JP2010059006A - Secondary sealing material composition for double-glazed glass, and double glazed glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a secondary sealing material composition for a double-glazed glass, which has excellently balanced pot life and curability. <P>SOLUTION: In the secondary sealing material composition for a double-glazed glass, which composition contains a polybutadiene polyol and a polyisocyanate compound, 0.01 to 2 pts.mass of an amine catalyst is contained based on 100 pts.mass of the polybutadiene polyol; 0.0001 to 0.1 pt.mass of a tin catalyst is contained based on 100 pts.mass of the polybutadiene polyol; and the content of the tin catalyst is 1 to 30 mass% to the mass of the amine catalyst. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a secondary sealing material composition for double glazing and double glazing.

2. Description of the Related Art In recent years, a double-glazed glass excellent in heat insulation has been attracting attention in the field of construction, vehicle production such as automobiles, etc., for maintaining the temperature in a room or in a vehicle.
In this multi-layer glass, a sealing material is usually used to seal the periphery between a plurality of glass plates. As the secondary sealing material, a polysulfide polymer, a silicone polymer, a urethane system is used. Polymers, saturated hydrocarbon polymers, hot melt sealants and the like are used.

Here, with respect to the urethane-based polymer, in Patent Document 1, "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 of a hydroxyl group-containing diene polymer having a number average molecular weight of 500 to 9000 and / or a hydroxide thereof, (B) an isocyanate for the hydroxyl group present in the hydroxyl group-containing compound (A) A polyisocyanate compound in an amount such that the molar ratio of the groups is in the range of 0.5 to 4, (C) 30 to 300 parts by weight of filler relative to 100 parts by weight of the hydroxyl group-containing compound (A), and (D) the hydroxyl group-containing compound (A) A sealant for a multilayer transparent plate obtained by blending 10 to 200 parts by weight of a viscosity reducing agent having a flash point of 40 ° C. or higher with respect to 100 parts by weight. ”
Patent Document 1 describes tertiary amines such as triethylenediamine and organometallic compounds such as dibutyltin dilaurate as catalysts for promoting the curing reaction (page 5, left column, lines 42 to right). Column 5th line).

In addition, by the present applicant, in Patent Document 2, “a curing agent containing a polyisocyanate compound (A) and a silane coupling agent (B) obtained by reacting a bisphenol F-type epoxy resin and iminosilane;
A composition for a two-pack type multi-layer glass secondary sealing material comprising a base containing a polybutadiene polyol (C). Is proposed.
Moreover, in patent document 2, metal catalysts, such as a tertiary amine compound, a metal soap compound, a metal alkylate, a metal chelate, are described as a curing catalyst, and each specific example is also described ([[ 0038] [0039]).

Furthermore, by the present applicant, in Patent Document 3, "a curing agent containing a polyisocyanate compound (A) and an 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 ′). "
Moreover, in patent document 3, metal catalysts, such as a tertiary amine compound, a metal soap compound, a metal alkylate, a metal chelate, are described as a curing catalyst, and each specific example is also described ([[ 0041] [0042]).

  Further, the present applicant has disclosed in Patent Document 4 a compound containing “a polybutadiene polyol, a polyisocyanate compound, a surface-treated calcium carbonate obtained by surface-treating colloidal calcium carbonate with a fatty acid, and a triethylenediamine compound. A secondary sealant composition for layer glass "has been proposed.

Japanese Patent No. 2855196 JP 2006-273641 A JP 2006-273976 A JP 2007-126305 A

  However, as a result of the inventor's examination of the composition for a double-layer glass secondary sealing material described in each of the above patent documents, the curability ( For example, the hardness after 3 hours and the hardness ratio between the hardness after 3 hours and the final hardness) are inferior, and it has been found that it is difficult to balance the pot life and curability.

  Then, this invention makes it a subject to provide the secondary sealing material composition for multilayer glass which is excellent in the balance of pot life and sclerosis | hardenability.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that a combination of an amine catalyst and a tin catalyst in a specific amount is excellent in the balance of pot life and curability, and completed the present invention. It was.
That is, the present invention provides the following (1) to (3).

(1) A secondary sealing material composition for multilayer glass containing a polybutadiene polyol and a polyisocyanate compound,
0.01 to 2 parts by mass of an amine catalyst with respect to 100 parts by mass of the polybutadiene polyol,
0.0001-0.1 part by mass of tin catalyst is contained with respect to 100 parts by mass of the polybutadiene polyol,
The secondary sealing material composition for multilayer glass whose content of the said tin catalyst is 1-30 mass% with respect to the mass of the said amine catalyst.

  (2) The secondary sealing material composition for multilayer glass according to (1), wherein the filler is contained in an amount of 300 to 500 parts by mass with respect to 100 parts by mass of the polybutadiene polyol.

  (3) Multi-layer glass using the secondary sealant composition for multi-layer glass as described in (1) or (2) above as a secondary sealant.

As will be described below, according to the present invention, it is possible to provide a secondary sealing material composition for double-glazed glass having an excellent balance between pot life and curability.
Therefore, the secondary sealing material composition for double-glazed glass according to the present invention is very useful because the expression rate of the effect on the kneading failure is increased and the reliability in on-site construction is improved.

The present invention is described in detail below.
The secondary sealant composition for double-glazed glass of the present invention (hereinafter also referred to as “the composition of the present invention”) is a secondary sealant composition for double-glazed glass containing a polybutadiene polyol and a polyisocyanate compound. And
0.01 to 2 parts by mass of an amine catalyst with respect to 100 parts by mass of the polybutadiene polyol,
0.0001-0.1 part by mass of tin catalyst is contained with respect to 100 parts by mass of the polybutadiene polyol,
It is a secondary sealing material composition for multilayer glass whose content of the said tin catalyst is 1-30 mass% with respect to the mass of the said amine catalyst.
Next, each component of the composition of the present invention will be described in detail.

<Polybutadiene polyol>
The polybutadiene polyol used in the composition of the present invention is a polybutadiene having two or more hydroxy groups.
Examples of polybutadiene include butadiene homopolymers, copolymers of butadiene and other monomer components, and the like.
Here, examples of the monomer component to be copolymerized with butadiene include styrene and acrylonitrile. A monomer component can be used individually or in combination of 2 or more types.

  In the present invention, the position of the hydroxy group bonded to the polybutadiene polyol is not particularly limited, but the hydroxy group is preferably bonded to the end of the polybutadiene.

  In the present invention, the number average molecular weight of the polybutadiene polyol is preferably 1000 to 5000 and 2000 to 3500 because the viscosity and workability of the resulting composition of the present invention are good. Is more preferable.

The said polybutadiene polyol is not specifically limited about the manufacture, For example, it can manufacture by a conventionally well-known method.
Moreover, the said polybutadiene polyol can use a commercial item. Examples of commercially available products include R45HT and R15HT (both manufactured by Idemitsu Kosan Co., Ltd.).

  Such polybutadiene polyols can be used alone or in combination of two or more.

<Polyisocyanate compound>
The polyisocyanate compound used in the composition of the present invention is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule.

Specific examples of the polyisocyanate compound include TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI)), MDI, and the like. (For example, 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI)), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene Hexamethyle aromatic polyisocyanates such as diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; Aliphatic polyisocyanates such as diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane (H ₆ XDI), alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate (H ₁₂ MDI); carbodiimide-modified polyisocyanates; isocyanurate-modified polyisocyanates; and the like.

In the present invention, the polyisocyanate compounds can be used alone or in combination of two or more.
Of these, polymethylene polyphenylene polyisocyanate (polymeric MDI) is preferred because it is inexpensive and easily available.
Further, the polyisocyanate compound is preferably in a liquid form for the reason that it is excellent in handleability. As such a polyisocyanate compound, for example, commercially available products such as polymeric MDI (PAPI-135, manufactured by Dow Chemical Japan Co., Ltd.), polymeric MDI (P20J, manufactured by Diachemical Co., Ltd.) can be used.

Moreover, as said polyisocyanate compound, the urethane prepolymer obtained by making the polyisocyanate compound and polyol compound mentioned above react can also be used, for example.
The polyol compound that can be used in the production of the urethane prepolymer is not particularly limited as long as it is a compound having two or more hydroxy groups. Examples thereof include 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.

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

Specific polyol compounds include, for example, polyether-based polyols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol; polyolefin-based polyols such as polybutadiene polyol and polyisoprene polyol; adipate Polyester polyols; lactone polyols; polyester polyols such as castor oil.
These can be used alone or in combination of two or more.

  The number average molecular weight of the polyol compound is preferably 500 to 10,000, more preferably 2000 to 6,000, because the viscosity and workability of the composition of the present invention to be obtained are good.

  The ratio of the number of isocyanate groups in the polyisocyanate compound to the number of hydroxy groups in the polyol compound (NCO / OH) was 1.0 It is preferable that it is above, and it is more preferable that it is 1.5-5.0.

  The production of the urethane prepolymer is not particularly limited. For example, it can be carried out by mixing the polyisocyanate compound and the polyol compound in the above quantitative ratio, and heating and stirring at 60 to 100 ° C. under normal pressure.

  In the present invention, the content of the polyisocyanate compound is such that the number of hydroxyl groups of the polyisocyanate compound relative to the number of hydroxy groups of the polybutadiene polyol is favorable for improving adhesiveness (especially, weather resistance adhesion and resistance to hot water). The number ratio (NCO / OH) is preferably such that the number is 0.9 to 1.5.

<Amine catalyst>
The amine catalyst used for the composition of this invention is not specifically limited, For example, a tertiary amine compound etc. can be used.

  Specific examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, trioctylamine, trilaurylamine, dimethylethylamine, dimethylpropylamine, Dimethylbutylamine, dimethylamylamine, dimethylhexylamine, dimethylcyclohexylamine, dimethyloctylamine, dimethyllaurylamine, triallylamine, tetramethylethylenediamine, triethylenediamine represented by the following formula (1) and derivatives thereof, N-methylmorpholine 4,4 '-(oxydi-2,1-ethanediyl) bis-morpholine, N, N-dimethylbenzylamine, pyridine, picoline, dimethylaminomethylphenol Diol, trisdimethylaminomethylphenol, 1,8-diazabicyclo [5.4.0] undecene-1,1,4-diazabicyclo [2.2.2] octane, triethanolamine, N, N'-dimethylpiperazine, Examples include tetramethylbutanediamine, bis (2,2-morpholinoethyl) ether, bis (dimethylaminoethyl) ether, and the like. These may be used alone or in combination of two or more.

  Examples of the triethylenediamine derivative include those having an alkyl group having 1 to 8 carbon atoms. Specific examples include 2-methyltriethylenediamine represented by the following formula (2).

  Of these, triethylenediamine represented by the above formula (1) and 2-methyltriethylenediamine represented by the above formula (2) are preferable because of excellent weather resistance and excellent hot water adhesion.

  In the present invention, the content of the amine catalyst is 0.01 to 2 parts by weight, preferably 0.02 to 0.06 parts by weight, based on 100 parts by weight of the polybutadiene polyol. .

<Tin catalyst>
As the tin catalyst used in the composition of the present invention, those conventionally known as a resin composition or a rubber composition can be used, and are not particularly limited.

  Specific examples of the tin catalyst include dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), Dibutyltin bis (ethyl maleate), dibutyltin bis (butylmaleate), dibutyltin bis (octylmaleate), dibutyltin bis (tridecylmaleate), dibutyltin bis (benzylmaleate), dibutyltin diacetate , Dioctyltin bis (ethyl maleate), dioctyltin bis (octyl maleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibutyltin bis (acetylacetonate), dibutyl Examples thereof include bis (ethylacetoacetonate), a reaction product of dibutyltin oxide and a silicate compound, a reaction product of dibutyltin oxide and a phthalate ester, etc. These may be used alone or in combination of two or more. You may use together.

In this invention, content of the said tin catalyst is 0.0001-0.1 mass part with respect to 100 mass parts of said polybutadiene polyol, It is preferable that it is 0.001-0.005 mass part.
Moreover, content of the said tin catalyst is 1-30 mass% with respect to the mass of the said amine catalyst, and it is preferable that it is 2-10 mass%.

In the present invention, by containing the amine catalyst and the tin catalyst in the ranges described above, the balance of pot life and curability of the resulting composition of the present invention is improved.
Specifically, when the composition of the present invention is a two-component type, the pot life after mixing and preparing the base material and the curing agent is 20 minutes or more, and the JIS A hardness after 3 hours is 25 or more.
This is considered to be due to a difference in catalytic function between the amine catalyst (amine compound) and the tin catalyst (tin compound). That is, the amine compound activates, for example, a carbon atom of an isocyanate group or a hydrogen atom of a hydroxyl group as an electron donor, whereas a tin compound serves as an electron acceptor as an oxygen atom of an isocyanate group or an oxygen atom of a hydroxyl group. Activate. Therefore, it is considered that conflicting characteristics such as pot life and curing speed are satisfied.

The composition of the present invention preferably further contains a filler from the viewpoint of workability, viscosity, hardness after curing, and the like.
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; surface-treated calcium carbonate (for example, heavy Calcium carbonate or calcium carbonate obtained by surface treatment of colloidal calcium carbonate), calcium carbonate other than surface treated calcium carbonate, magnesium carbonate, zinc carbonate; wax stone clay, kaolin clay, calcined clay; carbon black; and the like.
Among these, the surface treatment colloidal calcium carbonate and heavy carbonate are preferable because the properties (eg, viscosity) of the composition of the present invention obtained and the physical properties (eg, acidity, water resistance, hardness, etc.) of the cured product are excellent. Calcium is preferred.

  In the present invention, the fillers can be used alone or in combination of two or more.

  Moreover, in this invention, it is preferable that content of the said filler is 300-500 mass parts with respect to 100 mass parts of said polybutadiene polyols.

It is preferable that the composition of this invention contains a silane coupling agent from a viewpoint that it is excellent in weather-resistant adhesiveness and is excellent in hot water-resistant adhesiveness.
The silane coupling agent is not particularly limited, and specific examples thereof include vinyl silane, (meth) acryl silane, amino silane, epoxy silane, acid anhydride silane, and isocyanate silane.
Among these, epoxy silane is mentioned as one of the preferable embodiments.

The epoxy silane is not particularly limited as long as it is a silane coupling agent having an epoxy group. Specific examples thereof include γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycid. Xylpropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyltrimethoxysilane, β- (3,4- Epoxycyclohexyl) ethylmethyldimethoxysilane, epoxy group-modified silicone resin, silyl group-modified epoxy resin, and a copolymer composed of an epoxy resin and a silicone resin.
Of these, γ-glycidoxypropyltrimethoxysilane is preferred because it is more excellent in adhesiveness.

  In the present invention, the silane coupling agents can be used alone or in combination of two or more.

  Moreover, in this invention, content of the said silane coupling agent is 0.5-10 mass parts with respect to 100 mass parts of said polybutadiene polyols from the reason that it is more excellent in weather resistance adhesiveness, and is excellent in hot water-resistant adhesiveness. It is preferable that it is 1-5 mass parts.

  The composition of the present invention, if necessary, within a range that does not impair the purpose of the present invention, for example, reaction retarder, anti-aging agent, antioxidant, pigment (dye), plasticizer, thixotropic agent, Additives such as ultraviolet absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, adhesion-imparting agents, and antistatic agents can be contained.

Specific examples of the antioxidant include N, N′-diphenyl-p-phenylenediamine (DPPD), N, N′-dinaphthyl-p-phenylenediamine (DNPD), 2,2,4-trimethyl. Examples include -1,3-dihydroquinoline (TMDQ), N-phenyl-1-naphthylamine (PAN), and hindered phenol compounds.
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), diisononyl phthalate (DINP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate; Examples include methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester, 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 include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

From the viewpoint of storage stability, the composition of the present invention is preferably a two-component composition comprising a base material containing the polybutadiene polyol described above and a curing agent containing the polyisocyanate compound described above.
Moreover, an amine catalyst can be mix | blended with either one or both of a hardening | curing agent and a base. From the viewpoint of storage stability, it is preferable to blend in the base.
Similarly, the tin catalyst can be incorporated into either or both of the curing agent and the base.
Moreover, the filler (calcium carbonate etc.) contained depending on necessity can be mix | blended with either one or both of a hardening | curing agent and a base.
Similarly, the optionally contained silane coupling agent can be blended in either or both of the curing agent and the base. From the viewpoint of storage stability, it is preferable to blend in the curing agent.
Similarly, various additives optionally contained can be blended in either or both of the curing agent and the base.

The composition of the present invention is not particularly limited with respect to its production method.
For example, when the composition of the present invention is a two-component type, as described above, if a polybutadiene polyol is used as a base material and a polyisocyanate compound is used as a curing agent, the other components are the base material and / or cured. It can be used as an agent.
Specifically, it can be prepared as follows.

The base material is, for example, the above polybutadiene polyol and a filler, a triethylenediamine compound, a plasticizer, an anti-aging agent, etc. that can be used if necessary, and sufficiently using a stirrer such as a mixing mixer under reduced pressure. It can be obtained by stirring. The prepared substrate can be stored in a container whose interior is replaced with an inert gas.
Similarly, the curing agent can be obtained by sufficiently stirring the polyisocyanate compound and a filler, a silane coupling agent, a plasticizer, and the like that can be used as necessary. The prepared curing agent can be stored in a container whose interior is replaced with an inert gas.
And a hardening | curing agent and a base material can be mixed and used at the time of use.

Next, the multilayer glass of the present invention will be described below.
The double-glazed glass of the present invention uses the secondary sealant composition for double-glazed glass of the present invention as a secondary sealant.
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 interposed therebetween, or two glass plates, a spacer, and a part between the glass plate and the spacer or All are sealed by the primary sealing material, and then obtained by secondary sealing with the composition of the present invention the void formed by the outer peripheral surface of the spacer, the primary sealing material, and the inner surfaces of the peripheral portions of the two glass plates. It can be.

FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the multilayer glass of the present invention.
As shown in FIG. 1, the multi-layer glass 10 is configured such that two or more glass plates 5 are arranged to face each other with a spacer 3 interposed therebetween, and the two glass plates 5, the spacer 3, the glass plate 5, and the spacer 3 are arranged. A part between them is sealed with the primary sealing material 7.
By thus sealing with the primary sealing material 7, a hollow layer 9 is formed between the two glass plates 5.
In addition, the composition of the present invention is formed in a gap formed by the outer peripheral surface (not shown) of the spacer 3, the primary sealing material 7 and the inner surfaces of the peripheral portions (not shown) of the two glass plates 5. It is sealed with a secondary sealing material 1 that is filled and cured.
The spacer 3 can have a desiccant (hygroscopic material) 2 inside.

As long as the multilayer glass of the present invention uses the composition of the present invention as a secondary sealant, there are no particular limitations on other configurations, structures, and the like.
For example, a spacer / sealing material made of a resin composition in which the spacer 3 and the primary sealing material 7 are integrated may be used.
Further, an adhesive layer (not shown) may be provided between the primary sealing material 7 and the glass plate 5. Furthermore, the number of glass plates 5 is not limited to two, but may be three or more, and can be determined as necessary.

  As the spacer used in the double-glazed glass of the present invention, a spacer used in general double-glazed glass can be used. For example, a hollow portion of a hollow metal spacer filled with a desiccant (hygroscopic agent), resin A made spacer or the like can be used.

The glass plate used for the multilayer glass of this invention is not specifically limited, For example, the glass plate used for a building material and a vehicle can be used.
Specific examples include glass, float plate glass, mold plate glass, heat ray reflective glass, netted plate glass, heat ray absorbing plate glass, low radiation glass (Low-E glass), tempered glass, and organic glass. Moreover, the thickness of glass is not specifically limited.

  The primary sealing material used for the multilayer glass of the present invention is not particularly limited, and for example, a butyl rubber hot melt, a low moisture permeability material, or the like can be used. From the viewpoint of low gas permeability, a butyl rubber system is preferred.

  The multilayer glass of the present invention is not particularly limited for its production. For example, after installing a spacer between two parallel glass plates fixed to a machine, extruding a primary sealing material with a nozzle or the like connected to an extruder, and then bonding the composition of the present invention with an extruder. It can be manufactured by providing a secondary sealing material by extrusion. 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 addition, the composition of the present invention and the adhesive are directly put into the periphery of the glass plate using an extruder so that an adhesive is provided between the glass, the spacer and the primary sealant and the composition of the present invention. Can be co-extruded.

  Since the multilayer glass of the present invention uses the composition of the present invention as a secondary sealant, even when the amount of the curing agent to the substrate is partially reduced due to poor kneading or the like, it has good adhesiveness. Can be maintained.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
(Examples 1-9 and Comparative Examples 1-11)
Each component of the following Table 1 is mixed using a stirrer with the composition (parts by mass) shown in Table 1 to prepare each base component and curing agent component shown in Table 1, respectively. A secondary sealing material composition for double-glazed glass was obtained.

  The pot life and curability of the secondary sealing agent composition for multilayer glass obtained above were evaluated by the methods shown below using the test specimens shown below.

(1) Pot life The pot life (minutes) was measured by the snap-up method.
Specifically, a base material component and a curing agent component were mixed in a room at 20 ° C. and 65% RH to prepare each secondary sealing material composition for double-glazed glass and put in a 100 cc cup.
Next, the composition in the cup was scooped up using a wooden spatula having a length of 5 cm, and the time when the composition became torn without pulling the yarn was measured as the pot life.

(2) Curability Evaluation of curability was made after preparing a secondary sealing material composition for double-glazed glass, after standing for 3 hours at 20 ° C. and after standing at 20 ° C. for 7 days. The hardness ratio to the final hardness (3 hour hardness / final hardness) was measured.
Here, the hardness was measured according to JIS K6253: 2006 "Type A durometer hardness test".
Specifically, an aluminum container (depth 12 mm × width 26 mm × length 100 mm) is excessively injected with the secondary sealing material composition for each double-glazed glass, and the surface is flattened with a spatula. After that, what was cured for 3 hours and 7 days in an environment of 20 ° C. and 65% RH was used as a test piece.
Next, a hardness meter was pressed vertically against the test piece with a load of 1 kg, and the value after 5 seconds was measured.
As a result, if the 3-hour hardness is 25 or more and the hardness ratio is 50% or more, it can be evaluated that the curability is excellent.

Each component in Table 1 is as follows.
<Base material component>
Polybutadiene polyol: Hydroxyl group-terminated liquid polybutadiene, Poly bd R-45HT, manufactured by Idemitsu Kosan Co., Ltd., viscosity (JIS K2283) 16 Pa · s / 10 ° C., 5 Pa · s / 30 ° C. and 2 Pa · s / 50 ° C., containing hydroxy groups 0.83 mol / kg, hydroxy group value 46.6 mg KOH / g, number average molecular weight 2,800
・ Plasticizer: Diisononyl phthalate, DINP, manufactured by J Plus Co. ・ Calcium carbonate 1: Surface-treated colloidal calcium carbonate, Calfine 200M, manufactured by Maruo Calcium Co. ・ Calcium carbonate 2: Heavy calcium carbonate, Super SS, manufactured by Maruo Calcium Anti-aging agent: Tinuvin 327, manufactured by Ciba Specialty Chemicals Co., Ltd. Amine catalyst: Triethylenediamine (Methyl Dubco, manufactured by Air Products Japan)
・ Tin catalyst 1: StanBL (manufactured by Sansha Co., Ltd.)
-Tin catalyst 2: Scat4A (manufactured by Sansha Co., Ltd.)
Tin catalyst 3: Scat27 (manufactured by Sansha Gosei Co., Ltd.)
Tin catalyst 4: Scat1 (manufactured by Sansha Gosei Co., Ltd.)
Bismuth compound: Neostan U-660 (manufactured by Nitto Kasei Co., Ltd.)

<Curing agent>
Polyisocyanate compound 1: Polymeric MDI, PAPI-135, manufactured by Dow Chemical Japan Co., Ltd. Silane coupling agent: γ-glycidoxypropyltrimethoxysilane, SILQUEST A187, manufactured by Momentive Plasticizer: diisononyl phthalate, DINP, Made by J Plus ・ Carbon black: MA600, made by Mitsubishi Chemical

  As is apparent from Table 1, the compositions of Examples 1 to 9 in which the amine catalyst and the tin catalyst are used in combination at a specific amount have a pot life of 20 minutes or more and a 3 hour hardness of 25 or more. Since the ratio (3 hour hardness / final hardness) was 50% or more, it was found that the balance of pot life and curability was excellent.

FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the multilayer glass of the present invention.

Explanation of symbols

1 Secondary sealing material 2 Desiccant (Hygroscopic material)
3 Spacer 5 Glass plate 7 Primary sealing material 9 Hollow layer 10 Double layer glass

Claims (3)

A secondary sealant composition for double-glazed glass containing a polybutadiene polyol and a polyisocyanate compound,
0.01 to 2 parts by mass of an amine catalyst with respect to 100 parts by mass of the polybutadiene polyol,
0.0001 to 0.1 parts by mass of a tin catalyst with respect to 100 parts by mass of the polybutadiene polyol,
The secondary sealing material composition for multilayer glass whose content of the said tin catalyst is 1-30 mass% with respect to the mass of the said amine catalyst.   The secondary sealing material composition for multilayer glass of Claim 1 which contains a filler 300-500 mass parts with respect to 100 mass parts of said polybutadiene polyols.   Multi-layer glass using the secondary sealant composition for multi-layer glass according to claim 1 or 2 as a secondary sealant.

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