JP4862272B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition and a sealing agent for multi-layer glass using the same.

  In recent years, in order to maintain the temperature in the room or the interior of a vehicle, a double-glazed glass excellent in heat insulation has been attracting attention in the field of construction, vehicle manufacturing such as automobiles, etc. Polysulfide type, silicone type, polybutadiene urethane type and hot melt type are generally used.

  However, although polysulfide-based sealants have a high tolerance for fluctuation in the mixing ratio of the main agent and the curing agent, due to variations in the raw material of manganese dioxide used as the curing agent and the catalytic function depending on the manufacturing method, the curing characteristics and adhesion to glass In particular, the hot water resistant adhesiveness may be inferior. Further, although the silicone-based sealant is excellent in weather resistance, the water-resistant adhesion to glass is insufficient. Polybutadiene urethane-based sealants have good water-resistant adhesion to glass, but have low tolerance for the mixing ratio of the main agent and curing agent, and it is difficult to adjust the balance between pot life and hardness expression. In addition, since the isocyanate contained as a curing agent component is sensitive to moisture, the isocyanate may be cured inside the discharger, and there is a problem that the maintainability of the discharger is poor. In addition, hot-melt sealants are known to have poor heat resistance and weather-resistant adhesiveness due to temperature changes, and have problems with tolerance and reliability with respect to the type of glass and the degree of cleaning of the first glass surface. (For example, refer to Patent Documents 1 to 3.)

JP-A-11-209539 JP-A-11-209736 JP 2002-38128 A

  Accordingly, the present invention provides a curable resin composition having an excellent balance between pot life and hardness expression, and excellent adhesion to glass, particularly hot water-resistant adhesion, and a sealing agent for multilayer glass comprising the curable resin composition. It is an issue to provide.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that a polybutadiene having an acid anhydride group, a latent amine curing agent, and two silane coupling agents having a specific substituent are included. The present invention has been completed by discovering that the functional resin composition has an excellent balance between pot life and hardness development and excellent resistance to hot water with glass.
That is, this invention provides the curable resin composition shown to the following (1) and (2), the sealing compound for multilayer glass shown to (3), and the multilayer glass shown to (4)-(6). Is.

(1) Polybutadiene having an acid anhydride group, a latent amine curing agent, a silane coupling agent (A) having an acid anhydride group and an alkoxysilyl group, and a silane cup having a latent amino group and an alkoxysilyl group A curable resin composition containing a ring agent (B),
1 to 100 parts by mass of the latent amine curing agent is contained with respect to 100 parts by mass of the polybutadiene, and the total of the silane coupling agent (A) and the silane coupling agent (B) is 0.1 to 100 parts by mass. A curable resin composition containing 10.0 parts by mass , wherein the latent amine curing agent is a ketimine compound or an oxazolidine compound .

  (2) The curable resin composition according to the above (1), wherein the acid anhydride group of the polybutadiene and / or the silane coupling agent (A) is a maleic anhydride group.

  (3) A sealing agent for multi-layer glass comprising the curable resin composition according to (1) or (2).

(4) Two or more glass plates are arranged to face each other via a spacer so as to form a hollow layer, and a primary sealant is filled between the spacer and the glass plate, and the peripheral edge portion of the glass plate and the spacer A double-layer glass in which a secondary sealant is filled in a recess formed by the outer peripheral part of
Multi-layer glass wherein the secondary sealant is the multi-layer glass sealant described in (3) above.

  (5) The multilayer glass according to (4), wherein the spacer is formed of metal or resin, and the primary sealant is formed of a butyl sealer.

  (6) The compound described in (4) or (5) above, wherein the glass plate is any one of float glass, template glass, netted glass, heat ray reflective glass, and glass coated with a titanium oxide photocatalyst. Layer glass.

  As will be described below, according to the present invention, it is possible to provide a curable resin composition that has an excellent balance between pot life and hardness development, and has excellent adhesion to glass, particularly excellent resistance to hot water. In addition, the sealing agent for multi-layer glass comprising this curable resin composition is excellent in workability and excellent in resistance to hot water with glass, as well as easy in moisture management and discharger maintenance. Very useful.

The present invention is described in detail below.
The curable resin composition according to the first aspect of the present invention (hereinafter also simply referred to as “the composition of the present invention”) includes a polybutadiene having an acid anhydride group, a latent amine curing agent, and an acid anhydride. A curable resin composition containing a silane coupling agent (A) having a group and an alkoxysilyl group, and a silane coupling agent (B) having a latent amino group and an alkoxysilyl group, the polybutadiene having a mass of 100 mass 1 to 100 parts by mass of the latent amine curing agent with respect to parts, and the total of the silane coupling agent (A) and the silane coupling agent (B) is 0.1 to 10.0 mass. Part of a curable resin composition.
Next, polybutadiene, a hydrogen group-containing compound, a silane coupling agent (A) and a silane coupling agent (B) used in the composition of the present invention will be described in detail.

<Polybutadiene>
The polybutadiene used in the present invention is not particularly limited as long as it is a polybutadiene having an acid anhydride group (hereinafter also referred to as “acid anhydride-modified polybutadiene”).
Here, the acid anhydride group refers to a substituent having a structure (R—CO—O—CO—R) obtained by dehydration condensation of two molecules of carboxylic acid, and polybutadiene having such an acid anhydride group. Examples thereof include those formed by introducing a carboxylic acid anhydride (for example, phthalic anhydride, maleic anhydride, etc.) directly or via an organic group into the main chain and / or side chain of polybutadiene. In this specification, for example, an acid anhydride group formed by introducing maleic anhydride is referred to as a maleic anhydride group, and the same applies to acid anhydride groups derived from other carboxylic acid anhydrides.
Of these, polybutadiene having a maleic anhydride group (maleated polybutadiene) is preferable because of high reactivity with the latent amine curing agent described later.

  In the present invention, the acid anhydride group is formed by introducing phthalic anhydride or maleic anhydride directly or through an organic group into the main chain and / or side chain of polybutadiene. The introduction method is not particularly limited, and can be introduced by an ene reaction between unsaturated double bonds.

  The number average molecular weight of the polybutadiene used in the present invention is preferably 500 to 10,000. When the number average molecular weight is in this range, the viscosity before curing of the composition of the present invention containing such polybutadiene does not increase so much, so that the workability is not adversely affected and the glass or the like is deposited. It is preferable because wettability to the body can be secured and good adhesiveness is expressed.

  Moreover, it is preferable that the introduction rate (addition ratio) of the acid anhydride group with respect to the polybutadiene used for this invention is 0.5-10.0 (mol / mol). When the rate of introduction of the acid anhydride group is 0.5 (mol / mol) or more, crosslinking is sufficiently formed at the time of curing, resulting in a rubber-like cured product, and 10.0 (mol / mol) or less. The modulus of the cured product becomes good, and the composition of the present invention containing such polybutadiene is preferable because it exhibits good properties as a sealing agent for double-glazed glass.

  In the present invention, a commercially available product may be used as the acid anhydride-modified polybutadiene, and specific examples thereof include PolyvestOC 800 (manufactured by Degussa) used in Examples described later and Colnova MAH-1 (manufactured by Nippon Cima). Etc.

<Latent amine curing agent>
The latent amine curing agent used in the present invention is a curing agent for the acid anhydride-modified polybutadiene, and specific examples thereof include the following ketimine compounds and oxazolidine compounds.

  The ketimine compound suitably used as the latent amine curing agent is a compound having a ketimine bond derived from a ketone or aldehyde and an amine. Therefore, in this specification, a ketimine compound is used in the meaning including aldimine having a —HC═N bond.

  As the ketone or aldehyde used for the synthesis of the ketimine compound, widely known ones can be used. Specifically, for example, acetone, methyl ethyl ketone (MEK), diethyl ketone, methyl isobutyl ketone (MIBK), methyl-t-butyl ketone (MTBK), methyl isopropyl ketone (MIPK), diisopropyl ketone, methyl cyclohexyl ketone, cyclohexanone, methyl Examples include cyclohexanone, methyl amyl ketone, ethyl amyl ketone, propiophenone, benzophenone, acetophenone, benzaldehyde, and pivalaldehyde.

  In addition, as the amine compound that can be used as a raw material for the synthesis of the ketimine compound, widely known compounds can be used. Specifically, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2 -Diaminopropane, iminobispropylamine, methyliminobispropylamine, polyamidoamine, isophoronediamine, 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2 -Methylpropyl) piperazine, polyether polyol (PPG) having a primary amino group bonded to the terminal, 1,5-diamino-2-methylpentane, metaxylenediamine (MXDA), 1,3- Scan aminomethyl cyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl - cyclohexylamine, and the like diamines norbornane skeleton.

A widely known method can be used as a method for producing such a ketimine compound. Specifically, for example, a method in which a ketone compound and an amine compound are heated to reflux in the absence of a solvent or in the presence of a nonpolar solvent such as benzene, toluene, xylene, and the like, and the reaction is performed while removing water as a byproduct. Can be mentioned. When the amine compound used for the synthesis of the ketimine compound is a polyamine, the aldehyde or ketone compound bonded to the amino group may be the same or different from each other.
Moreover, such a ketimine compound may be used individually by 1 type, and may be used together 2 or more types.

  The oxazolidine compound suitably used as a latent amine curing agent is a compound having a saturated 5-membered heterocyclic ring containing oxygen and nitrogen and having an oxazolidine ring that opens in the presence of moisture (water). A compound. Specific examples include N-hydroxyalkyl oxazolidine and its polyisocyanate adduct, oxazolidine silyl ether, carbonate oxazolidine, ester oxazolidine, and the like. These may be used alone or in combination of two or more.

  The composition of the present invention containing such a latent amine curing agent has improved adhesion to glass (particularly hot water resistance) due to the carboxy group generated after reaction with an acid anhydride group, Storage stability is high because the reactivity with moisture is lower than that of isocyanate. Furthermore, the tolerance for the mixing ratio of polybutadiene having an acid anhydride group and latent amine curing agent is large (adhesion performance is stable). ), Excellent balance of pot life and hardness expression, and the amino group from which the latent amine curing agent is unblocked is an alkoxysilyl group of the silane coupling agent (A) and (B) described later and the glass surface. It has the advantage of increasing the reactivity.

In the present invention, a commercial product may be used as the latent amine curing agent.
Specific examples of the ketimine compound include EpiCure H-3 and EpiCure H-30 manufactured by Japan Epoxy Resin; HOK-01 manufactured by Toyo Gosei Kogyo; S340 manufactured by Chisso; Jeffermin D230 manufactured by Sun Techno Chemical Co., and Jeffer Min D400, Jeffermin D2000, Jeffermin EDR148; MPMD manufactured by DuPont Japan; X2000 manufactured by Sanwa Chemical; Sanmide 3155; 1,3BAC manufactured by Mitsubishi Gas Chemical; NBDA manufactured by Mitsui Chemicals; Asahi Denka Kogyo ADEKA HARDNER EH235G, EH235R, EH235R-2, EH235R-2S, EH235X;
Specific examples of the oxazolidine compound include MS-PLUS manufactured by ANGUS, Hardener OZ manufactured by Bayer.

  Moreover, in this invention, content of the said latent amine hardening | curing agent is 1-100 mass parts with respect to 100 mass parts of said acid anhydride modified polybutadiene, It is preferable that it is 5-50 mass parts, More preferably, it is 15-40 mass parts.

<Silane coupling agent (A)>
The silane coupling agent (A) used in the present invention is a silane coupling agent having an acid anhydride group and an alkoxysilyl group.
Here, the acid anhydride group is a substituent having a structure (R—CO—O—CO—R) obtained by dehydration condensation of two molecules of carboxylic acid, similar to that described in the acid anhydride-modified polybutadiene. Say.
In addition, the alkoxysilyl group is a silicon-containing group that can be crosslinked by forming a siloxane bond by causing a condensation reaction by using a catalyst or the like, if necessary, in the presence of moisture or a crosslinking agent. It refers to the substituent represented by the formula (1).

（式中、Ｒ¹およびＲ²はそれぞれ独立に炭素数１〜８の分岐していてもよいアルキル基であり、ｎは０〜２の整数である。また、複数のＲ¹またはＲ²はそれぞれ同一であっても異なっていてもよい。）

(In the formula, R ¹ and R ² are each independently an optionally branched alkyl group having 1 to 8 carbon atoms, and n is an integer of 0 to 2. In addition, a plurality of R ¹ or R ² are Each may be the same or different.)

Specific examples of the optionally branched alkyl group having 1 to 8 carbon atoms of R ¹ and R ² include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Examples include s-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, etc. The group may contain a double bond or a triple bond. Of these, a methyl group, an ethyl group, and a propyl group are preferable from the viewpoint of easy availability of raw materials.
As such an alkoxysilyl group represented by the general formula (1), specifically, a group represented by the following formula is suitably exemplified.

  The silane coupling agent (A) used in the present invention is not particularly limited as long as it is a silane coupling agent having the above acid anhydride group and the above alkoxysilyl group, and specific examples thereof are anhydrous as an acid anhydride group. Preferable examples include compounds represented by the following formulas (2) to (4) having a maleic acid group and having a methyldimethoxysilyl group, a trimethoxysilyl group or a triethylsilyl group as an alkoxysilyl group.

  In the present invention, a commercial product may be used as the silane coupling agent (A), and specific examples thereof include GF20 (manufactured by Wacker Chemical Co., etc.) used in Examples described later.

<Silane coupling agent (B)>
The silane coupling agent (B) used in the present invention is a silane coupling agent having a latent amino group and an alkoxysilyl group.
Here, the latent amino group refers to an amino group in which active hydrogen is blocked by introduction of an amino-protecting group, and specific examples thereof include ketimines derived from ketones or aldehydes and amines ( Preferable examples include C = N) group.
The alkoxysilyl group is a substituent represented by the general formula (1) as described in the silane coupling agent (A).

  The silane coupling agent (B) used in the present invention is not particularly limited as long as it is a silane coupling agent having the latent amino group and the alkoxysilyl group, and is a ketimine silane compound represented by the following general formula (5). Is preferably exemplified.

（式中、Ｒ¹およびＲ²はそれぞれ独立に炭素数１〜８の分岐していてもよいアルキル基であり、Ｒ³は炭素数１〜１２の二価の有機基であり、Ｒ⁴およびＲ⁵は、それぞれ独立に炭素数１〜１２の一価の有機基であり、ｎは０〜２の整数である。また、複数のＲ¹またはＲ²はそれぞれ同一であっても異なっていてもよい。）

(In the formula, R ¹ and R ² are each independently an optionally branched alkyl group having 1 to 8 carbon atoms, R ³ is a divalent organic group having 1 to 12 carbon atoms, R ⁴ and R ⁵ is each independently a monovalent organic group having 1 to 12 carbon atoms, and n is an integer of 0 to 2. In addition, a plurality of R ¹ or R ² may be the same or different. May be good.)

R ¹ and R ² are basically the same as those described in the general formula (1).
R ³ is a divalent organic group having 1 to 12 carbon atoms, and preferably an alkylene group having 2 to 6 carbon atoms. Specific examples of such R ³ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and an octamethylene group. Is more preferable from the viewpoint of superiority.
R ⁴ and R ⁵ are each independently a monovalent organic group having 1 to 12 carbon atoms, and are each independently a monovalent organic group having 1 to 6 carbon atoms (aliphatic group, alicyclic group, aromatic group) Group), more preferably each independently an alkyl group having 1 to 6 carbon atoms. Preferred examples of R ⁴ and R ⁵ include the alkyl groups exemplified for R ¹ and R ² .

  Here, as the ketimine silane compound represented by the general formula (5), specifically, for example, N- (1,2-dimethylpropylidene) -3- (trimethoxysilyl) -1-propanamine, N- (1,2-dimethylpropylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,2-dimethylpropylidene) -3- (methyldimethoxysilyl) -1-propanamine, N- (1,2-dimethylpropylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxysilyl) ) -1-propane amine, N-(1,3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-propanamine, and the like.

  In the present invention, a commercially available product may be used as the silane coupling agent (B), and specific examples thereof include S340 (manufactured by Chisso Corporation) used in examples described later, and KBE-9103 (Shin-Etsu Chemical Co., Ltd.). Manufactured) and the like.

  The composition of the present invention containing both such silane coupling agents (A) and (B) is excellent in adhesiveness to glass, in particular, hot water-resistant adhesiveness. This is because the silanol group obtained by hydrolysis of the alkoxysilyl group expresses adhesion to glass, while the acid anhydride group of the silane coupling agent (A) is a polybutadiene having an acid anhydride group. This is considered to be due to the strong adhesiveness between the entire composition and the glass through the bonding of.

  In the present invention, the total content of the silane coupling agent (A) and the silane coupling agent (B) is 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the acid anhydride-modified polybutadiene. It is preferably 0.2 to 5.0 parts by mass, more preferably 0.3 to 3.0 parts by mass, and particularly preferably 0.5 to 2.0 parts by mass.

In one preferred embodiment, the composition of the present invention further contains an amine compound other than the latent amine curing agent.
Specific examples of amine compounds include butylamine, hexylamine, octylamine, dodecylamine, oleylamine, ethylenediamine, propylenediamine, 1,2-diaminopropane, butylenediamine, diethylenetriamine, triethylenetriamine, and triethylenetetramine. Chain aliphatic amines such as tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, guanidine, cyclohexylamine, Triethylenediamine, morpholine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] -7-unde , Isophorone diamine, 1,3-bisaminomethylcyclohexane, N-aminoethylpiperazine, 3,3-dimethyl-4,4-diaminodicyclohexylmethane, mensendiamine, isophorone diamine, S Cure 211 manufactured by Iron & Chemicals , S Cure 212, 4,4-diaminodicyclohexylmethane, cycloaliphatic amines such as 1,3-bisaminomethylcyclohexane, and benzylamine, m-xylenediamine, Showamin X manufactured by Showa Denko KK, amine black, Aliphatic amines such as fatty aromatic amines such as Shawamine Black, Shawamine N, Shawamine 1001, Shawamine 1010;
aromatic amines such as m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diphenylguanidine;
Amine adducts (polyamine epoxy resin adducts), polyamine-ethylene oxide adducts;
Dibutylamine, benzyldimethylamine, diethanolamine, triethanolamine, tetramethylguanidine, N, N, N ', N'-tetramethyl-1,6-hexamethylenediamine, 2,4,6-tris (dimethylaminomethyl) Secondary or tertiary amines such as phenol, piperidine, pyridine;
Carboxylates of these amine compounds;
A polyamidoamine obtained by reacting dimer acid with a polyamine such as diethylenetriamine or triethylenetetramine;
Quaternary ammonium salts such as benzyltriethylammonium acetate; and the like.
These may be used alone or in combination of two or more.

  Among these, it is preferable to use a tertiary amine because the balance of the pot life and the expression of hardness of the obtained composition of the present invention is further improved.

  The content of the amine compound is preferably 1.0 to 3.0 parts by mass with respect to 100 parts by mass of the acid anhydride-modified polybutadiene.

In one preferred embodiment, the composition of the present invention contains calcium carbonate.
The calcium carbonate used in the present invention is not particularly limited, and examples thereof include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), and colloidal calcium carbonate.
Moreover, the surface treatment calcium carbonate surface-treated with a fatty acid, a resin acid, a fatty acid ester, a higher alcohol addition isocyanate compound, etc. can also be used. Specifically, as calcium carbonate surface-treated with a fatty acid, whiten 305 (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), white gloss flower CCR (colloidal calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd.), Calfine 200 (colloidal calcium carbonate) , Maruo Calcium Co., Ltd.), Calfine 500 (Colloidal Calcium Carbonate, Maruo Calcium Co., Ltd.), calcium carbonate surface-treated with a modified fatty acid, Ryton A-4 (heavy calcium carbonate, manufactured by Bihoku Flour Industries Co., Ltd.), Ryton 26A (heavy calcium carbonate, manufactured by Bihoku Flour & Chemical Co., Ltd.), calcium carbonate surface-treated with fatty acid ester, Snowlite SS (heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.), Sealets 200 (colloidal calcium carbonate, Maruo) Calcium) and the like are preferably used. Of these, those surface-treated with fatty acids, modified fatty acids, fatty acid esters, higher alcohol-added isocyanate compounds, and the like are particularly preferable. The surface-treated calcium carbonate contributes to shape retention and workability because the viscosity is increased, and contributes to storage stability because the surface is hydrophobic.
These may be used alone or in combination of two or more.

  The content of calcium carbonate is preferably 50 to 400 parts by mass with respect to 100 parts by mass of the acid anhydride-modified polybutadiene (A).

  The composition of the present invention can contain various additives as necessary in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of additives include fillers other than calcium carbonate, plasticizers, softeners, thixotropy imparting agents, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion imparting agents, and dispersions. Agents, solvents, antibacterial and antifungal agents.

  As fillers other than calcium carbonate, those having various shapes can be used. For example, calcium carbonate; fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; Examples include kaolin clay, calcined clay; organic or inorganic fillers such as carbon black; these fatty acids, resin acids, fatty acid ester-treated products, and fatty acid ester urethane compound-treated products.

  Examples of the plasticizer or softener include diisononyl phthalate (DINP), dioctyl phthalate, dibutyl phthalate; dioctyl adipate, isodecyl succinate; diethylene glycol dipenzoate, pentaerythritol ester; butyl oleate, acetylricinoleic acid Examples include methyl; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol polyester adipate; petroleum softeners such as paraffinic oil, naphthenic oil, and aroma oil.

Examples of the thixotropic property-imparting agent include dry silica, white carbon, hydrogenated castor oil, calcium carbonate, and Teflon (registered trademark).
Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride and sulfate; organic pigments such as azo pigments and copper phthalocyanine pigments. It is done.

Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.
The above additives can be used in combination as appropriate.

  The method for producing the composition of the present invention containing each of these components is not particularly limited, but each of the above components is stirred under a reduced pressure or an inert gas atmosphere such as nitrogen using a mixing device such as a mixing mixer. A method of sufficiently kneading and uniformly dispersing is preferable.

Further, the composition of the present invention is moisture curable and can be used as a one-component composition. Further, if necessary, the acid anhydride-modified polybutadiene and the silane coupling agent (A) are used as the main component (liquid A), and the latent amine curing agent, the silane coupling agent (B) and optionally contained. It can also be used as a two-component composition using an amine compound or the like that can be cured as a curing agent component (liquid B).
When the composition of the present invention is exposed to moisture, the curing reaction proceeds by hydrolysis of the alkoxysilyl groups in the silane coupling agents (A) and (B). In addition, the curing reaction can be advanced by appropriately supplying water.

The sealing agent for multilayer glass according to the second aspect of the present invention (hereinafter also simply referred to as “the sealing agent for multilayer glass of the present invention”) is a curable resin composition according to the first aspect of the present invention. It is the sealing compound for multilayer glass consisting of.
As described above, the sealing agent for double-glazed glass of the present invention is excellent in adhesiveness with glass, particularly hot water-resistant adhesive, so that the glass plates constituting the double-glazed glass are interposed via a spacer. It is very useful because it can adhere well, and can maintain sufficient adhesion even in summertime at high temperatures and high humidity.

  The multi-layer glass according to the third aspect of the present invention (hereinafter also simply referred to as “multi-layer glass of the present invention”) is disposed opposite to each other with a spacer so that two or more glass plates form a hollow layer. A multi-layer glass in which a primary sealant is filled between the spacer and the glass plate, and a concave seal formed by a peripheral portion of the glass plate and an outer peripheral portion of the spacer is filled with a secondary sealant. Then, the secondary sealant is a multilayer glass that is the multilayer glass sealant according to the second aspect of the present invention described above.

Here, an example of a preferred embodiment of the multilayer glass of the present invention will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view showing an example of the multilayer glass of the present invention.
As shown in FIG. 1, the double-glazed glass 10 has two glass plates 1 facing each other with a spacer 5 therebetween, and a hollow layer (air layer) 2 is formed between the glass plates 1. The primary sealing agent 3 is interposed between the plate 1 and the hollow layer 2 is cut off from the outside air. Further, in the gap at the end surrounded by the spacer 5, the primary sealing agent 3 and the opposing glass plate 1, It has a structure in which the sealing agent for multilayer glass of the present invention is provided as the secondary sealing agent 4.

In the present invention, the spacer is preferably formed of metal or resin. Specifically, the spacer is formed by bending a metal such as aluminum and is filled with a hygroscopic agent such as molecular sieve. It is preferably a metal spacer or a resin spacer formed of a resin described later.
The resin is preferably a thermoplastic resin, specifically, a polyolefin resin (for example, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), High molecular weight polyethylene (UHMWPE), isotactic polypropylene, syndiotactic polypropylene, ethylene propylene copolymer resin); polyamide resins (for example, nylon 6 (N6), nylon 6,6 (N6,6), nylon 4, 6 (N4,6), nylon 11 (N11), nylon 12 (N12), nylon 6,10 (N6,10), nylon 6,12 (N6,12), nylon 6 / 6,6 copolymer (N6 / 6,6), nylon 6 / 6,6 / 6,10 copolymer (N6 / 6,6 / 6,10), Niro MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 6,6 / PP copolymer, nylon 6,6 / PPS copolymer); polyester resin (for example, polybutylene terephthalate (PBT), Aromatic polyesters such as polyethylene terephthalate (PET); polyether resins (for example, polyphenylene oxide (PPO), modified polyphenylene oxide (modified PPO), polysulfone (PSF), polyether ether ketone (PEEK)); Resin (for example, polymethyl methacrylate (PMMA), polyethyl methacrylate); polyvinyl resin (for example, vinyl alcohol / ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), vinylidene chloride / methyl acrylate) Fluorine resin (for example, polyvinylidene fluoride (PVDF), polychlorofluoroethylene (PCTFE)), polyacrylonitrile resin (PAN), etc. It may be used.

  Among these, when used as a spacer of a double-glazed glass, the heat distortion temperature against the outside air temperature is good, and the heat distortion temperature is 50 ° C. or higher in terms of suppressing a decrease in water vapor permeability due to water absorption. Polyolefin resins, polyester resins, polyether resins, and fluorine resins are preferable.

The resin may be a resin-containing composition (resin composition). Specifically, the thermoplastic resin exemplified above and an unvulcanized rubber component (for example, natural rubber (NR)) , Isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), ethylene-propylene -A thermoplastic resin composition obtained by vulcanization while kneading with diene rubber (EPDM), ethylene-propylene rubber (EPM) or the like, that is, dynamic vulcanization, is preferably exemplified.
Such a resin composition may contain various additives exemplified in the composition of the present invention, and particularly preferably contains a hygroscopic agent such as a molecular sieve.

  In the present invention, the primary sealant is not particularly limited as long as it is a conventionally known one, but it is preferably formed of an extruded sealant mainly composed of butyl rubber or polyisobutylene (PIB), and mainly composed of butyl rubber. More preferably, it is formed by a butyl sealer which is an extruded sealant.

  In the present invention, the glass plate is not particularly limited, but is preferably any one of float glass, template glass, netted glass, heat ray reflective glass, and glass coated with a titanium oxide photocatalyst. .

  The method for producing the multilayer glass of the present invention is not particularly limited. For example, when the multilayer glass 10 shown in FIG. 1 is produced, first, the spacer 5 is disposed between the opposing glass plates 1 to form the glass. The width between the plates 1 is set at a predetermined interval, and the primary sealant 3 is placed to bond the glass plate 1 and the spacer 5 together. After bonding, the secondary sealant 4 can be produced by placing the secondary sealant 4 in the gap at the end surrounded by the opposing glass plate 1, the primary sealant 3 and the spacer 5.

  Since the double-glazed glass of the present invention uses the above-mentioned sealing agent for double-glazed glass of the present invention as a secondary sealant, the adhesive strength is very high, moisture permeation can be prevented, and in a humid environment. In this case, the glass plate becomes a multi-layer glass from which the glass film does not fog from the hollow membrane side.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
(Examples 1-4, Comparative Examples 1-7)
Each component shown in Table 1 below was mixed and dispersed using the stirrer with the composition (parts by mass) shown in Table 1 to obtain each curable resin composition shown in Table 1. In Comparative Example 5, a polysulfide sealant (SM8000 / B800, manufactured by Yokohama Rubber Co., Ltd.) was used, and in Comparative Example 6, a two-component liquid mainly composed of an isocyanate prepolymer and a polyol having an unsaturated double bond as a skeleton. Type double-layer glass sealant, which usually contains an inorganic filler such as calcium carbonate, an adhesion-imparting agent, and uses a urethane-based sealant obtained by kneading these appropriately. The same evaluation was performed using a sealant (IGS203A / B, manufactured by San Yulec).

<Adhesiveness>
(1) Normal adhesiveness The obtained curable resin composition was filled in a float glass assembled in an H shape, and cured at 20 ° C. for 3 days and at 50 ° C. for 3 days to prepare an H type specimen.
Using the produced H-shaped test specimen, a peel test was performed on the adhesive surface in which two glass plates were pulled vertically at a tensile speed of 50 mm / min in accordance with JIS A1439-1997, and the tensile strength (N / cm ² ) was measured, and the fracture form of the peeled surface was visually confirmed. The results are shown in Table 1 below. In Table 1, the peeled state is indicated by CF (cohesive failure) and AF (interface peeling).

(2) Warm water resistance (after 14 days at 80 ° C.) Adhesiveness The H-type specimen prepared in the normal adhesion test was immersed in warm water at 80 ° C. for 14 days and then left at 20 ° C. for 1 day.
A peel test similar to normal adhesiveness was performed using the test specimen after standing, the tensile strength (N / cm ² ) at the time of peeling was measured, and the fracture form of the peeled surface was visually confirmed. The results are shown in Table 1 below.

(3) Warm water resistant (after 90 days at 90 ° C.) Adhesiveness The H-type specimen prepared in the normal adhesion test was immersed in warm water at 90 ° C. for 14 days, and then left at 20 ° C. for 1 day.
A peel test similar to normal adhesiveness was performed using the test specimen after standing, the tensile strength (N / cm ² ) at the time of peeling was measured, and the fracture form of the peeled surface was visually confirmed. The results are shown in Table 1 below.

The components shown in Table 1 are as follows.
Acid anhydride-modified polybutadiene 1: Polybest OC800, manufactured by Degussa Co., Ltd. Latent amine curing agent 1: Sanmide 3155, manufactured by Sanwa Chemical Co., Ltd. Silane coupling agent A1: GF20, Wacker Chemical Co. Silane coupling agent B1: S340, Made by Chisso ・ Epoxy silane: A187, made by Nihon Unicar ・ Isocyanate silane: A1310, made by Nihon Unicar ・ Plasticizer 1: Diisononyl phthalate (DINP, made by Shin Nippon Rika)
・ Heavy calcium carbonate: Ryton 26A, manufactured by Bihoku Powder Chemical Co., Ltd. ・ Colloidal calcium carbonate: Calfine 500, manufactured by Maruo Calcium

  As is apparent from Table 1, the curable resin compositions of the present invention (Examples 1 to 4) were found to have a high tolerance for the mixing ratio fluctuation of the main agent and the curing agent, and obtained in Comparative Examples 1 to 4. It was found that the hot water-resistant adhesion with glass was superior to the obtained curable resin composition. In addition, it can be seen that the resistance to hot water with glass is equal to or better than the conventional sealants of Comparative Examples 5 to 7 from the viewpoint of strength retention, and in particular, the polysulfide system used in Comparative Example 5 Compared to the sealant, it was found that the adhesive property was excellent in warm water resistance (after 90 ° C. for 14 days).

<Balance between pot life and hardness expression>
FIG. 2 is a viscosity-time showing the balance between the pot life and hardness expression of the curable resin composition obtained in Example 1, the polysulfide sealant used in Comparative Example 5, and the urethane sealant used in Comparative Example 7. It is a graph. The viscosity is an mPas value measured at 20 ° C. and 1 rpm.
From the graph shown in FIG. 2, it can be seen that the curable resin composition obtained in Example 1 has a much better balance between pot life and hardness expression than the urethane sealant used in Comparative Example 7. It was found that the results were almost the same as the polysulfide sealant used in Comparative Example 5.

<Stability of curing agent component over time>
Curing agent containing latent amine curing agent 1, silane coupling agent B1 and plasticizer 1 in Table 1 as a two-component curing agent component in a mass ratio of 40.0: 1.0: 18.0 Ingredient 1 was prepared.
The adjusted curing agent component 1 was allowed to stand for the time shown in Table 2 below, and the change in appearance at that time was visually confirmed to evaluate the stability of the curing agent component over time. The same evaluation was performed for the curing agent component 2 (TDI urethane prepolymer: plasticizer = 40: 5 (mass ratio)) of the urethane sealant used in Comparative Example 6. The results are shown in Table 2 below.

  As is apparent from Table 2, the curing agent component when the curable resin composition of the present invention is used as a two-component type is more stable than the curing agent components used in conventionally known urethane sealants. It turns out that it is excellent, and it turns out that the moisture management at the time of using as a sealing agent and the maintainability of a discharge machine become easy.

FIG. 1 is a schematic cross-sectional view showing an example of the multilayer glass of the present invention. FIG. 2 is a viscosity-time showing the balance between the pot life and hardness expression of the curable resin composition obtained in Example 1, the polysulfide sealant used in Comparative Example 5, and the urethane sealant used in Comparative Example 7. It is a graph.

Explanation of symbols

1 Glass plate 2 Air layer (hollow layer)
3 Primary sealing material 4 Secondary sealing material 5 Spacer 10 Multi-layer glass

Claims (6)

A polybutadiene having an acid anhydride group, a latent amine curing agent, a silane coupling agent (A) having an acid anhydride group and an alkoxysilyl group, and a silane coupling agent having a latent amino group and an alkoxysilyl group ( A curable resin composition containing B),
The latent amine curing agent is contained in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the polybutadiene, and the total of the silane coupling agent (A) and the silane coupling agent (B) is 0.1 to 100 parts by mass. A curable resin composition containing 10.0 parts by mass , wherein the latent amine curing agent is a ketimine compound or an oxazolidine compound .   The curable resin composition according to claim 1, wherein the acid anhydride group of the polybutadiene and / or the silane coupling agent (A) is a maleic anhydride group.   The sealing agent for multilayer glass which consists of a curable resin composition of Claim 1 or 2. Two or more glass plates are arranged to face each other via a spacer so as to form a hollow layer, and a primary sealant is filled between the spacer and the glass plate, and the peripheral portion of the glass plate and the outer peripheral portion of the spacer A double-glazed glass in which a secondary sealant is filled in a recess formed by
Multi-layer glass in which the secondary sealant is the multi-layer glass sealant according to claim 3.   The multilayer glass according to claim 4, wherein the spacer is made of metal or resin, and the primary sealant is made of butyl sealer.   The multilayer glass according to claim 4 or 5, wherein the glass plate is any one of float glass, template glass, netted glass, heat ray reflective glass, and glass coated with a titanium oxide photocatalyst.

Images