JP2006273976A - Two-pack type composition used as secondary sealing material for double glazing and double glazing using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-pack type composition used as a secondary sealing material for double glazing which has excellent hardenability and shows excellent adhesive property in a short time. <P>SOLUTION: The two-pack type composition used as a secondary sealing material for double glazing contains a polyisocyanate compound (A), a hardener containing an aminosilane (B), a polybutadiene polyol (C), a silane compound (D) having a functional group reactable with an amino group and a hydrolyzable silicon-containing group, and/or a base agent containing a silane compound (D') obtained by reacting the silane compound (D) and the aminosilane. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composition for a two-pack type multi-layer glass secondary sealing material and a multi-layer glass using the same.

For multi-layer glass with excellent heat insulation and sound insulation effects, a plurality of glass plates are usually bonded at a predetermined distance via spacers, and the purpose is to prevent external air and water from entering between these glass plates. Sealing material is used. The sealing material is required to have a relatively high curing rate in order to improve the production efficiency of the multi-layer glass, in addition to the adhesiveness to the glass and the spacer.
As the secondary sealing material for the complex glass, polysulfide polymers, silicone polymers, urethane polymers, hot-melt sealing materials and the like are used. Among these polymers, urethane polymers are preferably used because they are excellent in adhesion and water resistance.

  As a sealing material using a urethane polymer, for example, in a sealant for a multilayer transparent plate for joining at least two transparent plates with a spacing member disposed between the transparent plates, (A ) At least 50% by weight or more exists in the hydroxyl group-containing diene polymer having a number average molecular weight of 500 to 9000 and / or a hydroxyl group-containing silane coupling agent comprising the hydroxide thereof, and (B) the hydroxyl group-containing compound (A). Polyisocyanate compound in an amount such that the molar ratio of isocyanate group to hydroxyl group is in the range of 0.5 to 4, (C) 30 to 300 parts by weight of filler with respect to 100 parts by weight of the hydroxyl group-containing compound (A), and (D ) For a multi-layer transparent plate comprising 10 to 200 parts by weight of a viscosity reducing agent having a flash point of 40 ° C. or more per 100 parts by weight of the hydroxyl group-containing compound (A). Zealand "is known (see Patent Document 1.).

Japanese Patent No. 2855196

  However, conventional sealing material compositions such as the sealant for multilayer transparent plates described in Patent Document 1 exhibit sufficient adhesiveness even if cured in a relatively short time (for example, after 24 hours at room temperature). There may not be. For this reason, peeling may occur if stress is applied to the adhesive surface due to external impact or change in internal pressure immediately after curing.

  Accordingly, an object of the present invention is to provide a composition for a two-pack type multi-layer glass secondary sealing material that has excellent curability and can exhibit excellent adhesive properties in a short time.

  As a result of diligent study on the above problems, the present inventor has found that a curing agent containing a polyisocyanate compound, an aminosilane, a polybutadiene polyol, a functional group capable of reacting with an amino group, and a hydrolyzable silicon-containing group. And a composition containing a compound and / or a base containing a silane compound obtained by reacting the silane compound and aminosilane, and having excellent curability and exhibiting excellent adhesiveness in a short time, As a result, the present invention was completed.

That is, the present invention provides the following (1) to (3).
(1) a curing agent containing a polyisocyanate compound (A) and aminosilane (B);
A polybutadiene polyol (C), a silane compound (D) having a functional group capable of reacting with an amino group and a hydrolyzable silicon-containing group and / or a silane compound obtained by reacting the silane compound (D) with aminosilane A composition for a two-pack type multi-layer glass secondary sealing material comprising a base containing (D ′).
(2) The ratio (Y / X) of the number (Y) of active hydrogens of the amino group and / or imino group of the aminosilane (B) to the number of isocyanate groups (X) of the polyisocyanate compound (A) The composition for a two-component multi-layer glass secondary sealing material according to the above (1), which is 0.001 to 0.05.
(3) Multi-layer glass using the composition for a two-pack type multi-layer glass secondary seal material described in (1) or (2) above as a secondary seal material.

  The composition for a two-component multi-layer glass secondary sealing material of the present invention has excellent curability and can exhibit excellent adhesive properties in a short time. Therefore, even if stress is applied to the bonding surface due to an impact from the outside, a change in internal pressure, or the like immediately after curing, peeling does not occur, and the production efficiency of the multilayer glass can be improved.

Hereinafter, the present invention will be described in more detail.
The composition for a two-pack type multi-layer glass secondary sealing material of the present invention (hereinafter also referred to as “the composition of the present invention”) comprises a polyisocyanate compound (A) and an aminosilane (B). And a polybutadiene polyol (C), a silane compound (D) having a functional group capable of reacting with an amino group and a hydrolyzable silicon-containing group and / or the silane compound (D) and aminosilane. A composition comprising a base containing a silane compound (D ′).

<Polyisocyanate compound (A)>
The polyisocyanate compound (A) used in the composition of the present invention is a compound having two or more isocyanate groups in the molecule. Specifically, for example, TDI such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate; MDI such as diphenylmethane-4,4′-diisocyanate; tetramethylxylylene diisocyanate (TMXDI), trimethylhexamethylene Diisocyanate (TMHMDI), 1,5-naphthalene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), triphenylmethane triisocyanate, norbornane skeleton And diisocyanate (NBDI) having a modified form thereof, and modified products thereof.
These may be used alone or in combination of two or more.
Of these, TDI and MDI are preferred. Since these polyisocyanates are general-purpose, they are inexpensive and easily available.

  Moreover, as the polyisocyanate compound (A), a urethane prepolymer obtained by reacting the isocyanate compound described above with a polyol compound can also be used.

  The polyol compound used for the urethane prepolymer is an alcohol in which a plurality of hydrocarbon hydrogens are substituted with hydroxy groups. For example, a product obtained by addition polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran to an active hydrogen-containing compound having two or more active hydrogens in the molecule can be given.

Examples of the active hydrogen-containing compound include polyhydric alcohols, amines, alkanolamines, polyhydric phenols and the like.
Specific examples of the polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, and pentaerythritol.
Specific examples of amines include ethylenediamine and hexamethylenediamine.
Specific examples of alkanolamines include ethanolamine and propanolamine.
Specific examples of polyhydric phenols include resorcin, bisphenols, and the like.

Specific examples of the polyol compound include polyether-based polyols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol; polyolefins such as polybutadiene polyol and polyisoprene polyol. Examples include polyols; adipate-based polyols; lactone-based polyols; polyester-based polyols such as castor oil.
These may be used alone or in combination of two or more.

  The polyol compound preferably has a number average molecular weight of about 500 to 10000, more preferably about 2000 to 6000.

  The ratio of the number of isocyanate groups of the isocyanate group-containing compound to the number of hydroxy groups of the polyol compound (NCO / OH) is the ratio of mixing the polyol compound and the isocyanate group-containing compound in the production of the urethane prepolymer. It is preferably 0 or more, more preferably 1.5 to 2.0.

  The production of the urethane prepolymer is usually carried out by mixing an isocyanate group-containing compound and a polyol compound in a predetermined amount ratio and heating and stirring at 60 to 100 ° C. under normal pressure in the same manner as a normal urethane prepolymer. be able to.

<Aminosilane (B)>
The aminosilane (B) contained in the curing agent of the composition of the present invention is a compound having a primary amino group and / or a secondary amino group (imino group) and a hydrolyzable silicon-containing group.
The hydrolyzable silicon-containing group has 1 to 3 hydroxy groups and / or hydrolyzable groups bonded to a silicon atom, and a catalyst or the like is used in the presence of moisture or a crosslinking agent as necessary. This is a silicon-containing group that can be crosslinked by causing a condensation reaction to form a siloxane bond. Examples thereof include an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, and an amidosilyl group. Specifically, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group and the like exemplified by the following formula are preferably used.

Among these, an alkoxysilyl group is preferable because it is easy to handle.
Although the alkoxy group couple | bonded with the silicon atom of an alkoxy silyl group is not specifically limited, Since acquisition of a raw material is easy, a methoxy group, an ethoxy group, or a propoxy group is mentioned suitably.
The group other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited. For example, a hydrogen atom or an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group An alkenyl group or an arylalkyl group is preferable.

  Specific examples of the aminosilane (B) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, Ureidopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane N-phenyl-3-aminopropyltrimethoxysilane, (N-cyclohexylaminomethyl) methyldiethoxysilane, (N-cyclohexylaminomethyl) triethoxysilane, (N-phenylaminomethyl) methyldimethoxysilane, (N- Phenyl Minomechiru) trimethyl silane and the following formula (1) to compounds represented by any one of (4) can be mentioned. These may be used alone or in combination of two or more.

  Among the aminosilanes (B), compounds represented by the formula (1) or any one of (3) to (4) are preferable. When these aminosilanes are used, the obtained composition can exhibit excellent adhesiveness in a short time.

  The composition of the present invention contains the polyisocyanate compound (A) and the aminosilane (B) in a curing agent. Since this polyisocyanate compound (A) and aminosilane (B) react rapidly at room temperature, the polyisocyanate compound (A) is present in the curing agent with the aminosilane (B) added. Therefore, the composition of the present invention is rapidly cured and can exhibit excellent adhesive properties in a short time.

  The ratio of mixing the polyisocyanate compound (A) and aminosilane (B) is not particularly limited, but the amino group of aminosilane (B) and the number of isocyanate groups (X) of polyisocyanate compound (A) and The ratio (Y / X) of the number (Y) of active hydrogens in the imino group is preferably 0.001 to 0.05, and more preferably 0.005 to 0.03. If it is this range, the composition obtained will be hardened | cured quickly and can exhibit the outstanding adhesiveness in a short time. Furthermore, it is possible to prevent deterioration in workability due to an increase in viscosity.

<Polybutadiene polyol (C)>
The polybutadiene polyol (C) used in the composition of the present invention is not particularly limited as long as it is a butadiene polymer having a hydroxyl group at the terminal and a copolymer of butadiene and other monomer components.
Examples of the monomer component copolymerized with butadiene include styrene and acrylonitrile. These may be used alone or in combination of two or more.

  1000-5000 are preferable and, as for the number average molecular weight of the said polybutadiene polyol (C), 2000-3500 are more preferable.

  The polybutadiene polyol (C) can be produced by a known method, and a commercially available product may be used.

  The content of the polybutadiene polyol (C) is such that the ratio (NCO / OH) of the number of isocyanate groups of the polyisocyanate compound (A) to the number of hydroxy groups of the polybutadiene polyol (C) is 1.0 to 3.0. An amount is preferable, and an amount of 1.1 to 1.4 is more preferable. If it is this range, it is excellent in adhesiveness, foaming resistance, the physical property of hardened | cured material, etc.

<Silane Compound (D) and Silane Compound (D ′)>
The silane compound (D) used in the composition of the present invention is a compound having a functional group capable of reacting with an amino group and a hydrolyzable silicon-containing group.
Here, the functional group capable of reacting with the amino group means a functional group capable of reacting with a primary amino group and / or a secondary amino group (imino group). Specifically, an epoxy group, an isocyanate group, etc. are mentioned, for example. Examples of the hydrolyzable silicon-containing group include the same hydrolyzable silicon-containing groups that the aminosilane (B) has.

Specific examples of the silane compound (D) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and other epoxy silanes; 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldiethoxysilane 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatoethyltrimethoxysilane, 3-isocyanatoethyltriethoxysilane, 3-isocyanateethylmethyldiethoxysilane, 3-isocyanate ether Isocyanate silane such as methyl dimethoxysilane; and the like.
These may be used alone or in combination of two or more. Among these, epoxy silane is preferable because it has a high effect of imparting adhesiveness (particularly adhesiveness to glass).

The silane compound (D ′) is a compound obtained by reacting a compound having a functional group capable of reacting with an amino group and a hydrolyzable silicon-containing group (silane compound (D)) with aminosilane.
As said aminosilane, the thing similar to the aminosilane (B) mentioned above is mentioned.

The silane compound (D ′) can be obtained by reacting the silane compound (D) with aminosilane. The reaction can be performed by a known method.
The mixing ratio of the silane compound (D) and aminosilane is not particularly limited, but the amino group and / or imino group of the aminosilane with respect to the number of functional groups (P) that can react with the amino group of the silane compound (D). The ratio (Q / P) of the number of active hydrogens (Q) is preferably 1/5 to 1/1, and more preferably 1/3 to 1/1. If it is this range, it is excellent in adhesiveness and storage stability.

  The 1st aspect of a preferable silane compound (D ') is a compound obtained by making epoxysilane and aminosilane react. Specifically, for example, a compound represented by the following formula (5) obtained by reacting 3-glycidoxypropyltrimethoxysilane with an aminosilane represented by the above formula (1) is preferably exemplified. .

  The 2nd aspect of a preferable silane compound (D ') is a compound obtained by making an isocyanate silane and aminosilane react. Specifically, for example, a compound represented by the following formula (6) obtained by reacting 3-isocyanatopropyltrimethoxysilane with an aminosilane represented by the above formula (3) is preferably exemplified.

  The silane compound (D ′) may be used alone or in combination.

In the composition of the present invention, the silane compound (D) and the silane compound (D ′) may be used alone or in combination.
The content of the silane compound (D) and / or the silane compound (D ′) is such that the total of the silane compound (D) and the silane compound (D ′) is 100 parts by mass of the polybutadiene polyol (C). On the other hand, it is preferable that it is 0.5-20 mass parts, and it is more preferable that it is 1-5 mass parts. Within this range, the resulting composition has excellent adhesion (particularly adhesion to glass).

<Curing catalyst>
The composition of the present invention preferably further contains a curing catalyst. The curing catalyst used for the composition of this invention will not be specifically limited if it is a catalyst which accelerates | stimulates hardening of a polyisocyanate compound (A). Specific examples include metal catalysts such as tertiary amine compounds, metal soap compounds, metal alkylates, and metal chelates.

Specific examples of the tertiary amine compound include N, N, N ′, N′-tetramethylpropylenediamine, N, N-dimethylbenzylamine, triethylenediamine, pentamethylenediethylenetriamine, and morpholine amine. , Triethylamine and the like.
Specific examples of the metal soap compound include organic acid salts such as tin, zinc, bismuth, zirconium, cobalt, calcium, cerium, and iron. As the metal alkylate, alkoxides of titanium and zirconium, specifically, tetrapropoxy titanium and tetrabutoxy titanium, and condensates thereof can be used.
As said metal chelate, chelates, such as titanium, aluminum, zirconium, iron, and cobalt, specifically, aluminum acetylacetonate etc. can be used.
These may be used alone or in combination of two or more.

Among the above curing catalysts, tertiary amine compounds are preferable from the viewpoint of hardness development.
Moreover, it is preferable to use a bismuth organic acid salt and a calcium organic acid salt in combination from the viewpoint of foamability.

Specific examples of the bismuth organic acid salt include bismuth organic carboxylates and bismuth resinates (bismuth rosinate).
More specifically, examples of the organic carboxylic acid bismuth include bismuth salts such as octylic acid, 2-ethylhexylic acid, neodecanoic acid, and neododecanoic acid. Among these, bismuth octylate, bismuth 2-ethylhexylate and bismuth neodecanoate are preferable.
Examples of bismuth resin acid include bismuth salts of alicyclic organic acids such as abietic acid, neoabietic acid, d-pimalic acid, iso-d-pimalic acid, podocarpic acid, benzoic acid, cinnamic acid, and p-oxycinnamic acid. Examples thereof include bismuth salts of aromatic organic acids such as acids. Among these, bismuth abietic acid is preferable.
These may be used alone or in combination of two or more.

Specific examples of the calcium organic acid salt include organic calcium carbonate and resin acid calcium (calcium rosinate).
More specifically, examples of calcium organic carboxylate include calcium salts such as octylic acid, 2-ethylhexylic acid, neodecanoic acid, neododecanoic acid and the like. Among these, calcium octylate, calcium 2-ethylhexylate and calcium neodecanoate are preferable.
Examples of calcium resinate include calcium salts of alicyclic organic acids such as abietic acid, neoabietic acid, d-pimalic acid, iso-d-pimalic acid, podocarpic acid, benzoic acid, cinnamic acid, and p-oxycinnamic acid. Examples thereof include calcium salts of aromatic organic acids such as acids. Among these, calcium abietate is preferable.
These may be used alone or in combination of two or more.

  The bismuth organic acid salt and the calcium organic acid salt are diluted with an organic acid such as octylic acid, 2-ethylhexylic acid and neodecanoic acid, a plasticizer such as polyol, and a solvent such as terpene and toluene in order to make it liquid. Can be used.

  The blending ratio of the bismuth organic acid salt and the calcium organic acid salt is preferably 5/1 to 1/5, more preferably 3/1 to 1/1 in terms of mass ratio (bismuth organic acid salt / calcium organic acid salt). preferable.

  The content of the curing catalyst is preferably 0.01 to 1 part by mass and more preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of the polyisocyanate compound (A).

  The composition of the present invention is, as necessary, a filler, a reaction retardant, an anti-aging agent, an antioxidant, a pigment (dye), a plasticizer, and a thixotropic agent, as long as the object of the present invention is not impaired. , Ultraviolet absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, adhesion-imparting agents, antistatic agents, and other various additives.

  Examples of the filler include organic or inorganic fillers having various shapes. Specifically, for example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; Waxite clay, kaolin clay, calcined clay; carbon black; these fatty acid treated products, resin acid treated products, urethane compound treated products, and fatty acid ester treated products.

  Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Specific examples of the pigment include inorganic pigments such as titanium oxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, etc .; azo pigment, phthalocyanine pigment, quinacridone Pigment, quinacridone quinone pigment, dioxazine pigment, anthrapyrimidine pigment, ansanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, perinone pigment, diketopyrrolopyrrole pigment, quinonaphthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone Examples thereof include organic pigments such as pigments, isoindoline pigments, and carbon black.

  Specific examples of the plasticizer include dioctyl phthalate (DOP) and dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; phosphorus Examples include tricresyl acid, trioctyl phosphate; propylene glycol polyester adipate, butylene glycol polyester adipate, and the like.

Specific examples of the thixotropic agent include aerosil (manufactured by Nippon Aerosil Co., Ltd.), disparon (manufactured by Enomoto Kasei Co., Ltd.), and the like.
Specific examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and the like.

Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl / methyl phosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether, and the like.
Examples of the antistatic agent generally include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

  The composition of the present invention includes a curing agent (agent A) containing the polyisocyanate compound (A) and the aminosilane (B), the polybutadiene polyol (C), and the above from the viewpoint of storage stability and the like. It is used as a two-component type consisting of a silane compound (D) and / or a base (B agent) containing the silane compound (D ′). The curing catalyst and various additives used as necessary can be blended in either or both of the curing agent and the base.

The curing agent (agent A) of the composition of the present invention is, for example, stirring the polyisocyanate compound (A), the aminosilane (B), the curing catalyst used as necessary, and various additives under a reduced pressure, such as a mixing mixer. It can be obtained with sufficient stirring using a machine.
Similarly, the base (agent B) used in the composition of the present invention is the above-mentioned polybutadiene polyol (C), the above-mentioned silane compound (D) and / or the above-mentioned silane compound (D ′) and a curing catalyst used as necessary. And various additives can be obtained by sufficiently stirring.
The composition of the present invention can be used by mixing the curing agent and the substrate.

As described above, the composition of the present invention has excellent curability and can exhibit excellent adhesive properties in a short time. Therefore, even if stress is applied to the adhesion surface due to an impact from outside, a change in internal pressure, or the like immediately after curing, peeling does not occur, and the production efficiency of the multilayer glass can be improved.
<Multilayer glass>
Hereinafter, the multilayer glass of the present invention will be described.
The multilayer glass of the present invention is a multilayer glass using the above-described composition of the present invention as a secondary sealing material. An example of a preferred embodiment of the multilayer glass of the present invention is that two or more glass plates are arranged to face each other with a spacer between the two glass plates, the spacer, and the glass plate and the spacer. A multi-layer glass in which a hollow layer is formed by a primary sealing material provided in a part or all of the space between the spacer outer peripheral surface, the primary sealing material, and the inner surfaces of the two glass plate peripheral portions. It is a double-glazed glass that seals the voids formed with the composition of the present invention.

FIG. 1 is a schematic cross-sectional view showing an example of the structure of the multilayer glass of the present invention.
The multi-layer glass 10 of the present invention is provided with a spacer 3 having a desiccant (hygroscopic material) 2 in the vicinity of the peripheral edge of the glass plate 5 so that the secondary sealing material 1 can be provided. 5 is provided between the outer peripheral surface of the spacer 3, the primary sealing material 7, and the inner surfaces of the peripheral portions of the two glass plates 5 with the composition of the present invention (filling). ).

As long as the multilayer glass of the present invention uses the composition of the present invention as a secondary sealing material, the other configurations, structures, and the like are not particularly limited. For example, a spacer / sealing material formed of a resin composition in which the spacer 3 and the primary seal material 7 are integrated may be used. Further, an adhesive layer may be provided between the primary sealing material 7 and the glass plate 5. Further, the number of glass plates 1 is not limited to two, and may be three or more, and can be determined as necessary.
In the multilayer glass of the present invention, the distance between the glass plates 5 forming the air layer is not particularly limited, but is preferably about 6 mm or about 12 mm, for example.

  As a spacer used for the double glazing of the present invention, a spacer generally used for double glazing can be used. For example, a hollow spacer of a hollow metal spacer filled with a desiccant (hygroscopic agent) or a resin spacer can be used.

  As a glass plate used for the multilayer glass of the present invention, a glass plate used for building materials, vehicles and the like can be used without particular limitation. For example, the glass normally used for a window etc., tempered glass, glass with a metal net | network, heat ray absorption glass, heat ray reflective glass, organic glass is mentioned. Moreover, the thickness of glass is determined suitably.

  The primary sealing material used for the multilayer glass of the present invention is preferably used as a composition containing the following main materials. As the main material, butyl rubber-based, polysulfide-based, silicone-based, and urethane-based materials are preferably used in terms of butyl rubber-based hot melt, low moisture permeability material, and rapid curing.

  The multilayer glass of the present invention was basically bonded by placing a spacer between two parallel glass plates fixed to the machine and extruding the primary sealing material with a nozzle or the like connected to the extruder. Thereafter, the composition of the present invention can be extruded by an extruder to provide a secondary sealing material. Under the present circumstances, a primer can be apply | coated to a glass plate and a spacer as needed, and also an adhesive agent can also be apply | coated as needed.

  The primer and adhesive may be applied manually by an applicator or the like, or by a robot that automatically pushes out the primer and adhesive. In particular, the composition of the present invention and the adhesive are coextruded by an extruder, extruded so that the outer layer has the structure of the adhesive, and the inside of the outer layer has the structure of the present invention, and the extruded composition of the present invention is bonded. The agent may be directly discharged between the peripheral edges of the glass plate.

  Since the double-glazed glass of the present invention uses the composition of the present invention as a secondary sealing material, even if stress is applied due to external impact or internal pressure change immediately after the composition is cured, it is difficult to peel off and is durable. Excellent in properties. Therefore, the member can be moved in a short time after curing, and the production efficiency can be improved.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Examples 1-5 and Comparative Examples 1-4>
Each component of the following Table 1 was mixed with the composition (parts by mass) shown in Table 1 using a stirrer to obtain a composition for each double-glazed glass sealing material shown in Table 1.
Using each of the obtained compositions, the adhesion was evaluated by the following method.

(Adhesiveness)
FIG. 2 is a perspective view of a test body used in the adhesion test of the present invention. FIG. 3 is a cross-sectional view of a specimen used for the adhesion test of the present invention. Hereinafter, a method for producing the specimen shown in FIGS. 2 and 3 will be described.
Float glass 13 (50 × 50 × 5 mm) with a 2 mm wide Teflon tape 11 attached to one end of the tin surface, and a 2 mm wide Teflon tape 11 attached to one end of the non-tin surface The float glass 15 (50 × 50 × 5 mm) is opposed to the surface on which the Teflon tape 11 is pasted via a spacer for specimen preparation (not shown), and is 50 × 12 × 12 mm A space was created and placed on a release material (not shown). After filling each space with the composition 17 for the double-layer glass secondary sealing material obtained in that space, the mold release material was removed, and the specimen was cured for 24 hours in an environment of 20 ° C. and 65% RH. Obtained.
The prepared specimen was pulled 10% in the vertical direction (in the direction of the arrow in FIG. 3) with a tension device and left in that state in an environment of 20 ° C. and 65% RH for 24 hours, and then the fracture state of the specimen was visually observed. did.
The seal material that did not cause cohesive failure and interfacial debonding was designated as “◯”, and the seal material that produced interfacial delamination as “AF”.
The results are shown in Table 1.

The components in Table 1 are as follows.
Liquid MDI: PAPI135, manufactured by Mitsubishi Kasei Dow Co., Ltd. Plasticizer (diisononyl phthalate): DINP, manufactured by J-plus Co., Ltd. Carbon black: MA600, manufactured by Mitsubishi Chemical Co., Ltd. Tertiary amine / DINP (1/9) mixed solution : 2-methylethyltriethylenediamine (Methyl-DABCO, manufactured by Air Products Japan) and diisononyl phthalate (DINP, manufactured by J-plus) at a mass ratio of 1 / 9-Aminosilane 1 (the above formula ( 3): A1170, manufactured by Nihon Unicar Co., Ltd. Aminosilane 2 (compound represented by the above formula (1)): A-Link15, manufactured by Nihon Unicar Co., Ltd. Silane coupling agent 3 (the above formula (4) ): Y11637, manufactured by Nihon Unicar Company

-Polybutadiene polyol: R45HT, manufactured by Idemitsu Kosan Co., Ltd.-Calcium carbonate 1: Shiraka Hana CCR, manufactured by Shiroishi Kogyo Co., Ltd.-Calcium carbonate 2: Lighton A4, manufactured by Bihoku Flour Industries Co., Ltd. Aminosilane reactant (compound represented by the above formula (5)): 30 g of epoxy silane (A187, manufactured by Nihon Unicar) and 10 g of aminosilane (A-Link15, manufactured by Nihon Unicar) were mixed at 80 ° C. and 8 g. A colorless transparent liquid obtained by stirring and reacting for a period of time. ・ Isocyanate silane / aminosilane reaction product (compound represented by the above formula (6)): 16.6 g of aminosilane (A1170, manufactured by Nihon Unicar Company) Nippon Unicar Co., Ltd.) is mixed with 10g and stirred at 80 ° C for 8 hours to react. Colorless transparent liquid, anti-aging agent obtained by 1: Tinuvin 327, Ciba-Geigy Japan Co., Antioxidant 2: Sanol LS-765, Sankyo Co., Ltd.

As is apparent from the results shown in Table 1, the compositions containing no aminosilane (B) (Comparative Examples 1 to 3) do not have sufficient adhesion and cause interfacial delamination with the tin surface of the float glass. It was. Further, the composition containing no silane compound (D) or the silane compound (D ′) (Comparative Example 4) also had insufficient adhesiveness and caused interfacial peeling with the tin surface of the float glass.
On the other hand, the compositions of Examples 1 to 5 did not cause interfacial peeling or cohesive failure, and exhibited excellent adhesion within a relatively short time.

FIG. 1 is a schematic cross-sectional view showing an example of the structure of the multilayer glass of the present invention. FIG. 2 is a perspective view of a test body used in the adhesion test of the present invention. FIG. 3 is a cross-sectional view of a specimen used for the adhesion test of the present invention.

Explanation of symbols

1 Secondary sealant 2 Desiccant (hygroscopic material)
DESCRIPTION OF SYMBOLS 3 Spacer 5 Glass plate 7 Primary sealing material 10 Double layer glass 11 Teflon tape 13, 15 Float glass 17 Composition for secondary glass secondary sealing material

Claims (3)

A curing agent containing a polyisocyanate compound (A) and aminosilane (B);
A polybutadiene polyol (C), a silane compound (D) having a functional group capable of reacting with an amino group and a hydrolyzable silicon-containing group and / or a silane compound obtained by reacting the silane compound (D) with aminosilane A composition for a two-pack type multi-layer glass secondary sealing material comprising a base containing (D ′).   The ratio (Y / X) of the number (Y) of active hydrogens of the amino group and / or imino group of the aminosilane (B) to the number of isocyanate groups (X) of the polyisocyanate compound (A) is 0. It is 001-0.05, The composition for 2 liquid type multilayer glass secondary sealing materials of Claim 1.   Multi-layer glass using the composition for a two-component multi-layer glass secondary seal material according to claim 1 or 2 as a secondary seal material.

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