JP2002038129A - Sealing material for double glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing material for double glass having improved temperature-dependence of structural strength and increased adhesion to substrate while keeping the moisture shielding property of hot-melt butyl rubber and suitably usable as a sealing material for the primary sealing of a dual seal or a single seal of double glass. SOLUTION: The sealing material for double glass contains (A) a silyl- containing ethylene/α-olefin/non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group having a specific structure in the molecule, (B) a hot-melt resin, (C) a curing catalyst and (D) water or a metal salt hydrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to (A) a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group, (B) a hot melt resin, and (C) The present invention relates to a sealing material for a double glazing containing a curing catalyst and (D) water or a metal salt hydrate.

[0002]

2. Description of the Related Art Sealing materials for double glazing are classified into two types: primary sealing and secondary sealing. The double glazing unit has a single seal that seals the glass end face with only one type of sealing material, and two types of sealing material (1
There is a dual seal that uses both a secondary seal and a secondary seal), which are mainly used for different purposes. The butyl rubber-based hot melt resin (hereinafter, sometimes referred to as "hot melt butyl") generally used as a hot melt resin for the above-mentioned single seal sealing material and dual seal primary sealing material includes the following: There is a feature. That is, hot melt butyl is a solid or waxy polymer at room temperature,
When the temperature is 0 to 250 ° C., it flows, and when used as an adhesive, it sticks to the surface of various substrates due to wetting in a molten state. Actually, in the manufacturing process of double glazing,
Hot melt butyl is discharged through heating and melting of a special applicator, and solidifies due to a rapid decrease in the temperature of the sealing material after filling. For this reason, compared with other reaction hardening type sealing materials, the curing time can be greatly reduced, and the management and filling work of the sealing material is also easy. It is expected that it will occupy an important position in the double glazing market in the future due to the work performance that can simultaneously achieve quick delivery of products and increase of production capacity.

[0003] However, in single-sealed double-glazed glass, mainly hot-melt butyl is used.
Structural strength is weak, and water vapor barrier properties to the inner surface of the multi-layer glass for a long period of time cannot be secured. As a result, its use is limited to industrial uses such as for showcases where units are replaced in relatively short cycles. In the case of a dual-seal double-layered glass, the secondary seal is excellent in mechanical properties (adhesion to glass and the like) but is inferior in water vapor barrier properties.
A secondary seal is required, and hot melt butyl is used to block water vapor that has passed through the secondary seal. This dual-sealed double-glazed glass has better long-term durability than the single type described above, but requires two types of sealing materials in the manufacturing process, and is more expensive than the single type. . Also, in the case of a dual-type double glazing, if the secondary seal deteriorates with time, the primary seal cannot be held, and the performance may be reduced as much as the single type.

[0004] Since the adhesiveness of hot melt butyl depends on the adhesive strength of butyl rubber, the adhesiveness decreases due to embrittlement at low temperatures, and a double-glazing unit due to softening of a sealing material due to thermoplasticity at high temperatures. A shift may occur, and a heat-resistant creep performance for suppressing the shift is required. However, at present, when comparing hot melt butyl thermoplastics with reactive curable sealants (polysulfide-based or silicone-based sealants), hot-melt butyl has an overwhelming advantage in workability, but depending on temperature, The disadvantage that physical properties such as mechanical characteristics fluctuate greatly remains. Therefore, there is a problem that usable glass size and weight are restricted as compared with the case where a reaction-curable sealing material is used.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve the temperature dependence of the structural strength and the adhesion to a substrate while maintaining the water vapor barrier properties of hot melt butyl, and to improve the properties of the double glazing application. An object of the present invention is to provide a sealing material for double glazing which can be suitably used as a sealing material for a dual seal primary seal or a single seal.

[0006]

SUMMARY OF THE INVENTION The present invention relates to the following sealing material for double glazing. 1. (A) a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the following general formula (1) in the molecule:

Embedded image (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group,
It represents a hydrolyzable group selected from an aminooxy group, a thioalkoxy group, an amino group, a mercapto group and an alkenyloxy group, and m is an integer of 0, 1 or 2. )
A sealing material for a double glazing comprising (B) a hot melt resin, (C) a curing catalyst, and (D) water or a metal salt hydrate. 2. The silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber has the following general formula (2) or (3)

Embedded image (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R ¹
Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X is a hydride group, a halogen group , An alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group, an amino group, a mercapto group and a alkenyloxy group, wherein m is 0, 1 or And n is an integer of 0 to 10
Is an integer. 2. The sealing material for a double glazing according to the above 1, which has at least one silyl group-containing unit represented by the formula (1). 3. The silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber has the following general formula (4) and / or (5)

Embedded image (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. , N is an integer of 0 to 10.) The ethylene / α-olefin / non-conjugated polyene random copolymer rubber having at least one type of norbornene compound having a terminal vinyl group as a non-conjugated polyene represented by the following general formula ( 6)

Embedded image (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group, Represents a hydrolyzable group selected from an amino group, a mercapto group and an alkenyloxy group, and m is an integer of 0, 1, or 2.) 3. The sealing material for a double glazing according to the above 1 or 2, wherein the bond is obtained by adding the SiH group of the silicon compound to the bond. 4. 4. The sealing material for a double glazing according to any one of the above 1 to 3, wherein X is an alkoxyl group. 5. The sealing material for a double glazing according to any one of the above items 1 to 4, wherein the hot melt resin as the component (B) is a butyl rubber-based hot melt resin. 6. The sealing material for a double glazing according to any one of the above items 1 to 5, which is used as a primary sealing material for dual sealing or as a sealing material for single sealing.

Hereinafter, the present invention will be described in more detail. The silyl group-containing silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (hereinafter sometimes also referred to as “silyl group-containing copolymer rubber”) as the component (A) is represented by the above general formula (1) a structural unit derived from a non-conjugated polyene having a hydrolyzable silyl group, preferably containing at least one terminal vinyl group represented by the above general formula (4) or (5) Ethylene / α-olefin / norbornene compound
The non-conjugated polyene random copolymer rubber contains a silyl group represented by the above general formula (1) on the side chain or terminal.

In the general formula (1), R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably one having no aliphatic unsaturated bond, for example, methyl, ethyl , An alkyl group such as propyl, butyl, hexyl, cyclohexyl, an aryl group such as phenyl and tolyl, and a group obtained by substituting part or all of the hydrogen atoms bonded to these carbon atoms with a halogen atom such as a fluorine atom. No. X is a hydride group, a halogen group,
Alkoxyl group, acyloxy group, ketoxime group,
And a group selected from an amide group, an acid amide group, an aminooxy group, a thioalkoxy group, an amino group, a mercapto group and an alkenyloxy group. Among these, an alkoxyl group, particularly an alkoxyl group having 1 to 4 carbon atoms, is preferred. m
Is an integer of 0, 1 or 2, preferably 0 or 1.
It is. In addition, R, X, and m in the general formulas (2), (3), and (6) are the same as above.

The number of silyl groups in one molecule of the silyl group-containing copolymer rubber is one or more, and the average of the number is 0.1-10.
It is preferred that there are. If the number of silyl groups contained in the molecule is less than 0.1, the curability becomes insufficient and good rubber elasticity may not be obtained.

The method for producing the silyl group-modified ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group of the present invention is not particularly limited. (4)
Or a hydrosilylation reaction of a silicon compound represented by the general formula (6) with an ethylene / α-olefin / non-conjugated polyene random copolymer rubber comprising at least one type of norbornene compound having a terminal vinyl group represented by the formula (5) Is preferred.

The ethylene / α-olefin / non-conjugated polyene random copolymer rubber which is reacted with the silicon compound represented by the general formula (6) comprises ethylene, α-olefin having 3 to 20 carbon atoms, It is a random copolymer with a conjugated polyene. 3 to 20 carbon atoms
As the α-olefin, specifically, propylene,
1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1- Pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-
Dodecene, 12-ethyl-1-tetradecene and the like. Among them, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used. These α-olefins are used alone or in combination of two or more.

The non-conjugated polyene preferably used in the present invention is a norbornene compound having a terminal vinyl group represented by the above general formula (4) or (5). General formula (4)
In the above, n is an integer of 0 to 10. R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
^As an alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group,
t-butyl group, n-pentyl group, isopentyl group, t-
Examples include a pentyl group, a neopentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. R ² is a hydrogen atom or a carbon atom having 1 to 1
5 alkyl groups. Specific examples of the alkyl group having 1 to 5 carbon atoms of R ² include the alkyl groups having 1 to 5 carbon atoms among the specific examples of the above R ¹ . In the general formula (5), R ³ represents a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl groups. Specific examples of the alkyl group of R ³ include the same alkyl groups as the specific examples of the alkyl group of R ¹ . Incidentally, R ^1, n in the general formula (2) is the same as R ^1, n in the general formula (4), R ³ in the general formula (3) is the general formula (5)
And R ³ is the same as described above.

As the norbornene compound represented by the general formula (4) or (5), specifically, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2 -Norbornene, 5-
(3-butenyl) -2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-
Pentenyl) -2-norbornene, 5- (1-methyl-
3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-
Heptenyl) -2-norbornene, 5- (3-methyl-
5-hexenyl) -2-norbornene, 5- (3,4-
Dimethyl-4-pentenyl) -2-norbornene, 5-
(3-ethyl-4-pentenyl) -2-norbornene,
5- (7-octenyl) -2-norbornene, 5- (2
-Methyl-6-heptenyl) -2-norbornene, 5-
(1,2-dimethyl-5-hexyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2- Norbornene and the like. Among them, 5-vinyl-2-norbornene, 5-methylene-2
-Norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene,
-(4-pentenyl) -2-norbornene, 5- (5-
Hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (7-octenyl) -2
-Norbornene is preferred. These norbornene compounds can be used alone or in combination of two or more.

In addition to the above norbornene compounds such as 5-vinyl-2-norbornene, the following non-conjugated polyenes can be used in combination as long as the physical properties aimed at by the present invention are not impaired. Specific examples of such a non-conjugated polyene include 1,4-hexadiene and 3-methyl-
Chains such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, and 7-methyl-1,6-octadiene Non-conjugated diene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-
Cyclic unconjugated dienes such as chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene;
3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2
And trienes such as -propenyl-2,2-norbornadiene.

[0015] Ethylene / α comprising the above components
-The olefin / non-conjugated polyene random copolymer has the following composition. (I) Molar ratio of ethylene to α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin) Ethylene / α-olefin / non-conjugated polyene random copolymer rubber is a unit derived from (a) ethylene And (b)
A unit derived from an α-olefin having 3 to 20 carbon atoms (hereinafter, sometimes simply referred to as α-olefin);
0/60 to 95/5, preferably 50/50 to 90/1
0, more preferably 55 / 45-85 / 15, particularly preferably 60 / 40-80 / 20 [(a) /
(B)]. When the molar ratio is within the above range, a sealing material for a double-glazed glass excellent in heat aging resistance, strength characteristics and rubber elasticity, and excellent in cold resistance and workability can be obtained.

(Ii) Iodine value The iodine value of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber is 0.5 to 50 (g / 100).
g), preferably 0.8 to 40 (g / 100 g), more preferably 1 to 30 (g / 100 g), particularly preferably 1.5 to 25 (g / 100 g). Here, the iodine value is a value corresponding to the amount of double bonds contained in the structural unit derived from norbornene having a terminal vinyl group represented by the above general formula (4) and / or general formula (5). When the iodine value is within the above range, the content of the hydrolyzable silyl group can be adjusted to a desired content, and the double glazing has excellent compression set resistance and excellent environmental degradation resistance (heat aging resistance). Sealing material is obtained. If the iodine value exceeds 50, it is disadvantageous in terms of cost, which is not preferable. (Iii) Intrinsic Viscosity The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber measured at 135 ° C. in decalin is 0.001 to 2 dl / g, preferably 0.0
1-2 dl / g, more preferably 0.05-1 dl / g
g, particularly preferably 0.05 to 0.7 dl / g, most preferably 0.1 to 0.5 dl / g. When the intrinsic viscosity [η] is in the above range, a sealing material for a double glazing having excellent strength properties and compression set resistance and excellent fluidity can be obtained.

(Iv) Molecular weight distribution (Mw / Mn) Molecular weight distribution (Mw / Mn) of ethylene / α-olefin / non-conjugated polyene random copolymer rubber measured by GPC
Mn) is 3 to 100, preferably 3.3 to 75, and more preferably 3.5 to 50. This molecular weight distribution (M
When the ratio (w / Mn) is within the above range, a sealant for a double-layer glass excellent in workability and excellent in strength properties can be obtained.

The ethylene / α-olefin / non-conjugated polyene random copolymer rubber is polymerized at a polymerization temperature of 30 to 60 ° C., particularly 30 to 60 ° C. in the presence of a catalyst containing the following compounds (H) and (I) as main components. 59 ° C, polymerization pressure 4-12
kgf / cm ^2, particularly 5~8kgf / cm ^2, the supply amount molar ratio of the non-conjugated polyene and ethylene (non-conjugated polyene /
Ethylene) Under conditions of 0.01 to 0.2, ethylene, an α-olefin having 3 to 20 carbon atoms and a norbornene compound having a terminal vinyl group represented by the above general formula (4) or (5) are randomly selected. It is obtained by copolymerization. The copolymerization is preferably carried out in a hydrocarbon medium.

(H) VO (OR) _n X _3-n wherein R is a hydrocarbon group, X is a halogen atom, and n is an integer of 0 or 1-3. A vanadium compound or a vanadium compound represented by VX ₄ (X is a halogen atom). The soluble vanadium compound (H) is a component that is soluble in a hydrocarbon medium of a polymerization reaction system, and specifically, has the general formula VO (OR) _{a Xb} or V (OR) _c X _d (where R Is a hydrocarbon group, and 0 ≦ a
≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦
Vanadium compounds represented by d ≦ 4, 3 ≦ c + d ≦ 4) or their electron donor adducts can be mentioned as typical examples. More specifically, VOCl ₃ , V
O (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₆ ) ₂ Cl, VO
_{(O-iso-C 3 H} 7) Cl 2, VO (O-n-C 4 H 9) C
l ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₃ , VCl ₄ , VOC
_{l 3, VO (O-n} -C 4 H 9) 3, VCl 3 · 2OC 6 H 12
OH and the like can be exemplified.

(I) An organoaluminum compound represented by R ' _m AlX' _3-m (R 'is a hydrocarbon group, X' is a halogen atom, and m is 1 to 3). Specific examples of the organoaluminum compound (I) include trialkylaluminums such as triethylaluminum, tributylaluminum and triisopropylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum sesquioxide;
Alkylaluminum sesquialkoxides such as butylaluminum sesquibutoxide; R _0.5 Al (OR ¹ ) _0.5
Partially alkoxylated alkylaluminum having an average composition represented by, for example; dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, and diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide Alkyl aluminum sesquihalides, ethyl aluminum dichloride, propyl aluminum dichloride, alkyl aluminum dihalides such as butyl aluminum dibromide and the like; partially halogenated alkyl aluminum; diethyl aluminum hydride;
Partially hydrogenated alkylaluminums such as dialkylaluminum hydrides such as dibutylaluminum hydride, alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide And partially alkoxylated and halogenated alkyl aluminum.

Of the above compound (H), a soluble vanadium compound represented by VOCl ₃ and the above compound (I)
Of these, Al (OC ₂ H ₅ ) ₂ Cl / Al ₂ (OC ₂ H ₅ ) ₃
When a blend of Cl ₃ (blend ratio is 1/5 or more) is used as a catalyst component, the insoluble content after Soxhlet extraction (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) is 1% or less. Ethylene ・ α-olefin ・
It is preferable because a non-conjugated polyene random copolymer rubber can be obtained. Further, as a catalyst used in the above copolymerization,
So-called metallocene catalysts, for example,
May be used.

Next, the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer rubber is subjected to a hydrosilylation reaction (hydrosilylation reaction) with a silicon compound represented by the above general formula (6) to give a silyl group-modified ethylene. A method for producing an α-olefin / non-conjugated polyene copolymer rubber will be described.

Examples of the hydrolyzable group represented by X in the general formula (6) will be described. A hydride group is a hydrogen atom. Examples of the halogen group include a chlorine atom,
Examples include a fluorine atom, a bromine atom and an iodine atom. Examples of the alkoxyl group include a methoxy group, an ethoxy group,
Propoxy group, propoxybutoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, tert-
Butoxy, pentyloxy, hexyloxy, phenoxy and the like. As the acyloxy group,
Examples include an acetoxy group and a benzoyloxy group. Ketoximate groups include acetoximate groups,
Examples thereof include a dimethyl keto xymate group, a diethyl keto oximate group, and a cyclohexyl keto oximate group.
Examples of the amide group include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, and a diphenylamide group. Examples of the acid amide group include a carboxylic acid amide group, a maleic acid amide group, an acrylic acid amide group, and an itaconic acid amide group. Examples of the thioalkoxy group include thiomethoxy, thioethoxy, thiopropoxy, thioisopropoxy, sec
-Thiobutoxy group, tert-thiobutoxy group, thiopentyloxy group, thiohexyloxy group, thiophenoxy group and the like. Examples of the amino group include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diphenylamino group, and the like. Among these, alkoxyl groups, especially those having 1 to 4 carbon atoms.
Are preferred.

As the silicon compound of the general formula (6), specifically, trichlorosilane, methyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane,
Halogenated silanes such as diethylchlorosilane, phenyldichlorosilane and diphenylchlorosilane; trimethoxysilane, triethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, butyldimethoxysilane, methyldiethoxysilane, ethyldiethoxysilane, butylethoxysilane, Alkoxysilanes such as phenyldimethoxysilane; acyloxysilanes such as triacetoxysilane, methyldiacetoxysilane and phenyldiacetoxysilane; tris (acetoxymate) silane and bis (dimethylketoxime) methylsilane;
Examples include ketoxime silanes such as bis (methylethylketoxime) methylsilane and bis (cyclohexylketoxime) methylsilane; and aminooxysilanes such as aminooxysilane and triaminooxysilane. Of these, alkoxysilanes are particularly desirable.

The amount of the silicon compound represented by the above general formula (6) is 0.01 to 0.01 per mole of double bond in the ethylene / α-olefin / non-conjugated polyene random copolymer rubber reacted therewith. 5 moles, preferably 0.05-3
It is preferred to be molar.

The reaction is preferably carried out using a transition metal complex catalyst. As the catalyst, for example, a Group VIII transition metal complex compound selected from platinum, rhodium, cobalt, palladium and nickel is effectively used. Of these, platinum-based catalysts such as chloroplatinic acid and platinum-olefin complexes are particularly preferred. In this case, the amount of the catalyst used is a catalytic amount, but is preferably 0.1 to 10000 ppm as a metal unit with respect to the reactant, more preferably 1 to 1 ppm.
000 ppm, particularly preferably 20 to 200 ppm. The preferred temperature for this hydrosilation reaction is 3
The temperature is 0 to 180 ° C, preferably 60 to 150 ° C. Moreover, you may make it react under pressure as needed. The reaction time is about 10 seconds to 10 hours.

The solvent may or may not be used, but when used, an inert solvent such as ethers and hydrocarbons is preferred.

By the above hydrosilylation reaction,
The SiH group of the silicon compound represented by the general formula (6) is added to the double bond derived from the non-conjugated polyene in the ethylene / α-olefin / non-conjugated polyene random copolymer rubber. In the case of the formula (4) or (5), a silyl group-containing unit represented by the general formula (2) or (3) is generated.

At the time of the reaction, a one-terminal hydrogen-modified siloxane represented by the following formula (7) is added together with the silicon compound represented by the above general formula (6) to provide weather resistance, slipperiness, and gas characteristics characteristic of the siloxane. It is also possible to impart transparency.

[0030]

Embedded image

(In the formula, R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly preferably an alkyl group. P is 5 to 200, particularly preferably p is 5 to 200. It is an integer of 10 to 150.)

The silyl group-containing copolymer rubber as the component (A) is a hydrocarbon polymer, and therefore has good moisture barrier properties and water resistance, and is suitable for various inorganic base materials such as glass and aluminum. The cured product has excellent adhesion performance and good moisture barrier properties.

In the sealing material for double glazing of the present invention,
From the viewpoint of obtaining a sufficient adhesive strength (initial adhesive strength) for temporarily fixing the glass and the spacer in the double-glazing production process, the content of the component (A) is preferably 5 to 50% by weight, More preferably, it is 10 to 50% by weight.

The hot melt resin used as the component (B) of the present invention is not particularly limited, and a commercially available hot melt resin can be used. For example, EVA-based, polyamide-based, polyester-based, polyurethane-based, acrylic-based, butyl rubber-based, and polyolefin-based hot melt resins can be used. Moreover, the softening point is 100 to 2 from the viewpoint of workability.
A temperature of about 50 ° C. is preferred, but not limited to this. Among them, a butyl rubber-based hot melt resin (hot melt butyl) is preferable. The hot-melt butyl that can be used in the present invention is not particularly limited, and those that are usually commercially available can be used. Any of those commercially available as butyl can be used, for example, butyl rubber (IIR) having a degree of unsaturation of about 0.5 to 5.0, Vistanex series (manufactured by Exxon), Telostat series (manufactured by Teloson),
Hamatite series (made by Yokohama Rubber) and the like.

The hot melt resin (B) used in the present invention, for example, hot melt butyl, is used without vulcanizing itself. The content of the component (B) in the sealing material for a double glazing of the present invention is determined from the viewpoint of obtaining sufficient adhesive strength (initial adhesive strength) for temporarily fixing the glass and the spacer in the double glazing manufacturing process. 20-95% by weight
Is more preferable, and more preferably 50 to 90% by weight.

The curing catalyst as the component (C) of the present invention comprises:
Conventionally known silanol condensation catalysts can be used. Specific examples of the curing catalyst include, for example, titanates such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin diurarate, dibutyltin maleate, dibutyltin diacetate, tin octylate,
Tin carboxylate salts such as tin naphthenate; a reaction product of dibutyltin oxide and a phthalate; dibutyltin diacetylacetonate; aluminum trisacetylacetonate, aluminum trisethylacetoacetate;
Organoaluminum compounds such as diisopropoxyaluminum ethyl acetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; 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-methylmorpholine, 2-ethyl-4-methylimidazole,
1,8-diazabicyclo [5.4.0] undecene-7
Amine compounds such as (DBU), or salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines with epoxy compounds A silanol condensation catalyst such as a silane coupling agent having an amino group such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane; and other acidic catalysts and basic catalysts. And other known silanol condensation catalysts. These catalysts
They may be used alone or in combination of two or more.

The compounding amount of the component (C) is set to an appropriate curing speed to avoid local heat generation and firing, and to obtain an appropriate pot life. 0.1 to 20 parts by weight per 100 parts by weight
It is 1 part by weight, more preferably 1 to 10 parts by weight.

Water or metal as the component (D) of the present invention
The hydrate of the salt is a copolymer having a silyl group as the component (A).
Acts as a source of necessary moisture during condensation curing of rubber,
It promotes the formation of a crosslinked structure. Water source is other than water
In the case of
For example, hydration of alkaline earth metal salts
And hydrates of other metal salts. Specifically
Is Al_TwoO_Three・ H_TwoO, Al_TwoO_Three・ 3H_TwoO, Al_Two(S
O_Four)_Three・ 18H_TwoO, Al_Two(C_TwoO_Four)_Three・ 4H_TwoO, Al
Na (SO_Four)_Two・ 12H_TwoO, AlK (SO_Four)_Two・ 12
H_TwoO, BaCl _Two・ 2H_TwoO, Ba (OH)_Two・ 8H
_TwoO, CaSO_Four・ 2H_TwoO, CaS_TwoO_Three・ 6H _TwoO, Ca
(NO_Three)_Two・ 4H_TwoO, CaHPO_Four・ 2H_TwoO, Ca
(C_TwoO_Four) ・ H_TwoO, Co (NO_Three)_Two・ 6H_TwoO, Co
(CH_ThreeCOO)_Two・ 4H_TwoO, CuCl_Two・ 2H_TwoO, C
uSO_Four・ 5H_TwoO, FeCl_Two・ 4H_TwoO, FeCl_Three・
6H_TwoO, FeSO_Four・ 7H_TwoO, Fe (NH_Four) (S
O_Four)_Two・ 12H_TwoO, K_TwoCO_Three・ 1.5H _TwoO, KNaC
O_Three・ 6H_TwoO, LiBr.2H_TwoO, Li_TwoSO_Four・ H
_TwoO, MgSO_Four・ H_TwoO, MgSO_Four・ 7H_TwoO, MgH
PO_Four・ 7H_TwoO, Mg_Three(PO_Four)_Two・ 8H_TwoO, MgCO
_Three・ 3H_TwoO, Mg_Four(CO_Three)_Three(OH)_Two・ 3H_TwoO, M
oO_Three・ 2H_TwoO, NaBr.2H_TwoO, Na_TwoSO_Three・ 7
H_TwoO, Na_TwoSO_Four・ 10H_TwoO, Na_TwoS_TwoO_Three・ 5H
_TwoO, Na_TwoS_TwoO₆・ 2H_TwoO, Na_TwoB_FourO₇・ 10H
_TwoO, NaHPHO_Three・ 2.5H_TwoO, Na_ThreePO_Four・ 12
H_TwoO, Na_TwoCO_Three・ H_TwoO, Na _TwoCO_Three・ 7H_TwoO, N
a_TwoCO_Three・ 10H_TwoO, NaCH_ThreeCOO ・ 3H_TwoO, N
aHC_TwoO_Four・ H_TwoO, NiSO_Four・ 6H_TwoO, NiC_TwoO_Four
・ 2H_TwoO, SnO_Two・ NH_TwoO, NiC_TwoO_Four・ 2H_TwoO,
Sn (SO_Four)_Two・ 2H_TwoO, ZnSO_Three・ 2H_ThreeO, Zn
SO_Four・ 7H_TwoO, Zn_Three(PO_Four)_Two・ 4H_TwoO, Zn (C
H_ThreeCOO)_Two・ 2H_TwoO, etc., but are not limited thereto.
It is not specified.

[0039] Among these, preferred hydrates and hydrates of alkaline earth metal salts of an alkali metal salt, in particular _{MgSO 4 · 7H 2 O, Na} 2 CO 3 · 10H 2 O, N
a ₂ SO ₄ · 10H ₂ O, Na ₂ S ₂ O ₃ · 5H ₂ O, Na ₃ P
_{O 4 · 12H 2 O, Na} 2 B 4 O 7 · 10H 2 O, and the like.

The water as the component (D) is preferably used in an amount of 0.01 to 25 parts by weight, more preferably 0.0 to 25 parts by weight, based on 100 parts by weight of the silyl group-containing copolymer rubber.
It is in the range of 5 to 15 parts by weight, more preferably 0.2 to 5 parts by weight. The hydrate of the metal salt used as the component (D) is based on 100 parts of the silyl group-containing copolymer rubber.
Preferably used in the range of 0.01 to 50 parts by weight,
It is more preferably in the range of 0.1 to 30 parts by weight, and still more preferably in the range of 1 to 10 parts by weight. The water and metal salt hydrate may be used alone or in combination of two or more.

Various additives can be used in combination in the sealing material for double glazing of the present invention. Typical additives are adhesion promoters. A typical example thereof is a silane coupling agent. Of course, an adhesion-imparting agent other than the silane coupling agent can also be used. The silane coupling agent is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter, referred to as a hydrolyzable silicon group) and a functional group other than the group. As the hydrolyzing group, a methoxy group, an ethoxy group, and the like are preferable because of a high hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly preferably 3 or more. Examples of the functional group other than the hydrolyzable silicon group include primary, secondary, and tertiary amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, and halogens. Of these, primary, secondary, and tertiary amino groups, epoxy groups,
Isocyanate groups and isocyanurates are preferred, and isocyanate groups and epoxy groups are particularly preferred.

Specific examples of the silane coupling agent include:
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl)
Aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ-
(2-aminoethyl) aminopropyltriethoxysilane, γ-ureidopropylpropyltrimethoxysilane, n-β- (n-vinylbenzylaminoethyl) -γ
Amino group-containing silanes such as -aminopropyltriethoxysilane and γ-anilinopropyltrimethoxysilane;
mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane; γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,
Epoxy group-containing silanes such as 4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, n-β- (n-carboxymethylaminoethyl) ) Carboxysilanes such as -γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ
-Vinyl-type unsaturated group-containing silanes such as acroyloxypropylmethyltriethoxysilane; halogen-containing silanes such as gamma-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; Isocyanate-containing silanes such as isocyanatepropyltrimethoxysilane and γ-isocyanatepropyltriethoxysilane can be exemplified.

Also, derivatives of these derivatives, such as amino-modified silyl polymers, silylated amino polymers, unsaturated amino silane complexes, blocked isocyanate silanes, phenylamino long-chain alkyl silanes, amino silylated silicones, silylated polyesters, and the like can be used in silane cups. It can be used as a ring agent. Such a silane coupling agent is easily decomposed in the presence of moisture, but can be stably present when added to the component (A) of the sealing material for double glazing of the present invention.

As the adhesion-imparting agent other than the silane coupling agent, a commonly used adhesive or other compound can be used. Specific examples of such an adhesion improver include phenol resin, epoxy resin, coumarone-indene resin, rosin ester resin, terpene-phenol resin, α-methylstyrene-vinyltoluene copolymer, polyethylmethylstyrene, and alkyl. Examples include titanates and aromatic polyisocyanates. The adhesion-imparting agent is usually used in an amount of 0.01 to 100 parts by weight of the silyl group-containing copolymer rubber as the component (A).
Preferably, it is used in the range of 20 parts by weight. In particular, 0.
It is preferable to use in the range of 1 to 10 parts by weight. The above-mentioned adhesiveness-imparting agents may be used alone or in combination of two or more.

The sealing material for double glazing of the present invention includes:
By blending various fillers, physical properties can be further improved. Such fillers include reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, talc and carbon black; heavy calcium carbonate, colloidal calcium carbonate, diatomaceous earth, calcined clay, Fillers such as clay, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide and activated zinc white; fibrous fillers such as glass fibers and filaments can be used.

When a high-strength curable sealing material is desired to be obtained with these fillers, it is mainly necessary to use reinforcing agents such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, talc and carbon black. The filler (A) of the present invention
If the component is used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the silyl group-containing copolymer rubber, a cured product having high strength and high modulus in mechanical properties can be obtained. On the other hand, when it is desired to obtain a cured product having low modulus and high elongation, heavy calcium carbonate, colloidal calcium carbonate, diatomaceous earth, calcined clay, clay, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide And 5 parts by weight of a filler such as active zinc white with respect to 100 parts by weight of the silyl group-containing copolymer rubber which is the component (A) of the present invention.
It may be used in the range of up to 400 parts by weight. Of course, these fillers may be used alone or in combination of two or more. The filler may be added to the component (A), may be added to the component (B), or may be added to both.

In the sealing material for double glazing of the present invention, when a plasticizer is used in combination with a filler, the elongation of the cured product can be increased and a large amount of the filler can be mixed. More useful. As a plasticizer,
Although generally used plasticizers can be used, those having good compatibility with the silyl group-containing copolymer rubber used in the present invention are preferable. When introducing a hydrolyzable silyl group into the ethylene / α-olefin / non-conjugated polyene / random copolymer rubber, the plasticizer is used instead of a solvent for the purpose of adjusting the reaction temperature, adjusting the viscosity of the reaction system, and the like. May be used. The plasticizer is not particularly limited, and any commonly used plasticizer can be used, but a plasticizer having good compatibility with various components blended in the rubber composition of the present invention is preferable. Specific examples of such a plasticizer include, for example, polybutene, hydrogenated polybutene, ethylene / α-olefin oligomer,
α-methylstyrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylenetriphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyldiphenyl, partially hydrogenated terphenyl, paraffin oil, naphthenic oil, hydrocarbons such as atactic polypropylene Compounds; chlorinated paraffins; phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate; Dibasic acid esters; esters of polyalkylene glycols such as diethylene glycol benzoate and triethylene glycol dibenzoate; tricresyl phosphate, tributy Phosphoric acid esters such as phosphate and the like. These may be used alone or in combination of two or more. Among these, hydrocarbon compounds having no unsaturated group (specifically, hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, atactic polypropylene, etc.) are compounded in the composition of the present invention. It is preferable because the compatibility with various components is good, the influence on the curing speed of the rubber composition is small, and the cured product obtained has good weather resistance and is inexpensive.

Further, the anti-aging agent, the light stabilizer, the flame retardant, the thixotropic agent, the pigment, the surfactant and the like may be appropriately added to the sealing material for double glazing of the present invention, if necessary. can do.

Examples of the above-mentioned antioxidants include known antioxidants which are generally used, for example, sulfur-based antioxidants, radical inhibitors, ultraviolet absorbers and the like. Examples of the sulfur-based antioxidants include mercaptans, salts of mercaptans, sulfides including sulfide carboxylate esters and hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, sulfoxides and the like. Specific examples of the sulfur-based antioxidant include 2-mercaptobenzothiazole which is a mercaptan, zinc salt of 2-mercaptobenzothiazole which is a salt of mercaptan, and sulfides which are 4,4.
4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-thio-bis (2-methyl-6-t-butylphenol), 2,2'-thio-bis (4-methyl −
6-t-butylphenol), bis (3-methyl-4-)
(Hydroxy-5-t-butylbenzyl) sulfide, terephthaloyldi (2,6-dimethyl-4-t-butyl-
3-hydroxybenzyl) sulfide, phenothiazine, 2,2'-thio-bis (4-octylphenol) nickel, dilaurylthiodipropionate, distearylthiodipropionate, dimyristylthiodipropionate, ditridecylthiodipropionate , Distearyl β, β'-thiodibutyrate, lauryl-stearylthiodipropionate, 2,2-thio [diethyl-bis-3- (3,5-di-t-butyl-4-hydroxyphenol) propionate ], 2-benzothiazole disulfide which is a polysulfide, tinc dibutyl dithiocarbamate which is a dithiocarboxylate, tinc diethyldithiocarbamate, nickel dibutyldithiocarbamate, tincdi-n-butyldithiocarbamate, dibutylammonium Butyl dithiocarbamate, Chinkuechiru - phenyl - dithiocarbamate, Tink dimethyl geo carbamate is thioureas 1
-Butyl-3-oxy-diethylene-2-thiourea,
Examples thereof include di-o-tolyl-thiourea, ethylene thiourea, and trilauryl trithiophosphate, which is a thiophosphite. When such a sulfur-based antioxidant is used in the rubber composition of the present invention as compared with other antioxidants, it can significantly prevent degradation of the main chain due to heat, and has a surface tack (stickiness). ) Can be prevented.

Examples of the radical inhibitor include 2,2
2-methylene-bis (4-methyl-6-t-butylphenol), tetrakis [methylene-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] a phenolic radical inhibitor such as methane, phenyl-β-naphthylamine, α-naphthylamine, N, N ′
And amine-based radical inhibitors such as -sec-butyl-p-phenylenediamine, phenothiazine, and N, N'-diphenyl-p-phenylenediamine. Examples of the ultraviolet absorber include 2- (2′-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. When the antioxidant is incorporated, the amount is preferably about 0.1 to 20 parts by weight, more preferably about 1 to 10 parts by weight, per 100 parts by weight of the component (A).

[0051]

The sealing material for double glazing of the present invention comprises:
(A) a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the above general formula (1) in the molecule, (B) a hot melt resin, ) Since it contains a curing catalyst and (D) water or a metal salt hydrate, it maintains the water vapor barrier property of the conventional hot melt resin while maintaining the temperature dependence of the structural strength and the effect on the substrate. The adhesiveness is improved, and it can be suitably used as a sealing material for a dual seal primary seal or a single seal in a double glazing application.

[0052]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in detail with reference to examples, but the present invention is not limited to the examples. In the following, “parts” are based on weight.

(Production Example 1) [Silyl group-containing ethylene / propylene / 5-vinyl-2]
-Production of norbornene random copolymer rubber] Ethylene, propylene and 5-vinyl-2-norbornene are continuously used using a stainless steel polymerization vessel (stirring rotation speed = 250 rpm) equipped with a stirring blade and having a substantial internal volume of 100 liters. Was terpolymerized. 60 liters of hexane, 2.5 kg of ethylene, 4.0 kg of propylene, and 3 parts of 5-vinyl-2-norbornene per hour were added to the liquid phase from the side of the polymerization vessel.
At a rate of 80 g, 700 liters of hydrogen, 45 mmol of VO (OC ₂ H ₅ ) ₂ Cl as a catalyst, Al (E
t) _1.5 Cl _1.5 was fed continuously at a rate of 315 mmol. When the copolymerization reaction was carried out under the conditions described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber was obtained in a uniform solution state. Thereafter, a small amount of methanol was added to the polymerization solution continuously withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction, and the polymer was separated from the solvent by steam stripping, followed by vacuum drying at 55 ° C. for 48 hours. Was done. The ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber obtained as described above has an ethylene content of 68 mol%, an iodine value of 10, and an intrinsic viscosity [η].
0.2 dl / g and molecular weight distribution (Mw / Mn) were 15.

2% for 100 g of the produced ethylene / propylene / 5-vinyl-2-norbornene copolymer rubber
0.3 g of a toluene solution of chloroplatinic acid was added, 1.5 g of methyldimethoxysilane was charged, and reacted at 120 ° C. for 2 hours. After the reaction, excess methyldimethoxysilane and the solvent were distilled off to obtain 101.5 g of a dimethoxymethylsilyl group-containing copolymer rubber.

Examples 1-3 and Comparative Example 1 100 parts of the polymer obtained in Production Example 1 were mixed with 30 parts of paraffin-based process oil (Diana Process PS-32, trade name, manufactured by Idemitsu Kosan Co., Ltd.), butyl Hot melt (Yamato Rubber Co., Ltd., trade name HAMATITE HOTMELT)
M-120) 130 parts of Glauber's salt (reagent, Na ₂ SO ₄ · 1
0H ₂ O), 3 parts of tin octylate (Nitto Kasei Co., Ltd., trade name: Neostan U-28) and 0.75 part of laurylamine (Wako Pure Chemical Industries, Ltd.) are added, and three paint rolls are added. And kneaded well. The composition prepared by the above method was used for preparing the test sample of Example 1. Example 1
Example 2 was changed to only 303.3 parts of the butyl-based hot melt, and Example 1 was changed to only 1169 parts of the butyl-based hot melt. In addition, as Comparative Example 1, a similar sample was prepared using only hot melt and used for a tensile test.

The test sample was JIS A 6850.
According to the sample preparation method of the tensile shear adhesive strength test method of the adhesive specified in -1976, the composition was applied using an aluminum substrate, pressed, and then cured in an oven. The curing conditions are all 50 ° C. for 4 days. The base material used for the test was J based on JIS K 6850-1976.
Aluminum conforming to ISH 4000 (Tayo base material: A1050P, dimensions: 2.5 × 10 × 0.3c)
m), and these adherends were washed with methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd .: special grade) and wiped with a clean cotton cloth before applying a sealing material.

The test sample prepared by the above method was
According to a tensile adhesion test method specified in IS A 6850, the test was carried out in a constant temperature room at a temperature of 23 ° C. and a humidity of 65 ± 5% at a tensile speed of 50 mm / min. Table 1 shows the results.

Reference Examples 1 to 3 In Examples 1 to 3, paragraphs [0041] to [0050] of JP-A-11-209540 were used instead of the silyl group-containing copolymer rubber obtained in Production Example 1. Example 1 was repeated except that an isobutene polymer having reactive silicon-containing groups at both terminals was synthesized by the method described and used.
Performed similarly to # 3. The results are shown in Table 1 together with the results of the curing speed and the weather resistance.

The curing speed and weather resistance were determined according to the following methods. Curing speed: Film tonicity at room temperature was measured using the blend of the above main agent and catalyst. That is, curing speed: (film expandability) The curable composition is filled in a mold (20 × 80 × 5 mm) and left to cure in a room at 23 ° C. and 50% RH, and peeled off after 24 hours, and the cured portion has a weak spring. Measure the thickness to 0.1 mm with a dial gauge. (Evaluation) Cured part <1 mm × Cured part ≧ 1 mm ○

Weather resistance: Accelerated weather test: JIS B7
753 compliant Sunshine carbon arc weatherometer Irradiation / rain cycle: 120 minutes irradiation / 18 minutes rain Black panel temperature: 63 ± 2 ° C. In-bath temperature: 40 ± 2 ° C. Irradiation time: Surface condition after 500 hours was observed . (Evaluation) ○: No crack dissolving part △: Slight crack or slight dissolving part ×: Crack or dissolving part

[0061]

[Table 1]

Example 4 and Reference Example 4 Each of the composition prepared in Example 1 and the composition prepared in Reference Example 1 was used to prepare a cured sheet having a thickness of about 2 mm. Table 2 (Example 4) and Table 3 (Reference Example 4) show the results of punching a No. 3 dumbbell specified in JIS K 6301 from these cured products and conducting a tensile test. The test specimen was taken out after curing at 23 ° C. for 7 days and then at 50 ° C. for 7 days, and the H-type mechanical properties were measured. The test is J
According to a tensile test method specified in IS K6301, a tensile speed of 200 in a constant temperature bath at a temperature of 23 ° C., 50 ° C., and 70 ° C.
mm / min.

[0063]

[Table 2]

[0064]

[Table 3]

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 3/00 C08K 3/00 5/00 5/00 C08L 23/26 C08L 23/26 101/00 101/00 (72 ) Inventor Yoshiharu Kikuchi 3 Chizukaigan, Ichihara-shi, Chiba F-term within Mitsui Chemicals Co., Ltd. CF002 CK022 CL002 DD077 DD087 DE097 DE227 DF027 DG037 DG047 DH047 EC076 EE046 EG046 EG047 EN026 EN046 EN066 EN076 EN096 EN106 EU116 EU136 EU236 EZ006 EZ046 FD146 FD207 4J100 AA01Q AA02P AA03A AQAAQAAQAAQ HA61 HB30 HC77 HC78 HC91 HD00 JA03

Claims (6)

[Claims] 1. A (A) silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the following general formula (1) in the molecule: (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group,
It represents a hydrolyzable group selected from an aminooxy group, a thioalkoxy group, an amino group, a mercapto group and an alkenyloxy group, and m is an integer of 0, 1 or 2. )
A sealing material for a double glazing comprising (B) a hot melt resin, (C) a curing catalyst, and (D) water or a metal salt hydrate. 2. A silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) having the following general formula (2) or (3): (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R ¹
Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X is a hydride group, a halogen group , An alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group, an amino group, a mercapto group and a alkenyloxy group, wherein m is 0, 1 or And n is an integer of 0 to 10
Is an integer. The sealing material for a double glazing according to claim 1, which has at least one silyl group-containing unit represented by the formula: 3. A silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) represented by the following general formula (4) and / or (5): (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. , N is an integer of 0 to 10.) The ethylene / α-olefin / non-conjugated polyene random copolymer rubber having at least one type of norbornene compound having a terminal vinyl group as a non-conjugated polyene represented by the following general formula ( 6) (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group, Represents a hydrolyzable group selected from an amino group, a mercapto group and an alkenyloxy group, and m is an integer of 0, 1, or 2.) The sealing material for a double glazing according to claim 1 or 2, wherein a SiH group of the silicon compound is added to the bond. 4. The method according to claim 1, wherein X is an alkoxyl group.
The sealing material for a double glazing according to any one of the above. 5. The sealing material for a double glazing according to claim 1, wherein the hot melt resin (B) is a butyl rubber-based hot melt resin. 6. The sealing material for a double glazing according to claim 1, which is used as a primary sealing material for dual sealing or as a sealing material for single sealing.