JP3304956B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxypropylene polymer containing a reactive silicon group, and a hindered polymer.
The present invention relates to a novel curable composition containing a knol-based and / or hindered amine-based antioxidant.

[0002]

BACKGROUND OF THE INVENTION An oxy group having a reactive silicon group (a silicon atom-containing group containing a silicon atom to which a hydroxyl group or a hydrolyzable group is bonded and which can form a siloxane bond). The propylene polymer can be a liquid polymer and is cured at room temperature by moisture or the like to produce a rubber-like cured product. For this reason, this polymer is used as an elastic sealant for buildings. When this polymer is used, it may be used as a composition to which an antioxidant has been added in order to improve the weather resistance and heat resistance of the cured product.

The present inventors have studied a curable composition containing an oxypropylene polymer having a reactive silicon group having excellent weather resistance. As a result, a oxypropylene polymer having a narrow molecular weight distribution was used. It was further found that the weather resistance and heat resistance were further improved, leading to the present invention.

[0004]

The curable composition of the present invention comprises (A) a polymer having a main chain of

Embedded image In consists repeating unit represented, a oxypropylene polymer having at least one silicon atom-containing group (reactive silicon group) containing bound silicon atom of a hydroxyl group or a hydrolyzable group, Mw / Mn (weight-average (Molecular weight / number average molecular weight) of 1.6 or less and a number average molecular weight (Mn) of 6.0
Oxypropylene polymer is 00 or more, and (B) hindered phenol-based antioxidant and inhibit Sunda <br/> Doamin antioxidant (hereinafter, simply referred to as "antioxidants") comprising a.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The reactive silicon group referred to in the present invention is not particularly limited.
For example, a group represented by the following general formula and Chemical Formula 3 can be mentioned.

[0006]

Embedded image [Wherein, R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
An aralkyl group of 20 or a triorganosiloxy group represented by (R ′) ₃ SiO—, wherein R ¹ or R ² is 2
When there are more than one, they may be the same or different. Here, R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. Also,
m

Embedded image B in may be different. m shows the integer of 0-19. However, it is assumed that a + Σb ≧ 1 is satisfied. ].

The hydrolyzable group represented by X is not particularly limited, and may be any conventionally known hydrolyzable group. Specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoxime group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group,
An alkenyloxy group and the like can be mentioned. Of 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, but from the viewpoint of gentle hydrolysis and easy handling, alkoxy groups such as methoxy group are preferred. Groups are particularly preferred.

This hydrolyzable group or hydroxyl group can be bonded to one to three silicon atoms, and (a + Δb) is 1
-5 is preferred. When two or more hydrolyzable groups or hydroxyl groups are present in the reactive silicon group, they may be the same or different.

The reactive silicon group may have one silicon atom or two or more silicon atoms. In the case of a reactive silicon group in which silicon atoms are linked by a siloxane bond or the like, 20 silicon atoms are required. There may be degrees.

[0010] A reactive silicon group represented by the following general formula (5) is preferable from the viewpoint of easy availability.

[0011]

Embedded image (In the formula, R ² , X and a are the same as described above.).

Specific examples of R ¹ and R ² in the above general formula and Chemical Formula 3 include alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group and the like. And an aralkyl group such as a benzyl group, and a triorganosiloxy group represented by (R ′) ₃ SiO—, wherein R ′ is a methyl group or a phenyl group. As R ¹ , R ² and R ′, a methyl group is particularly preferred.

It is preferable that at least one, preferably 1.1 to 5 reactive silicon groups be present in one molecule of the oxypropylene polymer. When the number of reactive silicon groups contained in one molecule of the polymer is less than one, the curability becomes insufficient,
It becomes difficult to exhibit good rubber elasticity behavior.

The reactive silicon group may be present at the terminal of the molecular chain of the oxypropylene polymer or may be present therein. When the reactive silicon group is present at the terminal of the molecular chain, the effective network chain amount of the oxypropylene polymer component contained in the finally formed cured product increases, so that high strength, high elongation, and low elastic modulus are obtained. The resulting rubber-like cured product is easily obtained.

The oxypropylene polymer constituting the polymer main chain in the component (A) used in the present invention includes:

Embedded image In it is made of repeating units represented. The oxypropylene polymer may be linear or branched, or a mixture thereof.

As the number average molecular weight (Mn) of the oxypropylene polymer, those having a number average molecular weight (Mn) of 6,000 or more can be effectively used, but those having a number average molecular weight of 6,000 to 30,000 are preferred. . Furthermore, in this oxypropylene polymer, the ratio (Mw / Mn) between the weight average molecular weight and the number average molecular weight is 1.6 or less, and the molecular weight distribution is extremely narrow (high monodispersity). Mw / Mn
Is preferably 1.5 or less, more preferably 1.4 or less. The molecular weight distribution can be measured by various methods, and is usually determined by gel permeation chromatography (GPC).
Measurement by the method is common. Since the molecular weight distribution is narrow despite the large number average molecular weight, the composition of the present invention has a low viscosity before curing and is easy to handle, and shows good rubber-like elastic behavior after curing. .

The oxypropylene polymer having a reactive silicon group as the component (A) of the present invention is preferably obtained by introducing a reactive silicon group into an oxypropylene polymer having a functional group.

An oxypropylene polymer having a high molecular weight and a narrow molecular weight distribution and having a functional group can be obtained by a usual polymerization method of oxypropylene (anionic polymerization method using caustic alkali) or a chain extension reaction method using this polymer as a raw material. Although it is extremely difficult to obtain, Japanese Patent Application Laid-Open Nos. 61-197632 and 61-215622, which are special polymerization methods,
JP-A-61-215623, JP-A-61-21863
No. 2, JP-B-46-27250 and JP-B-59-1
No. 5,336, and the like. When a reactive silicon group is introduced, the molecular weight distribution tends to be broader than that of the polymer before the introduction, so that the molecular weight distribution of the polymer before the introduction is preferably as narrow as possible.

The introduction of the reactive silicon group may be performed by a known method. That is, for example, the following method is used.

(1) An oxypropylene polymer having a functional group such as a hydroxyl group at the terminal is reacted with an organic compound having an active group and an unsaturated group having reactivity to the functional group, and then obtained. Hydrosilylation is performed by reacting a hydrosilane having a hydrolyzable group on the reaction product.

(2) An oxypropylene polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group (hereinafter referred to as a Y functional group) at a terminal thereof is reacted with a functional group (hereinafter referred to as a Y functional group) , Y ′ functional group) and a compound having a reactive silicon group.

Examples of the silicon compound having a Y 'functional group include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane Amino group-containing silanes such as γ-
Mercapto group-containing silanes such as mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane; γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Epoxysilanes; vinyl-type unsaturated group-containing silanes such as vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane; and γ-chloropropyltrimethoxysilane. Silanes containing chlorine atoms;
γ-isocyanatopropyltriethoxysilane, γ-
Isocyanate-containing silanes such as isocyanate propyl methyl dimethoxy silane; hydrosilanes such as methyl dimethoxy silane, trimethoxy silane, methyl diethoxy silane and the like can be specifically exemplified, but are not limited thereto. Absent.

Of the above methods, the method (1) or the method (2) of reacting a polymer having a terminal hydroxyl group with a compound having an isocyanate group and a reactive silicon group is preferable.

[0024] (B) antioxidant of the component, a hindered phenol, also because the hindered amine. Specific examples of these include various antioxidant handbooks published by Taiseisha and “Deterioration and stabilization of polymer materials” published by CMC Corporation (pages 235 to 242). But are not limited by these.

That is, as a hindered phenol-based antioxidant, 2,6-di-tert-butyl-4-
Methylphenol, 2,6-di-tert-butyl-4
-Ethylphenol, mono (or di or tri) (α-methylbenzyl) phenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol),
2,2'-methylenebis (4-methyl-6-tert-
Butylphenol), 4,4'-butylidenebis (3-
Methyl-6-tert-butylphenol), 4,4 '
-Thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis [3- (3-t-butyl −
5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6-
(4-hydroxy-3,5-di-t-butylanilino)
-1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, N, N'-hexamethylenebis (3,
5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene, calcium bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate), tris- (3,5-di-
t-butyl-4-hydroxybenzyl) -isocyanurate, 2,4-bis [(octylthio) methyl] -O-
Cresol, N, N'-bis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-
3,5-bis (α, α-dimethylbenzyl) phenyl]
-2H-benzotriazole, 2- (3,5-di-t-
Butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
-5-chlorobenzotriazole, 2- (3,5-di-
t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, methyl-3- [3-t-
Butyl-5- (2H-benzotriazol-2-yl)
-4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3,5
-Di-t-butyl-4-hydroxybenzyl) -2-n
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -butylmalonate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, adeca Mark AO manufactured by Argus Co., Ltd.
-30, Mark AO-80; Ciba Geigy
IrganoxMD 1024, Irg
anox 1425, Irganox 245,

Embedded image S. F. O. Antioxidant manufactured by S Corporation
HPM-12; Isonox 129 manufactured by Schenectady KK; Sa manufactured by Sumitomo Chemical Co., Ltd.
milizerGM, SumilizerGA-80,

Embedded image Naugard XL- manufactured by Uniroyal Co., Ltd.
1;

Embedded image And the like.

Examples of the hindered amine antioxidant include dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate polycondensate and poly [｛6 − (1,1,3,3-
(Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2
2,6,6-tetramethyl-4-piperidyl) imino}], N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,
2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl)
Sebacate, bis- (2,2,6,6-tetramethyl-4-piperidinyl) succinate, Ciba G
Irgafos 168 manufactured by Eigy Corporation; Sa
Sandstab P-EP manufactured by ndoz Co., Ltd.
Q: Cyanox 1790 manufactured by ACC; B
org Warner (Ultranox)
626; Mark P manufactured by Adeka Argus Co., Ltd.
EP-36; manufactured by Sumitomo Chemical Co., Ltd.

Embedded image And the like.

The amount of the antioxidant used is not particularly limited, but is preferably 0 parts by weight based on 100 parts by weight of the reactive silicon-containing oxypropylene polymer (A). 0.11 to 10 parts,
More preferably, it is 0.1 to 5 parts. The antioxidants may be used alone or in combination of two or more. In particular, it is preferable to use a mixture of a hindered phenol compound and a hindered amine compound.

In curing the composition of the present invention, a curing catalyst may or may not be used. When a curing catalyst is used, conventionally known curing catalysts can be widely used. Specific examples thereof include titanates such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylate salts such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate; dibutyltin oxide and phthalate Dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; chelates such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate Compounds; lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine , Diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) Phenol, morpholine, N
Amine compounds such as -methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicyclo (5.4.0) undecene-7 (DBU), or salts of these amine compounds with carboxylic acids and the like; Low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, N- (β
Silanol condensation catalysts such as silane coupling agents having an amino group such as -aminoethyl) aminopropylmethyldimethoxysilane; and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts.
These catalysts may be used alone or in combination of two or more.

These curing catalysts are used in an amount of 0.1 to 100 parts of the reactive silicon group-containing oxypropylene polymer.
It is preferably about 1 to 20 parts, more preferably about 1 to 10 parts. If the amount of the curing catalyst used is too small relative to the reactive silicon group-containing oxypropylene polymer, the curing rate becomes slow, and the curing reaction does not easily proceed sufficiently. On the other hand, if the amount of the curing catalyst is too large relative to the reactive silicon group-containing oxypropylene polymer, local heat generation or foaming occurs during curing, and it is difficult to obtain a good cured product, which is not preferable.

The reactive silicon group-containing oxypropylene polymer can be modified by incorporating various fillers. As fillers, reinforcing fillers such as fume silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic Fillers such as bentonite, ferric oxide, zinc oxide, activated zinc white, hydrogenated castor oil and shirasu balloon; fibrous fillers such as asbestos, glass fibers and filaments.

When it is desired to obtain a cured composition having high strength with these fillers, mainly, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, If a filler selected from active zinc white and the like is used in an amount of 1 to 100 parts based on 100 parts of the reactive silicon group-containing oxypropylene polymer, preferable results can be obtained. In addition, when it is desired to obtain a cured composition having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon, etc. Is used in the range of 5 to 200 parts with respect to 100 parts of the reactive silicon group-containing oxypropylene polymer, a preferable result can be obtained. Of course, these fillers may be used alone or in combination of two or more.

In the curable composition of the present invention, the use of a plasticizer in combination with a filler is more effective because the elongation of the cured product can be increased or a large amount of filler can be mixed. As this plasticizer, dioctyl phthalate,
Phthalates such as dibutyl phthalate and butyl benzyl phthalate; aliphatic dibasic esters such as dioctyl adipate, isodecyl succinate and dibutyl sebacate; glycol esters such as diethylene glycol dibenzoate and pentaerythritol; Aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; Phosphates such as tricresyl phosphate, trioctyl phosphate and octyl diphenyl phosphate; Epoxy plastics such as epoxidized soybean oil and epoxy benzyl stearate Polyester plasticizers such as polyesters of dibasic acid and dihydric alcohol; Polyethers such as polypropylene glycol and its derivatives; Poly-α-methylstyrene, polystyrene Polystyrenes such emissions; polybutadiene, butadiene - acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, can be used in any form of plasticizers alone or a mixture of two or more of such chlorinated paraffins. The amount of the plasticizer is 0 to 10 based on 100 parts of the reactive silicon group-containing oxypropylene polymer.
When used in the range of 0 parts, a preferable result is obtained.

The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-mentioned components are mixed and kneaded at room temperature or under heat using a mixer, roll, kneader, or the like, or a suitable solvent is added. Conventional methods such as dissolving and mixing components using a small amount can be employed. Also, by appropriately combining these components, a one-pack or two-pack composition can be prepared and used.

When the curable composition of the present invention is exposed to the atmosphere, the curable composition forms a three-dimensional network by the action of moisture and cures into a solid having rubber-like elasticity.

In using the curable composition of the present invention, if necessary, an adhesion improver, a physical property modifier,
Various additives such as a storage stability improver, a lubricant, a pigment, and a foaming agent can be appropriately added.

The curable composition of the present invention is particularly useful as an elastic sealant and can be used as a sealant for buildings, ships, automobiles, roads and the like. Further, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin moldings alone or with the aid of a primer, it can be used as various types of sealing compositions and adhesive compositions. . Further, it is also useful as a food packaging material, a cast rubber material, a molding material, and a paint.

[0037]

The composition of the present invention has excellent weather resistance and heat resistance of the cured product as compared with a composition using a polymer having a wide molecular weight distribution as the component (A).

The reactive silicon group-containing oxypropylene polymer used as the component (A) in the curable composition of the present invention has a narrow molecular weight distribution despite its large number average molecular weight. Therefore, before curing, the composition of the present invention has a lower viscosity and is easier to handle than a conventional composition containing a reactive silicon group-containing oxypropylene polymer having the same molecular weight and a wide molecular weight distribution.

As described above, since the viscosity before curing is low, not only the workability is good, but also a large amount of filler can be blended to obtain an excellent room temperature curable composition.

Further, chemical resistance such as acid resistance is unexpectedly greatly improved, and water resistance is also excellent.

[0041]

EXAMPLES In order to further clarify the present invention, examples are given below.

Synthesis Example 1 A 1.5-liter pressure-resistant glass reaction vessel was charged with a molecular weight of 15.0
00 polyoxypropylene triol (Mw / Mn =
1.38 g (0.081 equivalent) of 1.38 and a viscosity of 89 poise were charged and placed under a nitrogen atmosphere.

At 137 ° C., 19.1 g (0.099%) of a 28% methanol solution of sodium methoxide was added through a dropping funnel.
Was added dropwise and reacted for 5 hours, followed by devolatilization under reduced pressure.
Return under nitrogen atmosphere, 9.0 g of allyl chloride (0.118
Was added dropwise and reacted for 1.5 hours, and then 5.6 g of a 28% methanol solution of sodium methoxide (0.5 g) was added.
029 equiv) and 2.7 g of allyl chloride (0.035 equiv)
Allylation was carried out using.

The reaction product was dissolved in hexane and subjected to adsorption treatment with aluminum silicate, and then hexane was removed under reduced pressure to obtain 311 g of a yellow transparent polymer (viscosity: 68 poise).

270 g (0.065 equivalent) of this polymer
Was charged into a pressure-resistant glass reaction vessel and placed under a nitrogen atmosphere. Catalyst solution of chloroplatinic acid _{(H 2 PtCl 6 · 6H 2} O
0.075 ml of a solution obtained by dissolving 25 g in 500 g of isopropyl alcohol) was added thereto, followed by stirring for 30 minutes. 6.24 g (0.059 equivalents) of dimethoxymethylsilane was added from a dropping funnel, reacted at 90 ° C. for 4 hours, and then devolatilized to obtain 260 g of a yellow transparent polymer.

Synthesis Example 2 A polyoxypropylene triol having a number average molecular weight of 15,000 (Mw / Mn = 1.38,
220 g (0.0447 equivalent) of viscosity and 89 g of dibutyltin dilaurate were charged, and 8.45 g (0.0447 equivalent) of γ-isocyanatopropylmethyldimethoxysilane was added dropwise at room temperature under a nitrogen atmosphere.
After the completion of the dropwise addition, the reaction was carried out at 75 ° C. for 1.5 hours. And IR spectrum, after confirming the formation of C = O absorption near disappearance 1730 cm ^-1 of the NCO absorption at about 2280 cm ^-1, the reaction was terminated. 213 g of a colorless and transparent polymer were obtained.

Comparative Synthesis Example 1 420 g of polyoxypropylene glycol having a number average molecular weight of 3,000 and 80 g of polyoxypropylene triol having a number average molecular weight of 3,000 were charged into a nitrogen-resistant pressure-resistant glass reaction vessel. Sodium hydroxide 40
g was added and reacted at 60 ° C. for 13 hours, and then 19 g of bromochloromethane was reacted at 60 ° C. for 10 hours. (The Mw / Mn of the obtained polymer is 2.1 and the viscosity is 38
5 poise. Subsequently, 15 g of allyl chloride was added and reacted for 36 hours. After the completion of the reaction, the pressure was reduced to remove volatile substances.

The contents were taken out into a beaker and dissolved in hexane. After adsorption treatment with aluminum silicate, hexane was removed under reduced pressure.

500 g of this polymer was charged into a reaction vessel purged with nitrogen, and a catalyst solution of chloroplatinic acid (H ₂ PtCl
The ₆ · _6H 2 O 25g Isopropyl alcohol 500
g), and then added with 12 g of dimethoxymethylsilane and reacted at 80 ° C. for 4 hours. After the completion of the reaction, the pressure was reduced to remove volatile substances, and 550 g of a pale yellow transparent polymer was obtained.

The viscosities of the polymers obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Example 1 were measured using a B-type viscometer (BM type rotor N).
o. 4, 12 rpm) at 23 ° C. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of each polymer were analyzed by GPC. GPC was analyzed at a oven temperature of 40 ° C. using tetrahydrofuran as a distillation solvent in a column packed with polystyrene gel (manufactured by Tosoh Corporation). Table 1 shows the results.

[0051]

[Table 1]

Example 1 and Comparative Example 1 Polymer 10 obtained in Synthetic Example 1 or Comparative Synthetic Example 1
NOCRAC SP manufactured by Ouchi Shinko Chemical Co., Ltd. as a hindered phenolic antioxidant
Part, TINUVIN3 manufactured by CIBA-GEIGY Co., Ltd.
27 parts, 27 parts of Sanol LS770 manufactured by Sankyo Co., Ltd. as a hindered amine antioxidant, 3 parts of tin octylate and 0.5 part of laurylamine as a curing catalyst were added and uniformly kneaded. Among the obtained compositions, Example 1
The composition of Example 1 (using the polymer of Synthesis Example 1) is the composition of Comparative Example 1 (using the polymer of Comparative Synthesis Example 1).
The viscosity was lower than that of, and the handling was easy.

After a sheet having a thickness of 3 mm was prepared using these compositions, the sheet was heated at 23 ° C. for 2 days and then at 50 ° C. for 3 days.
Cured for days. When this cured composition was evaluated by Sunshine WOM, the composition of Example 1 was 7%.
After 20 hours, the surface slightly dissolved. On the other hand, the surface of the composition of Comparative Example 1 was slightly dissolved after 480 hours.

Reference Example Polymer 10 obtained in Synthesis Example 1 or Comparative Synthesis Example 1
To 0 part, 3 parts of tin octylate and 0.5 part of laurylamine were added and kneaded uniformly.

After a sheet having a thickness of 3 mm was prepared using these compositions, the sheet was heated at 23 ° C. for 2 days and then at 50 ° C. for 3 days.
Cured for days. When this cured composition was evaluated by Sunshine WOM, the surface was slightly dissolved after 72 hours in each case.

Example 2 A curable composition was obtained in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 2 was used instead of the polymer obtained in Synthesis Example 1. The cured product of this composition had excellent weather resistance similar to that of Example 1.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-43449 (JP, A) JP-A-61-233043 (JP, A) JP-A-61-37839 (JP, A) JP-A-57-379 155249 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 71/00-71/14

Claims (4)

(57) [Claims] (A) The polymer main chain is represented by the following formula: In consists repeating unit represented, a oxypropylene polymer having at least one silicon atom-containing group containing bound silicon atom of a hydroxyl group or a hydrolyzable group, M
w / Mn contains several oxypropylene polymer average molecular weight of 6,000 or more, and (B) hindered phenol-based antioxidant and inhibit Sunda <br/> Doamin antioxidants in 1.6 Curable composition. 2. The polymer of component (A) has a Mw / Mn of 1.5.
The curable composition according to claim 1, wherein: 3. The polymer of component (A) has a number average molecular weight of 6,
The curable composition according to claim 1, which has a molecular weight of 000 to 30,000. 4. The polymer according to claim 1, wherein a silicon atom-containing group is present at a molecular chain terminal in the polymer of the component (A).
The curable composition according to item.