JPH08283048A - Multi-ply glass and its production - Google Patents

Abstract

PURPOSE: To decrease damp permeability and to improve weather resistance, weathering adhesive property, heat resistance and mechanical strength by interposing a specific cross-linking saturated hydrocarbon-based sealing agent between glass plates held opposite to each other at a certain interval. CONSTITUTION: The cross-linking saturated hydrocarbon-based sealing agent 7 of 50-100% gel fraction is obtained by combining (A) a hydrocarbon-based polymer having at least one alkenyl group in a molecule and 5000000-300000 molecular weight, (B) a hardening agent having at least 2 hydrosilyl groups in a molecule, (C) a hydrosilylation catalyst and (D) an adhesion imparting agent expressed by formula I-V (each of R1 , R3 , R8 and R11 is a 1-20C bivalent organic group, R2 is an alkoxysilyl group or a group expressed by formulae VI-VIII, R12 is a 1-6C alkyl group, each of R4 and R9 is H, a 1-10C univalent organic group, each of R5 to R7 is H or a 1-20C univalent organic group, R10 is an alkoxyl group and (a) is 1-2). Two glass plates 2, 3 are temporarily fixed with a spacer 4 interposed by a primary sealing agent 6 to frame them with a flask 10 and the sealing agent 7 is poured between the flask 10 and the glass plates 2, 3 and cured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a double glazing and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, various sealing materials have been used for the purpose of adhering or reinforcing / replenishing materials of the same kind or different kinds during assembly processing in construction, automobiles, etc. Various materials having different curing modes and main chain structures have been proposed depending on the application. However, the conventionally used multi-layer glass sealing materials include (1) high weather resistance, (2) high heat resistance, (3) fast curing property,
There are no known materials that combine various properties such as (4) low moisture permeability, (5) adhesiveness with inorganic materials, and (6) materials that also consider one-liquid stability are completely known. There wasn't.

For example, a silicone-based sealing material having an addition type curing method satisfies the characteristics (1), (2), (3), (5), and in some cases, the characteristic (6). (4)
It has also been observed that when used as a sealing agent, it causes environmental problems such as contamination of the surroundings. Further, even in a polymer material having a saturated hydrocarbon polymer as a main chain disclosed in JP-A-1-198673, since the curing mode is a condensation type, the above property (3) may be satisfied. Can not.

Further, conventionally, in order to improve the heat insulating property and soundproofing property of glass, a double-layered glass in which two or more glass plates are laminated and joined is used. In the case of double glazing, the air between the glass plates is blocked from the outside, resulting in a dead air pace. In order to form this dead air pace, a sealing agent for interposing a spacing member around the glass plates is used between the glass plates as needed.

The characteristics required for the sealing agent used in the production of this double glazing are as follows: a) Two glass plates or a spacing member made of metal or the like for holding two glass plates at a distance. And the two glass plates are stably bonded over a long period of time. B) Preventing moisture from permeating or penetrating into the dry air sealed in the dead air pace.

[0006] However, in the conventionally used sealing agents, no material has been known that satisfies both the characteristics a) and b) with one kind of sealing agent, and a sealing agent having each characteristic is used. Two types will be used together. For example, as a material having the characteristics of a), a silicone-based or thiocol-based sealing agent, b)
A butyl-based hot-melt sealing agent is used as a material having the above-mentioned properties, and the properties required for a so-called double seal are imparted. However, when the butyl-based hot melt sealant having the characteristics of b) is used alone, satisfactory results cannot be obtained with respect to weathering adhesiveness and mechanical properties, and the characteristics of a) may be satisfied. There is a problem that you cannot do it.

[0007]

Therefore, in view of the above-mentioned circumstances, the object of the present invention is to provide a multi-layer structure having the various characteristics (1) to (6) together and having excellent mechanical characteristics. To get the glass. That is, the present invention uses a saturated hydrocarbon-based sealing agent that satisfies the above-mentioned characteristics a) and b), has a fast curing property by addition-type curing, and can be produced on a line, and makes a single seal. An object of the present invention is to provide a possible double glazing and a manufacturing method thereof.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a curing mode different from the technique described in the above-mentioned JP-A-1-198673 is used. We have found a sealing agent that is adopted and that also satisfies the characteristics of (5) adhesiveness with inorganic materials and organic materials, and (6) stability of one liquid. As a result, a double glazing capable of achieving the above object can be obtained, and the present invention has been completed.

That is, according to the present invention, the gel fraction is 50 to 1 between the glass plates which are held facing each other at a constant interval.
The gel fraction is 50 to 10 between the double glazing having a cross-linking type saturated hydrocarbon sealing agent of 00% and the glass plates held facing each other at regular intervals.
A method for producing a double glazing, which comprises interposing a 0% cross-linking type saturated hydrocarbon sealing agent.
Further, in the present invention, it is preferable that the saturated hydrocarbon sealant contains the following components (A), (B), (C) and (D) as essential components. (A) a hydrocarbon-based polymer having a molecular weight of 500 to 300,000 having at least one alkenyl group in the molecule,
(B) a curing agent having at least two hydrosilyl groups in the molecule, (C) a hydrosilylation catalyst, and (D) an adhesiveness-imparting agent. Further, in the double glazing and the method for producing the same of the present invention, the polymer of the component (A) contains 50 wt% or more of the repeating unit of the isobutylene monomer, and the curing agent of the component (B) is at least in the molecule. An organic curing agent having at least two monovalent groups derived from a polyorganohydrogensiloxane containing one hydrosilyl group, or other than a monovalent group derived from a polyorganohydrogensiloxane in the molecule. An organic curing agent containing at least two hydrosilyl groups, wherein the component (D) adhesiveness-imparting agent is a diglycidyl amine (I) or acrylic acid represented by the following general formulas (I) to (V). Epoxy group-containing esters (II), 2,4,6-trioxotriazines (III), alkoxysilyl isocyanates (IV) and diisocyanates (V) It is preferable that each contains at least one adhesive compound selected from the group consisting of adhesive compounds selected from the above.

Further, when the present invention is intended to impart a one-component property to a saturated hydrocarbon type sealing agent, the components (A) to (D) are further improved in storage stability of the component (E). Agents can be included.

The component (A) is a hydrocarbon-based polymer having a molecular weight of 500 to 300,000 having at least one alkenyl group in the molecule and having 1 to 1 alkenyl group in one molecule.
It is preferable to have 10 and more preferable to have 1 to 5.

The term "hydrocarbon polymer" as used herein means a polymer which does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring in its main skeleton, and the main chain excluding the alkenyl group is It means that the constituent repeating unit is composed of a saturated hydrocarbon.

The polymer which forms the skeleton of the hydrocarbon polymer which is the component (A) is obtained by polymerizing 1) an olefin compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene as a main monomer. 2) It can be obtained by a method such as homopolymerization of a diene compound such as butadiene or isoprene, or copolymerization of the above olefin compound and a diene compound, followed by hydrogenation.

Among the polymers obtained by these methods, the isobutylene-based polymer is advantageous in that it is easy to introduce a functional group at the terminal, it is easy to control the molecular weight, and a large number of terminal functional groups can be introduced. A hydrogenated polybutadiene-based polymer or a hydrogenated polyisoprene-based polymer is preferable.

The isobutylene-based polymer may be a homopolymer in which all of the monomer units are composed of isobutylene, and in order to improve the moisture impermeability, a monomer unit copolymerizable with isobutylene is used. May be contained in the isobutylene polymer in an amount of preferably 50% (% by weight, the same applies hereinafter), more preferably 30% or less, and particularly preferably 10% or less.

Examples of such copolymerization components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinylsilanes, allylsilanes and the like. Specific examples of such a copolymerizable monomer include:
For example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-
1-pentene, hexene, vinylcyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, pt-butoxystyrene, p-hexenyloxystyrene, p-allyloxystyrene, p-hydroxy. Styrene, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,
In addition to 3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldimethoxysilane, diallyldimethylsilane, etc., β-pinene, indene, γ-methacryloyloxypropyltrisilane Examples thereof include methoxysilane and γ-methacryloyloxypropylmethyldimethoxysilane.

In the hydrogenated polybutadiene-based polymer and other hydrocarbon-based polymers as well, as in the case of the isobutylene-based polymer, in addition to the monomer unit as the main component, its copolymerizable monomer. Units may be included. Further, the hydrocarbon-based polymer used as the component (A) contains butadiene, isoprene, 1,
A small amount of monomer units, such as 5-hexadiene, 1,9-decadiene and 1,13-tetradecadiene, which leave a double bond after polymerization, preferably 10
You may make it contain in the range of% or less.

As described above, the hydrocarbon polymer having a molecular weight of 500 to 300,000 is used as the component (A). However, a hydrocarbon having a number average molecular weight of about 500 to 100,000 is preferable, and a flow of about 1,000 to 40,000 is particularly preferable. A viscous liquid having a property is preferable from the viewpoint of easy handling.

Regarding the method of introducing an alkenyl group into a hydrocarbon polymer, various proposals can be adopted, but a method of introducing an alkenyl group after polymerization and a method of introducing an alkenyl group during polymerization. Can be roughly divided into As a method of introducing an alkenyl group after the polymerization, for example, when the terminal, the main chain or the side chain has a hydroxyl group, after converting the hydroxyl group to a metaloxy group such as -ONa or -OK, the following general formula (VI) A hydrocarbon-based polymer having an alkenyl group is produced by reacting the unsaturated halogen compound represented by.

CH ₂ ═CH—R ₁₃ —X (VI) [In the formula, X represents a halogen atom such as a chlorine atom or an iodine atom. R _{13 is, -R 14 -, - R 14} '-OC (= O) - or _{-R 14 "-C (= O)} - ( wherein, R _14, R _14',
R ₁₄ ″ is a divalent hydrocarbon group each having 1 to 20 carbon atoms, and preferable examples include a divalent organic group represented by an alkylene group, a cycloalkylene group, an arylene group and an aralkylene group. Represents a methylene group or the following structural formula

[0021]

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A divalent hydrocarbon group represented by (wherein R ₁₅ is a divalent hydrocarbon group having 1 to 10 carbon atoms) is particularly preferable. ]

As a method for converting, for example, a terminal hydroxyl group of the hydroxy hydrocarbon polymer into a metaloxy group,
Alkali metals such as Na and K, metal hydrides such as NaH,
A method of reacting with a metal alkoxide such as NaOCH ₃ or a caustic alkali such as caustic soda or caustic potash may be used. Specific examples of the unsaturated halogen compound represented by the general formula (VI) include allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl). ) Ether, allyl (chloromethoxy) benzene, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene and the like, but not limited thereto. Of these unsaturated halogen compounds (VI), allyl chloride is preferable because it is inexpensive and easily reacts.

In the etherification reaction, a terminal alkenyl group-containing hydrocarbon polymer having almost the same molecular weight as the terminal hydroxy group-substituted hydrocarbon polymer used as the starting material is obtained. On the other hand, in order to obtain a polymer having a higher molecular weight, before reacting with the unsaturated halogen compound (VI), one molecule of methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether, etc. should be prepared. It may be reacted with a polyvalent organic halogen compound containing two or more halogen atoms. Then, by subsequently reacting with the unsaturated halogen compound (VI), a hydrocarbon polymer having a higher molecular weight and having an alkenyl group at the terminal can be obtained.

The method of introducing an alkenyl group into an isobutylene polymer having a covalently bonded chlorine atom is not particularly limited, but i) Friedel-Crafts of various alkenyl phenyl ethers and the above polymer. A reaction method, ii) a substitution reaction of allyltrimethylsilane or the like with the above-mentioned polymer in the presence of a Lewis acid, and iii) a Friedel-Crafts reaction of various phenols with the above-mentioned polymer to form a hydroxyl group. And a method of using the above alkenyl group introduction method together.

Other methods for introducing an alkenyl group during polymerization include, for example, the following methods. That is, a compound having a halogen atom as an initiator and a chain transfer agent, in which the carbon atom to which the halogen atom is bound is bound to an aromatic ring carbon, and / or the compound in which the carbon atom is a tertiary carbon atom is used. And, in the cationic polymerization of the cationically polymerizable monomer containing isobutylene using a Lewis acid as a catalyst, a method for producing an isobutylene-based polymer having an allyl group at the end by adding allyltrimethylsilane to the polymerization system is is there. Alternatively,
By adding non-conjugated dienes such as 1,9-decadiene and alkenyloxystyrenes such as p-hexenyloxystyrene to the polymerization system, an isobutylene-based polymer having an alkenyl group at the end of the main chain or side chain is prepared. A manufacturing method may be mentioned.

The Lewis acid used as the cationic polymerization catalyst component is represented by the general formula MX'b (wherein M is a metal atom, X'is a halogen atom, and b is the valence of the metal atom). Applied, eg BCl ₃ , Et ₂ Al
Cl, EtAlCl ₂ , AlCl ₃ , SnCl ₄ , Ti
Examples thereof include Cl ₄ , VCl ₅ , FeCl ₃ , BF _{3, and the} like, but are not limited thereto. Of these Lewis acids, BCl ₃ , SnCl ₄ , BF _{3 and the} like are preferable, and TiCl ₄ is more preferable.
The amount of the Lewis acid used is preferably 0.1 to 10 times, and more preferably 2 to 10 times the number of moles of the initiator / chain transfer agent.
5 times.

In the present invention, the curing agent which is the component (B) is not limited as long as it has at least two hydrosilyl groups in the molecule. Here, one hydrosilyl group means one SiH group. Therefore, when two hydrogen atoms are bonded to the same Si, it is calculated as two hydrosilyl groups. As the component (B), polyorganohydrogensiloxane is mentioned as one of the preferable ones,
The structure is specifically shown as follows.

[0029]

[Chemical 4]

Examples thereof include chain-like and cyclic ones. As the component (B), an organic curing agent having at least two monovalent groups derived from polyorganohydrogensiloxane having at least one hydrosilyl group in the molecule is also preferable. Preferred examples of such an organic curing agent include organic curing agents represented by the following general formula (VII).

R ₁₆ Yc (VII) (In the formula, Y is a monovalent group derived from polyorganohydrogensiloxane containing at least one hydrosilyl group, and R ₁₆ is a monovalent group having 2 to 2000 carbon atoms. Hydrocarbon group, c is an integer selected from 2 to 4.)

In the formula (2), Y represents a monovalent group derived from a polyorganohydrogensiloxane containing at least one hydrosilyl group.

[0033]

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Examples thereof include chain-like and cyclic ones. Among the monovalent groups derived from the above various polyorganohydrogen siloxanes, the compatibility of the hydrosilyl group-containing curing agent which is the component (B) of the present invention with various organic polymers such as the component (A) may be impaired. Considering that the property is low, the following are particularly preferable.

[0035]

[Chemical 6]

In the formula (VII), R ₁₆ has 2 to 2 carbon atoms.
It is a monovalent to tetravalent hydrocarbon group of 000 and is not limited, but a saturated hydrocarbon group and the like are particularly preferable in view of compatibility with various organic polymers and reactivity of hydrosilyl groups. Further, as the component (B), an organic curing agent containing at least two hydrosilyl groups other than the monovalent group derived from polyorganohydrogensiloxane in the molecule is also preferable. As a preferred example of this organic curing agent,
An organic curing agent represented by the following formula (VIII) can be given.

R ₁₇ Yd (VIII) where Y contains at least two hydrosilyl groups,
Groups other than monovalent groups derived from polyorganohydrogensiloxane, R ₁₇ is a monovalent to tetravalent hydrocarbon group having 2 to 2000 carbon atoms. d is an integer selected from 1 to 4. )

To specifically exemplify Y in the above general formula (VIII), --Si (H) _d (CH ₃ ) _3-d , --Si (H) _{d
(C 2 H 5) 3-} d, -Si (H) d (C 6 H 5) 3-d, -Si
A group containing only one silicon atom such as H ₂ (C ₆ H ₁₃ ) (in the above formula, d is an integer of 1 to 3), or the following structural formulae, for example.

[0039]

[Chemical 7]

Examples thereof include a group containing two or more silicon atoms. Further, in the formula (VIII), R ₁₇ has 2 to 20 carbon atoms.
It is a monovalent to tetravalent hydrocarbon group of 00 and is not limited, but if the possibility of impairing the compatibility with various organic polymers is small and the reactivity of the hydrosilyl group is taken into consideration, particularly saturated hydrocarbon group, etc. Is preferred.

The number of hydrosilyl groups contained in the formulas (VII) and (VIII) may be at least 2 in one molecule, but is preferably 2 to 15 and particularly preferably 3 to 12. When the saturated hydrocarbon-based sealing agent of the present invention is cured by a hydrosilylation reaction, if the number of the hydrosilyl groups is less than 2, the curing is slow and the curing often occurs. Further, when the number of the hydrosilyl groups is more than 15, the stability of the curing agent as the component (B) becomes poor, and moreover, a large amount of hydrosilyl groups remains in the cured product even after curing, causing voids and cracks. Becomes

There are no particular restrictions on the method of producing the curing agent of component (B), and any method may be used. For example, i) a method of treating a hydrocarbon compound having a Si—Cl group in the molecule with a reducing agent such as LiAlH ₄ or NaBH ₄ to reduce the Si—Cl group in the compound to a Si—H group,
ii) A method of reacting a hydrocarbon compound having a functional group W in the molecule with a compound having a functional group Z that reacts with the functional group W and a hydrosilyl group in the molecule at the same time, iii)
An example of such a method is to add a polyhydrosilane compound having at least two hydrosilyl groups to an unsaturated hydrocarbon compound so that the hydrosilyl group remains in the molecule of the hydrocarbon compound after the reaction.

Of the above methods, the method iii) can be preferably used because the manufacturing process is generally simple. In this case, two or more of the hydrosilyl groups of some polyhydrosilane compounds may react with the alkenyl groups of the unsaturated hydrocarbon compound to increase the molecular weight, but the reaction product is used as the component (B). But it doesn't matter.

The hydrosilyl group in the component (B) produced as described above and the alkenyl group in the component (A) are preferably in a molar ratio of 0.2 to 5.0, more preferably 0. 4-2.5 is especially preferable. When the molar ratio is less than 0.2, when the composition of the present invention is cured, curing is insufficient and only a cured product having low strength and stickiness can be obtained. On the other hand, when the molar ratio is more than 5.0, a large amount of active hydrosilyl groups remain in the cured product even after curing, so that cracks and voids occur, and there is a tendency that a uniform and strong cured product cannot be obtained. is there.

The hydrosilylation catalyst which is the component (C) of the present invention is not particularly limited and any one can be used. Specific examples of the above catalyst include platinum complexes, chloroplatinic acid, alumina, silica, carbon black, and other solid platinum-supported carriers, as well as the following platinum complexes. Platinum - vinylsiloxane complex _{example, (Pt) e (ViMe 2} SiOSiMe 2 Vi)
_{e, Pt [(MeViSiO) 4} ] f; platinum - phosphine complex _{example, Pt (PPh 3) 4,} Pt (PBu 3) 4; platinum - phosphite complex _{example, Pt [P (OPh) 3} ] 4, Pt [ P (OB
u) ₃ ] ₄ Platinum-active hydrogen-containing compound complex For example, bisacetylacetonatoplatinum [Pt (AcC
H ₂ Ac) ₂ ] Bisethylacetoacetatoplatinum [Pt (AcCH ₂ C
OOEt) ₂ ] (wherein, Vi is a vinyl group, Me is a methyl group, Ph is a phenyl group, Bu is a butyl group, Ac is an acetyl group, Et is an ethyl group, and e and f are integers. ) Also, Ashby US Pat. No. 3,159.
No. 601 and U.S. Pat. No. 3,159,662, the platinum-hydrocarbon composite Lamoreau (La).
Also included are the platinum alcoholate catalysts described in US Pat. No. 3,220,972 to Moreaux).

Examples of hydrosilylation catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ and Rh.
/ Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ ,
AlCl ₃ , PdCl ₂ · 2H ₂ O, NiCl ₂ , Ti
Cl _{4 and the} like can be mentioned. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, bisacetylacetonatoplatinum and the like are preferable. The amount of the catalyst is not particularly limited, but the component (A)
10 ^-1 to 10 ^-8 mo with respect to ¹ mol of the alkenyl group in
It is preferable to use it in the range of 1. Preferably 10 ^-2 to 10 ^-6
It is preferable to use it in the range of mol. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and since a large amount of hydrogen gas may be generated and the cured product may foam,
It is desirable not to use more than 10 ^-1 mol.

In the present invention, in the presence of the hydrosilylation catalyst of component (C), Si--H for the alkenyl group is used.
Since the saturated hydrocarbon-based sealing agent is cured by the addition reaction of the group, the curing rate is very fast, which is convenient for line production.

The adhesiveness-imparting agent which is the component (D) of the present invention is preferably a compound represented by the following general formulas (I) to (V), which also causes a problem of curing failure during addition type curing. Can be used without.

[0049]

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[In the formula, R ₁ , R ₃ , R ₈ and R ₁₁ represent a divalent organic group having 1 to 20 carbon atoms and may be the same or different. R ₂ is an alkoxysilyl group or the following structural formula

[0051]

[Chemical 9]

(Wherein R ₁₂ is an alkyl group having 1 to 6 carbon atoms), and R ₄
Represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. R ₅ , R ₆ and R ₇ are each a hydrogen atom or a carbon number of 1 to 20.
Represents a monovalent organic group, and may be the same or different. R ₉ represents hydrogen or a monovalent organic group having 1 to 10 carbon atoms, and R ₁₀ represents an alkoxy group. In addition, a means an integer of 1 or 2. ]

R ₁ in the above general formulas (I) to (V),
Preferred organic groups as R ₈ and R ₁₁ are an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group and an aralkylene group. A preferred organic group for R ₃ is
Alkylene group, alkenylene group, cycloalkylene group,
It is an arylene group, an aralkylene group, or the like, and an oxygen atom may be substituted at the end of these hydrocarbon residues, or 1 to 3 oxygen atoms may be interposed between chain carbon atoms.

Preferred organic groups for R ₄ are alkyl groups, aryl groups, aralkyl groups and the like. R ₅ , R ₆ , R
Preferred organic groups as ₇ and R ₉ are alkyl groups, alkoxy groups, cycloalkyl groups, alkenyl groups, alkenyloxy groups, aryl groups, aryloxy groups, aralkyl groups, aralkyloxy groups, glycidyl groups, glycidyloxy groups and hydroxyalkyl. Etc.

Specific examples of the adhesion-imparting agent that can be used as the component (D) include the following compounds. Diglycidyl amines (I)

[0056]

[Chemical 10]

Acrylic acid epoxy group-containing ester (I
I)

[0058]

[Chemical 11]

2,4,6-trioxotriazines (II
I)

[0060]

[Chemical 12]

Alkoxysilyl isocyanates (IV)
And diisocyanates (V)

[0062]

[Chemical 13]

The storage stability improver which is the component (E) is added to improve the storage stability of the saturated hydrocarbon sealing agent, and is known as the storage stabilizer of the component (B). It is not particularly limited as long as it is an ordinary stabilizer as long as it achieves the intended purpose. Specifically, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide and the like can be preferably used. More specifically, 2-benzothiazolyl sulfide, benzothiazole, thiazole, dimethylacetylene dicarboxylate, diethyl acetylene dicarboxylate, BHT, butylhydroxyanisole, vitamin E, 2- (4-morphodinyldithio) Benzothiazole, 3-methyl-1-buten-3-ol, acetylenically unsaturated group-containing organosiloxane, acetylene alcohol, 3-methyl-1-butyl-3-ol, diallyl fumarate, diallyl maleate, diethyl fumarate , Diethyl maleate, dimethyl maleate, 2-pentene nitrile, 2,3-dichloropropene and the like. Particularly preferred are thiazole and benzothiazole from the viewpoint of compatibility of pot life / fast curing property, but are not limited thereto. By the way No. The amount of storage stability improver used is
From 10 ⁻⁶ to 1 mol of the component (A) and the component (B)
It is preferably used in the range of 10 ^-1 mol. This amount is 1
When it is less than 0 ^-6 , the storage stability of the component (B) is not sufficiently improved, and when it exceeds 10 ^-1 mol, curing may be hindered. The storage stability improvers may be used alone or in combination of two or more.

If necessary, various additives are added to the saturated hydrocarbon type sealing agent used in the present invention. Examples of such additives include plasticizers, fillers, antioxidants, radical inhibitors, ultraviolet absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, phosphorus peroxide decomposers. , Lubricants, pigments and the like.

The above-mentioned plasticizer is not particularly limited, and commonly used plasticizers can be used, but those having good compatibility with the composition of the present invention are preferable. Specific examples of such a plasticizer include polybutene, hydrogenated polybutene, ethylene-α-olefin oligomer, α-methylstyrene oligomer, biphenyl, triphenyl, and the like.
Triaryldimethane, alkylene triphenyl, hydrogenated liquid polybutadiene, alkyldiphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil, atactic polypropylene, etc., preferably hydrogenated polybutene containing no unsaturated bond, hydrogenated liquid polybutadiene Hydrocarbon compounds such as paraffin oil, naphthene oil and atactic polypropylene; chlorinated paraffins; phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate Acid esters; Aliphatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; Polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate Esters; tricresyl phosphate, and the like phosphoric acid esters such as tributyl phosphate. These may be used alone or in combination of two or more.

Of these, hydrocarbon compounds having no carbon-carbon unsaturated bond have good compatibility with the hydrocarbon polymer (A) and good weather resistance, and have a high curing rate of the sealing agent. It is preferable because it has little influence and is inexpensive. When a plasticizer is used, the amount used is preferably 10 to 500 parts per 100 parts of the hydrocarbon polymer (A), 2
0 to 300 parts is more preferable.

Specific examples of the filler include, for example, glass fiber, carbon fiber, mica, graphite, diatomaceous earth, clay, fume silica, precipitated silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, and oxidation. Examples thereof include titanium, magnesium carbonate, quartz, aluminum fine powder, flint powder, zinc dust and the like. Among these fillers, precipitated silica, fume silica,
Fillers having a structural viscosity (thixotropic property) such as carbon black, calcium carbonate, titanium oxide, talc and the like are preferable.

When a filler is used, the amount used is preferably 10 to 500 parts, more preferably 20 to 300 parts, based on 100 parts of the hydrocarbon polymer (A).

As the antiaging agent, generally used antiaging agents such as citric acid type, phosphoric acid type and sulfur type antiaging agents are used. Examples of the sulfur-based antioxidant include mercaptans, mercaptan salts, sulfides including sulfide carboxylic acid esters and hindered phenolic sulfides, polysulfides, dithiocarbamate salts, thioureas, thiophosphates, and sulfonium compounds. , Thioaldehydes, thioketones, mercaptars, mercaptols, monothio acids, polythio acids, thioamides, sulfoxides and the like.

Specific examples of such a sulfur-based antioxidant include mercaptans such as 2-mercaptobenzothiazole; salts of mercaptans such as zinc salt of 2-mercaptobenzothiazole; 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, terephthaloyl-di (2,2
6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, 2,2'-thio-bis (4-octylphenol) nickel, lauryl thiodipropionate, stearyl thiodipropionate, thiodipropionic acid Myristyl, tridecyl thiodipropionate, β, β'-thiodibutyric acid stearyl, lauryl-stearyl ester of thiodipropionic acid, 2,2'-thio-bis [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) ethyl propionate] and the like; polysulfides such as 2-benzothiazole disulfide; zinc di-i-butyldithiocarbamate, zinc diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc di-n-butyldithio Carbamate, dibutylan Monium dibutyl dithiocarbamate, zinc ethyl-phenyl-dithiocarbamate,
Dithiocarbamates such as zinc dimethylcarbamate; thioureas such as 1-butyl-3-oxy-diethylene-2-thiourea, di-o-tolyl-thiourea and ethylenethiourea; thiophosphines such as trilauryltrithiophosphate Can be mentioned.

When the above antiaging agent is added to the saturated hydrocarbon-based sealing agent of the present invention, the decomposition and deterioration of the main chain due to heat can be largely prevented as compared with other antiaging agents, and the surface tack ( It is possible to prevent the occurrence of stickiness). The amount of the antioxidant used is preferably 0.01 to 50 parts with respect to 100 parts of the hydrocarbon polymer (A),
0.1 to 5 parts is more preferable.

Examples of the radical inhibitor include 2,
2'-methylene-bis (4-methyl-6-t-butylphenol), tetrakis [methylene-bis-3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate] a phenolic radical inhibitor such as methane,
β-naphthylaniline, α-naphthylamine, N, N ′
-Aminic radical inhibitors such as secondary butyl-p-phenylenediamine, phenothiazine, N, N'-diphenyl-p-phenylenediamine and the like.

Examples of the ultraviolet absorber include 2-
(2-hydroxy-3,5-di-t-butylphenyl)
Examples thereof include benzotriazole and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. As described above, the polymer used for the saturated hydrocarbon sealant can be easily cured at room temperature, has excellent mechanical properties, and can be stably adhered to glass or spacing members for a long period of time. It can be made into a rubber-like material. Further, the saturated hydrocarbon-based sealing agent used in the present invention has good storage stability and is stable for a long time in a state where moisture is blocked, and therefore it can be used as a one-component sealing agent having good workability. It is possible. Further, the saturated hydrocarbon-based sealing agent can be made into a fluid material having appropriate viscosity and thixotropic property at room temperature, and has good workability in the production of double glazing. The rubber-like material obtained by curing the saturated hydrocarbon sealing agent used in the present invention has low moisture permeability and good weather resistance and weather resistance.

The saturated hydrocarbon-based sealing agent used in the present invention has the above-mentioned characteristics and can be used as a sealing agent for a one-component double glazing which does not require double sealing. Of course, it can be used not only for a conventional double-sealed double-layer glass, but also as a two-component sealing agent.

The glass to which the saturated hydrocarbon sealant used in the present invention is applied is generally an inorganic glass, but may be an organic glass. Further, the spacing member used for manufacturing the double glazing is typically made of metal such as aluminum or iron, but made of non-metal such as plastic, reinforced plastic, glass, wood, concrete, etc. It may be a member.

The double glazing of the present invention may be a double glazing manufactured so that it can be handled as a single piece of glass, such as a laminated glass, and a window in which glass can be inserted from both inside and outside. The frame may be a spacing member and glass may be inserted from both sides to form the frame. Further, it may be of a type that uses a concrete wall as a spacing member such that glass is put inside and outside a portion corresponding to a window of a building made of concrete or the like. However, when a moisture permeable material such as concrete is used for the spacing member, it is preferable that moisture does not enter the inside of the double-glazing unit.

[0077]

Embodiments of the present invention will be described below with reference to the drawings. 1 and 2 are cross-sectional views of a double glazing relating to an example of the present invention.
The glass plates 2 and 3 are provided with spacers 4 along the periphery thereof.
To form a hollow layer 5 between the glass plates 2 and 3, and the hollow layer 5 side between the glass plates 2 and 3 and the spacer 4 and the glass plates 2 and 3 and the spacer 4. In this case, a saturated hydrocarbon sealing agent 7 is sealed on the peripheral side of the double glazing 1. In addition, 6 is a primary sealing agent for temporarily fixing the spacer 4, and 8 is a desiccant. In the multi-layer glass of the present invention, the sealing agent interposed between the glass plates held opposite to each other at a constant interval is a saturated hydrocarbon-based sealing agent that cures and crosslinks by a hydrosilylation reaction, and the gel of the cured product. Fraction is 50 to 10
It is characterized by being 0%.

This gel fraction was obtained by weighing a sample of the cured product of the sealant, immersing it in 100 ml of toluene for 24 hours, and then drying the solvent at 100 ° C. for 24 hours to completely evaporate the solvent. It is a product calculated by measuring the weight of the cured product sample of 1. Gel fraction = [{(weight before immersing in solvent)-(dry weight after immersing in solvent)} / (weight before immersing in solvent)] × 100 The ratio is represented by a gel fraction, preferably 50 to 100%, particularly preferably 70 to 100%. Gel fraction is 5
If it is less than 0%, the glass may be displaced due to melting of the sealing member by heat, which is not preferable.

In the present invention, the sealing member is
Both the structure shown in FIG. 1 and the structure shown in FIG. 2 need to be integrally molded, and as a preferable molding method therefor, the RIM method or the injection molding method is used. For example, in the RIM method, FIG.
As shown in FIG. 2, a mold 10 having a space in the shape of a sealing member is temporarily fixed with a primary sealing agent 6 through two plate glasses 2 and 3 and a spacer 4, and the mold 10 is used around the peripheral part. The frame is closed, and the space between the mold 10 and the glass sheets 2 and 3 is sealed with a sealant 9, and a saturated hydrocarbon sealing agent 7 is injected into the mold through an injection port in the direction of an arrow 11, Then, these raw materials are subjected to reaction hardening by heating or super-high frequency heating. In this method, in order to improve the releasability from the mold, it is effective to apply a fluorine-based resin or a silicon-based resin inside the mold in advance.

On the other hand, also in the injection molding method, similarly, a method in which a saturated hydrocarbon sealing agent is injection-pressed into the mold and cured inside is adopted. Even with this injection molding method, RI
As in the M method, it is effective to apply a release agent in the mold. As a characteristic of the molding method, an injection molding method with a high pressure in the mold is applied to a relatively small area product, and a RIM method with a low pressure in the mold is applied to a slightly large area product. But,
It is also effective from the economical aspect. The embodiments of the present invention have been described above. However, if the spacer itself has adhesiveness, the primary sealing agent can be omitted. Therefore, a single seal can be formed only with a saturated hydrocarbon sealing agent. It will be possible.

The glass plate constituting the double glazing of the present invention may be raw glass, and may be subjected to tempering treatment, bending treatment, coloring treatment, heat reflection treatment, conductivity treatment, and other various optical treatments. It may be a given one, or
It may be a plate glass, a plastic film, or a product that has been subjected to processing such as combination processing with a plastic plate.
In addition, the double glazing may be composed of two plate glasses, or may be composed of three or four or more glass plates. Further, the glass plate is not limited to the inorganic glass, and may be a transparent plastic plate called organic glass such as an acrylic plate and a polycarbonate plate. The spacer is usually formed of aluminum, iron or the like in a shape having a hollow portion for enclosing a desiccant therein, and the width thereof is appropriately determined according to the interval of the voids of the double glazing. In the case of a double seal, a waterproof polyisobutylene-based or butyl rubber-based material for adhering glass and a spacer can be generally used as a primary sealing agent, but the present invention is a saturated hydrocarbon sealing agent. By using, a crosslinked product is obtained after curing, and therefore weather resistance adhesion to the glass and the spacer is improved. These sealing agents may be extruded into a string shape at the time of use, or may be previously formed into a string shape or a tape shape.

[0082]

EFFECTS OF THE INVENTION The double glazing of the present invention has a low moisture permeability, and is excellent in weather resistance, weather resistance adhesiveness, and heat resistance due to the use of the saturated hydrocarbon sealing agent. Furthermore, there is an advantage that the conventional double seal can be changed to a single seal. Of course, by using this method, it is possible to manufacture a double glazing by a conventional double seal. Further, in the case of producing a double glazing by the method of the present invention, since the line speed can be increased for fast curing, the curing time is almost unnecessary, and thus the working time in the assembly process of the double glazing is reduced. Shortened.

[Brief description of drawings]

FIG. 1 is a conceptual diagram showing an example of a basic structure of a double glazing obtained by the present invention.

FIG. 2 is a conceptual diagram showing another example of the basic structure of the double glazing obtained by the present invention.

FIG. 3 is a conceptual diagram showing a method for producing double glazing according to the present invention.

[Explanation of symbols]

 1 Double-Layered Glass 2 Glass Plate 3 Glass Plate 4 Spacer 5 Hollow Void 6 Primary Sealing Agent 7 Saturated Hydrocarbon Sealing Agent 8 Drying Agent 9 Sealing Material 10 Formwork 11 Arrows Showing Inlet

Claims (12)

[Claims] 1. A multi-layer glass comprising a glass plate held opposite to each other at regular intervals with a cross-linking type saturated hydrocarbon sealing agent having a gel fraction of 50 to 100% interposed therebetween. 2. The double glazing according to claim 1, wherein the saturated hydrocarbon sealing agent contains the following components (A), (B), (C) and (D) as essential components; A hydrocarbon-based polymer having a molecular weight of 500 to 300,000 having at least one alkenyl group in
(B) a curing agent having at least two hydrosilyl groups in the molecule, (C) a hydrosilylation catalyst, and (D) an adhesiveness-imparting agent. 3. The double glazing according to claim 2, wherein the polymer of the component (A) contains 50 wt% or more of repeating units of isobutylene monomer. 4. The component (B) curing agent contains at least 2 monovalent groups derived from a polyorganohydrogensiloxane containing at least one hydrosilyl group in the molecule.
The multi-layer glass according to claim 2 or 3, which is an organic curing agent having one glass. 5. The curing agent as component (B) is an organic curing agent containing in the molecule at least two hydrosilyl groups other than the monovalent group derived from polyorganohydrogensiloxane. The described double glazing. 6. The double glazing according to claim 2, wherein the adhesiveness-imparting agent of the component (D) contains at least one of the adhesive compounds represented by the following general formulas (I) to (V). Embedded image [In the formula, R ₁ , R ₃ , R ₈ and R ₁₁ represent a divalent organic group having 1 to 20 carbon atoms and may be the same or different. R ₂ is an alkoxysilyl group or the following structural formula: (Wherein R ₁₂ is an alkyl group having 1 to 6 carbon atoms), and R ₄ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. R ₅ , R ₆ ,
R ₇ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different. R ₉ represents hydrogen or a monovalent organic group having 1 to 10 carbon atoms, R ₁₀
Represents an alkoxy group. In addition, a means an integer of 1 or 2. ] 7. A process for producing a double glazing, characterized in that a cross-linking type saturated hydrocarbon sealing agent having a gel fraction of 50 to 100% is interposed between glass plates held facing each other at regular intervals. Method. 8. The method for producing a double glazing according to claim 7, wherein the saturated hydrocarbon sealing agent contains the following components (A), (B), (C) and (D) as essential components. ) A hydrocarbon-based polymer having a molecular weight of 500 to 300,000 having at least one alkenyl group in the molecule,
(B) a curing agent having at least two hydrosilyl groups in the molecule, (C) a hydrosilylation catalyst, and (D) an adhesiveness-imparting agent. 9. The method for producing a double glazing according to claim 8, wherein the polymer of the component (A) contains 50 wt% or more of repeating units of an isobutylene monomer. 10. The curing agent of component (B) is an organic curing agent having at least two monovalent groups derived from polyorganohydrogensiloxane having at least one hydrosilyl group in the molecule. 8. The method for producing a double glazing according to 8 or 9. 11. The curing agent as component (B) is an organic curing agent containing at least two hydrosilyl groups other than the monovalent group derived from polyorganohydrogensiloxane in the molecule. A method for producing a double glazing as described above. 12. The adhesiveness-imparting agent of component (D) contains at least one of the adhesive compounds represented by general formulas (I) to (V) according to claim 6. Method for producing double glazing.