafter referred to as “B
A ") 5.5 g, 2-ethylhexyl acrylate (hereinafter" HA ") 7.9 g, vinyl laurate (hereinafter" VLu ") 12.3
g and vinyltrimethoxysilane (hereinafter “VMS”)
1.4 g) and di-2-ethoxyethylperoxydicarbonate (hereinafter referred to as “EE”) as a polymerization initiator.
3.8 g). Next, after degassing and nitrogen replacement were repeated three times, degassing was performed under reduced pressure, and 510 g of chlorotrifluoroethylene (hereinafter referred to as “CTFE”) was charged. The temperature was raised to 50 ° C. to start the polymerization, and during 7 hours,
A mixed solution of 49.9 g of BA, 71.8 g of HA, 36.7 g of VLu and 12.6 g of VMS was pumped into the autoclave at a constant speed using a pump. After a lapse of 7 hours from the start of the polymerization, the temperature was raised to 60 ° C., and the polymerization was carried out for a total of 9 hours. After purging unreacted CTFE, 12 g of sodium borate was added, the temperature was raised to 40 ° C., and the mixture was stirred for 2 hours. After cooling,
The autoclave was opened to obtain a copolymer solution. The resulting solution was filtered to remove sodium borate, dried and dried.
g of the copolymer was obtained. The number average molecular weight in terms of polystyrene of the obtained copolymer measured by GPC was 4,800. When the fluorine content of this copolymer was measured, it was 2
2.2%, and the analyzed value of Si was 0.8%. ¹
From H-NMR and ¹³ C-NMR, the composition of the copolymer was C
TFE / BA / HA / VLu / VMS = 54.3 / 1
It was 7.2 / 16.8 / 7.8 / 3.9 (mol%).

Synthesis Example 2 The VMS of the initially charged monomer was trimethoxysilylpropyl methacrylate (hereinafter referred to as “MMS”) 3.2.
g, and VMS of the additional monomer was changed to 28.8 g of MMS.
g was obtained. The number average molecular weight of the obtained copolymer is 4,600.
Met. When the fluorine content of this copolymer was measured, it was 18.8%, and the analyzed value of Si was 1.0%. Analysis was performed in the same manner as in Synthesis Example 1, and the composition of the copolymer was
CTFE / BA / HA / VLu / MMS = 48.7 / 1
It was confirmed to be 8.6 / 18.4 / 8.5 / 5.5 (mol%).

Synthesis Example 3 Synthesis Example 1 except that VMS of the initially charged monomer was 1.1 g of 2-hydroxyethyl acrylate (hereinafter referred to as “HEA”) and VMS of the additional monomer was 9.9 g of HEA.
After drying, 330 g of a copolymer was obtained. The number average molecular weight of the obtained copolymer was 4,100. When the fluorine content of this copolymer was measured, it was 23.0%.
Met. Analysis was performed in the same manner as in Synthesis Example 1, and the composition of the copolymer was calculated as follows: CTFE / BA / HA / VLu / HEA = 55.
8 / 16.3 / 16.2 / 8.1 / 3.6 (mol%).

[Reaction of Hydroxyl-Containing Fluorinated Copolymer with Isocyanate Having Hydrolyzable Silyl Group] Synthesis Example 4 Hydroxyl-containing fluorinated copolymer 100 obtained in Synthesis Example 3
g, trimethoxysilylpropyl isocyanate 7.3
g and butyl acetate (200 g) were placed in a 1 L flask, and the atmosphere was replaced with a nitrogen atmosphere, followed by stirring at 50 ° C. for 24 hours.
Thereafter, the solvent was distilled off under reduced pressure to obtain 105 g of a hydrolyzable silyl group-containing fluorinated copolymer.

[Synthesis of Polymer by Reaction of Polymer Having Two or More Hydroxyl Groups and Isocyanate Having Hydrolyzable Silyl Group] Synthesis Example 5 100 g of polyoxyalkylene having an average molecular weight of 2,000 and having hydroxyl groups at both ends 22.2 g of trimethoxysilylpropyl isocyanate and 200 butyl acetate
g was placed in a 1-liter flask, and the atmosphere was replaced with a nitrogen atmosphere, followed by stirring at 50 ° C. for 24 hours. Thereafter, the solvent was distilled off under reduced pressure to obtain 116 g of a hydrolyzable silyl group-containing fluorinated copolymer.

Synthesis Example 6 Desmophen 1652, a polyester polyol
[Product name: Sumitomo Bayer Urethane Co., Ltd.] 100
g, trimethoxysilylpropyl isocyanate19.
3 g and 200 g of butyl acetate were placed in a 1-liter flask and synthesized under the same conditions as in Synthesis Example 5, to obtain 109 g of a hydrolyzable silyl group-containing fluorinated copolymer.

Examples 1-5 and Comparative Examples 1-2 The fluorinated copolymers (A) of Synthesis Examples 1, 2 and 4, the polymers (B) of Synthesis Examples 5 and 6, a curing accelerator (reagent dibutyltin) Dilaurate), calcium carbonate (Calfine 500, Maruo Calcium Co., Ltd.), titanium oxide (CR-97, manufactured by Ishihara Sangyo Co., Ltd.), plasticizer (RS-, manufactured by Asahi Denka Co., Ltd.)
705], an ultraviolet absorber [Tinuvin B75 manufactured by Ciba Geigy Co., Ltd.] and a dehydrating agent (trimethoxymethylsilane)
Was blended in parts by weight shown in Table 1 below. The blended composition was cured at 20 ° C. for one week, and further cured at 50 ° C. for one week, and the following test was conducted. The results are shown in Table 2 below.

Comparative Example 3 MS20A (trade name: polypropylene glycol containing alkoxysilyl groups at both ends, manufactured by Kaneka Chemical Co., Ltd.) was blended in place of the polymer (B), and the same test as in Example 1 was performed. Was. Table 2 shows the test results.

Test Method Breaking strength, breaking elongation, 50% tensile stress (the adherend is aluminum), and the durability test were measured by the methods described in JIS A 5758 (sealing material for building) and classification code 10030. . For the accelerated weathering test, the sample was JIS 575
8 and the surface state and elongation retention (%) after a 2,000-hour test were measured with a sunshine weatherometer (manufactured by Suga Test Instruments). The criteria for determining the surface state and the method for calculating the elongation retention are shown below.・ Criteria for determining surface condition ○: no change, Δ: slight crack, ×: deep crack ・ Elongation retention (%) = (elongation after accelerated weathering test / initial elongation) × 100

[0037]

[0038]

[Table 2]

[0039]

The sealing material composition of the present invention is a one-component type that can be cured at room temperature, has excellent weather resistance, maintains high elongation as well as has high durability, and is used as a sealing material composition for various applications. Can be used.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 3/10 C09K 3/10 M

Claims (1)

[Claims] 1. A fluoroolefin monomer unit: 10 to 7
0 mol%, (meth) acrylic acid alkyl ester monomer unit represented by the following formula (1): 10 to 70 mol%, vinyl ester monomer unit represented by the following formula (2): 3 to 4
0 mol% and an olefinic monomer unit having a hydrolyzable silyl group: 0.5 to 30 mol%, a fluorine-containing copolymer (A), and a polymer having two or more hydroxyl groups and a hydrolyzate in the molecule. A highly weather-resistant sealing material composition comprising a polymer (B) obtained by reaction with an isocyanate having a decomposable silyl group as an essential component. CH ₂ ＣCXCOOR (1) (wherein, R represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or a halogen-containing alkyl group, and X represents a hydrogen atom or a methyl group) R ¹ COOCH ＝ CH ₂ (2) (wherein, R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or a phenyl group which may have a substituent)