WO2019077731A1

WO2019077731A1 - Double glazing and method for manufacturing same

Info

Publication number: WO2019077731A1
Application number: PCT/JP2017/037967
Authority: WO
Inventors: 周浩筬部; 美果森山; 雅秀佐藤
Original assignee: 白石工業株式会社
Priority date: 2017-10-20
Filing date: 2017-10-20
Publication date: 2019-04-25

Abstract

Provided are double glazing and a method for manufacturing the same with which glass sheets can be sealed within a short time without a reduction in strength, coefficient of extension, etc. of a sealing material, and with which efficient production is possible. The double glazing includes: a pair of glass sheets 2, 3 that are provided spaced apart by a predetermined gap therebetween, a spacer 4 that is disposed between the pair of glass sheets 2, 3 at peripheral edges of the pair of glass sheets 2, 3 to maintain the gap and to form an inner space 6 internally; and a sealing material 7 that is provided along an outer side of the spacer 4 and seals between the pair of glass sheets 2, 3. The sealing material 7 comprises a polyurethane resin composition that contains an inorganic filler and contains an alkali metal in a range of 100 to 2000 μg/g.

Description

Double layer glass and method of manufacturing the same

The present invention relates to a multilayer glass and a method of manufacturing the same.

In general, in a double-glazed glass, at least two glass plates are made to face each other via a spacer, and the glass plate and the spacer are closely adhered with an adhesive to form an internal space, and then a sealing material is formed on the outer periphery of the spacer It manufactures by apply | coating and sealing between glass plates (patent document 1 grade | etc.,). As a sealing material, a room temperature curing resin such as a polysulfide resin, a silicone resin, and a polyurethane resin is generally used.

JP 2000-17958 A

The sealing with the conventional sealing material is required for a long time, and in order to improve the productivity, it is necessary to cure the sealing material in a short time. However, conventionally, when the sealing material is cured in a short time, there has been a problem that the strength, the elongation and the like of the sealing material after curing decrease.

An object of the present invention is to provide a multilayer glass capable of sealing between glass plates in a short time without lowering the strength, elongation and the like of a sealing material, and a method of manufacturing the same. It is to do.

The multi-layer glass of the present invention is a pair of glass plates provided at a predetermined distance, and a pair of glass plates to maintain a space at the periphery of the pair of glass plates and to form an internal space inside A spacer disposed between the plates, and a sealing material provided along the outside of the spacer and sealing between a pair of glass plates, the sealing material containing an inorganic filler, in the range of 100 to 2000 μg / g And a polyurethane resin composition containing an alkali metal.

The inorganic filler is preferably calcium carbonate.

The alkali metal is preferably contained as sodium hydroxide.

The method for producing a multilayer glass according to the present invention is a method capable of producing the multilayer glass according to the present invention, wherein an interval is held at the peripheral portion of a pair of glass plates and an inner space is formed inside. For this purpose, the method comprises the steps of disposing a spacer between a pair of glass plates, and applying a sealing material along the outside of the spacer to seal between the pair of glass plates.

ADVANTAGE OF THE INVENTION According to this invention, between the glass plates can be sealed in a short time, without reducing the intensity | strength of a sealing material, elongation rate, etc., and it can manufacture efficiently.

FIG. 1 is a schematic cross-sectional view for explaining a multilayer glass according to an embodiment of the present invention. FIG. 2 is a view showing time-dependent changes in Shore A hardness in Examples and Comparative Examples of the present invention. FIG. 3 is a view showing time-dependent changes in Shore A hardness in Examples and Comparative Examples of the present invention. FIG. 4 is a view showing time-dependent changes in Shore A hardness in Examples and Comparative Examples of the present invention.

Hereinafter, preferred embodiments will be described. However, the following embodiments are merely illustrative, and the present invention is not limited to the following embodiments.

FIG. 1 is a schematic cross-sectional view for explaining a multilayer glass according to an embodiment of the present invention. As shown in FIG. 1, the double glazing 1 of this embodiment includes a pair of

glass plates

2 and 3, a spacer 4 disposed between the pair of

glass plates

2 and 3, and an outer side of the spacer 4. And a sealant 7 provided along the same. The spacer 4 holds the pair of

glass plates

2 and 3 at a predetermined distance at the periphery of the pair of

glass plates

2 and 3 and forms the inner space 6 inside the pair of glass plates It is arranged between 2 and 3. The spacers 4 are attached to the pair of

glass plates

2 and 3 by an adhesive 5 such as butyl rubber, for example. The spacer 4 may contain a desiccant for drying the internal space 6.

The sealing material 7 is provided along the outside of the spacer 4 to seal between the pair of

glass plates

2 and 3. The sealing material 7 in the present embodiment is made of a polyurethane resin composition containing an inorganic filler and containing an alkali metal in the range of 100 to 2000 μg / g.

(Inorganic filler)
As the inorganic filler, for example, calcium carbonate, talc, calcium magnesium carbonate, basic magnesium carbonate, quartz powder, silica powder, finely powdered silica, finely powdered calcium silicate, finely powdered aluminum silicate, kaolin clay, piophyrite clay, Seri Sites, mica, bentonite, nepheline sainite, aluminum hydroxide, magnesium hydroxide, barium sulfate and the like. Among these, calcium carbonate is particularly preferred. Specific examples of calcium carbonate include synthetic calcium carbonate, natural calcium carbonate (heavy calcium carbonate) and the like. The calcium carbonate may be surface-treated calcium carbonate which has been surface-treated with at least one of fatty acids, resin acids and derivatives thereof.

The content of the inorganic filler in the polyurethane resin composition is preferably 10 to 80% by mass, and more preferably 15 to 70% by mass. If the content is too low, the viscosity of the sealing material is low and the workability is poor, and dripping or stringing may occur, which may cause problems in the coating operation. If the content is too high, the viscosity of the sealing material becomes high. It may be too mixed at the time of preparation.

(Alkali metal)
The alkali metal content in the polyurethane resin composition is in the range of 100 to 2000 μg / g, preferably in the range of 150 to 1500 μg / g, and more preferably in the range of 180 to 1200 μg / g. If the alkali metal content is too small, the effect of the present invention that the glass plates can be sealed in a short time without lowering the strength, elongation and the like of the sealing material may not be sufficiently obtained. . If the alkali metal content is too high, an effect proportional to the content may not be obtained.

The alkali metal is preferably at least one of sodium and potassium. The alkali metal is preferably contained in the polyurethane resin composition by containing an alkali metal compound in the polyurethane resin composition. Examples of the alkali metal compound include hydroxides and carbonates of sodium or potassium. Among these, sodium hydroxide and sodium carbonate are preferable as the alkali metal compound. In particular, it is preferable to contain as sodium hydroxide. Only one type of alkali metal compound may be used, or a plurality of types may be used.

The alkali metal compound may be added directly to the polyurethane resin, but in the present invention, it is preferable to add it to the polyurethane resin together with the inorganic filler. For example, it is preferable to dissolve the alkali metal compound in a medium such as water and mix it with the inorganic filler in the form of a solution, and then to dry it to remove the medium, and then add the mixture to the polyurethane resin.

(Polyurethane resin)
The polyurethane resin mainly consists of polyisocyanate and polyol.

As the isocyanate, tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, tolidine diisocyanate (TODI), xylene diisocyanate, hexamethylene diisocyanate and modified products thereof, dicyclohexylmethane diisocyanate (water And MDI), isophorone diisocyanate (IPDI) and the like.

The polyol is not particularly limited as long as it has two or more hydroxy groups. For example, polyether polyols, polyester polyols, other polyols, mixed polyols thereof and the like can be mentioned. Examples of polyether polyols include ethylene oxide, butylene oxide, and poly at least one selected from glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, hexanetriol, trimethylolpropane and the like. The polyol etc. which are obtained by adding at least 1 sort (s) selected from the group which consists of oxy tetramethylene oxide, etc. are mentioned. Specifically, polypropylene ether diol and polypropylene ether triol are exemplified. Moreover, as another polyol, a castor oil type polyol and a polybutadiene type polyol are mentioned. A castor oil-based polyol is a fatty acid ester-based polyol using a glycerin ester of ricinoleic acid as a raw material, and examples thereof include "URIC" manufactured by Ito Oil Co., Ltd. The polybutadiene-based polyol is a polybutadiene type liquid polymer having a hydroxyl group at the molecular terminal, and examples thereof include “poly bd R-15 HT” and “poly bd R 45-HT” manufactured by Idemitsu Kosan Co., Ltd.

The polyurethane resin composition may further contain a plasticizer, a filler and an additive.

As a plasticizer, dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), diheptyl phthalate (DHP), dioctyl phthalate (DOP), diisononyl phthalate (DINP) , Diisonodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butyl benzyl phthalate (BBP), dicyclohexyl phthalate (DCHP), tetrahydrophthalic acid ester, tetrahydrophthalic acid ester, dioctyl adipate (DOA), diisononyl adipate (DINA), adipine Diisodecyl acid (DIDA), di-n-alkyl adipate, dibutyl diglycol adipate (BXA), bis (2-ethylhexyl) azelate (DOZ), dibutyl sebacate (DBS), dioctyl sebacate (DOS), Murray Dibutyl acid (DBM), di-2-ethylhexyl maleate (DOM), dibutyl fumarate (DBF), tricresyl phosphate (TCP), triethyl phosphate (TEP), tributyl phosphate (TBP), tris · (2-ethylhexyl) phosphate (TOP), tri (chloroethyl) phosphate (TCEP), tris dichloropropyl phosphate (CRP), tributoxyethyl phosphate (TBXP), tris (β-chloropropyl) phosphate (TMCPP), triphenyl phosphate (TPP), octyl diphenyl Phosphate (CDP), acetyl triethyl citrate, tributyl acetyl citrate etc. Others include trimellitic acid plasticizer, polyester plasticizer, chlorinated paraffin, stearic acid Further, dimethylpolysiloxane and the like can be mentioned.

Examples of fillers (including thickeners) include inorganic and organic fillers. Examples of the inorganic type include the above-mentioned inorganic fillers, carbon black (furness, thermal, acetylene), graphite, needle-like and fibrous, sepiolite, wollastonite, sonotolite, potassium titanate, carbon fiber, mineral Examples of fibers, glass fibers and balun beads include silas balun, fly ash balun, glass balun, silica beads, alumina beads and glass beads. As organic type, wood flour, walnut powder, cork powder, flour, starch, ebonite powder, rubber powder, lignin, phenol resin, high styrene resin, polyethylene resin, silicone resin, urea resin, cellulose powder in fibrous form, Pulp powder, synthetic fiber powder and the like can be mentioned.

The additives include waxes such as amide wax and castor oil wax.

Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited to the following examples.

<Synthesis of calcium carbonate A to J>
(Calcium carbonate A)
Water was added to 1000 g of synthetic calcium carbonate having a BET specific surface area of 22 m ² / g so that the solid content was 10% by mass, and the mixture was stirred at 40 ° C. to prepare a calcium carbonate slurry.

Next, a 10% by mass aqueous solution of mixed fatty acid sodium salt (manufactured by NOF Corp .; Marcel Soap) was prepared and used as a surface treatment agent solution. This surface treatment agent solution was added to the above-mentioned calcium carbonate slurry to surface treat calcium carbonate. The addition amount of the mixed fatty acid sodium salt is 3.0 parts by mass with respect to 100 parts by mass of calcium carbonate.

Next, the slurry of calcium carbonate treated with fatty acid was dehydrated to obtain a cake having a solid content of 60% by mass. The obtained cake was dried by a drier to obtain surface-treated calcium carbonate A.

The BET specific surface area of the obtained calcium carbonate A was 20.8 m ² / g. In addition, the pH of the obtained calcium carbonate A was 9.2. The pH was measured by adding and dispersing the powder to be measured in distilled water so that the powder to be measured was 5% by mass, and measuring the pH value of the obtained slurry. The following pH was also determined in the same manner.

(Calcium carbonate B)
Water was added to 1000 g of synthetic calcium carbonate having a BET specific surface area of 22 m ² / g so that the solid content was 10% by mass, and the mixture was stirred at 40 ° C. to prepare a calcium carbonate slurry.

Next, to this slurry of calcium carbonate treated with fatty acid, an aqueous solution of sodium hydroxide having a concentration of 2.5 mol / l was added and stirred. Next, the obtained slurry was dewatered to obtain a cake with a solid content of 60% by mass. The obtained cake was dried in a drier to obtain surface-treated calcium carbonate. The addition amount of the sodium hydroxide aqueous solution was adjusted so that the alkali metal content contained in the mixture of surface-treated calcium carbonate and sodium hydroxide after dehydration and drying was 500 μg / g.

The BET specific surface area of the obtained mixture of surface-treated calcium carbonate and sodium hydroxide (hereinafter referred to as “calcium carbonate B”) was 21.0 m ² / g. The pH of calcium carbonate B was 9.8.

(Calcium carbonate C)
Surface-treated calcium carbonate was obtained in the same manner as calcium carbonate B, except that an aqueous solution of sodium hydroxide was added so that the alkali metal content contained in the mixture of surface-treated calcium carbonate and sodium hydroxide would be 1000 μg / g. .

The BET specific surface area of the obtained mixture of surface-treated calcium carbonate and sodium hydroxide (hereinafter referred to as “calcium carbonate C”) was 21.1 m ² / g. The pH of calcium carbonate C was 10.3.

(Calcium carbonate D)
Surface-treated calcium carbonate was obtained in the same manner as calcium carbonate B, except that an aqueous solution of sodium hydroxide was added so that the alkali metal content contained in the mixture of surface-treated calcium carbonate and sodium hydroxide would be 1,500 μg / g. .

The BET specific surface area of the obtained mixture of surface-treated calcium carbonate and sodium hydroxide (hereinafter referred to as “calcium carbonate D”) was 21.1 m ² / g. The pH of calcium carbonate D was 10.6.

(Calcium carbonate E)
Surface-treated calcium carbonate was obtained in the same manner as calcium carbonate B, except that an aqueous solution of sodium hydroxide was added so that the alkali metal content contained in the mixture of surface-treated calcium carbonate and sodium hydroxide would be 2500 μg / g. .

The BET specific surface area of the obtained mixture of surface-treated calcium carbonate and sodium hydroxide (hereinafter referred to as “calcium carbonate E”) was 20.7 m ² / g. The pH of calcium carbonate E was 11.3.

(Calcium carbonate F)
The ground calcium carbonate having a BET specific surface area of 2.6 m ² / g was named calcium carbonate F. The pH was 9.1.

(Calcium carbonate G)
Water was added to 1000 g of ground calcium carbonate having a BET specific surface area of 2.6 m ² / g so that the solid content was 10% by mass, and a calcium carbonate slurry was prepared. Next, to this slurry of calcium carbonate, an aqueous solution of sodium hydroxide having a concentration of 2.5 mol / l was added and stirred. Thereafter, the obtained slurry was dewatered to obtain a cake having a solid content of 60% by mass. The resulting cake was dried in a dryer. The addition amount of the sodium hydroxide aqueous solution was adjusted so that the alkali metal content in the mixture of calcium carbonate and sodium hydroxide after dehydration and drying was 500 μg / g.

The BET specific surface area of the obtained mixture of calcium carbonate and sodium hydroxide (hereinafter referred to as “calcium carbonate G”) was 2.6 m ² / g. The pH of calcium carbonate G was 10.3.

(Calcium carbonate H)
Calcium carbonate was obtained in the same manner as calcium carbonate G, except that an aqueous sodium hydroxide solution was added so that the alkali metal content contained in the mixture of calcium carbonate and sodium hydroxide was 1000 μg / g.

The BET specific surface area of the obtained mixture of calcium carbonate and sodium hydroxide (hereinafter referred to as “calcium carbonate H”) was 2.6 m ² / g. The pH of calcium carbonate H was 10.5.

(Calcium carbonate I)
Calcium carbonate was obtained in the same manner as calcium carbonate G, except that an aqueous sodium hydroxide solution was added so that the alkali metal content contained in the mixture of calcium carbonate and sodium hydroxide would be 1,500 μg / g.

The BET specific surface area of the obtained mixture of calcium carbonate and sodium hydroxide (hereinafter referred to as “calcium carbonate I”) was 2.5 m ² / g. The pH of calcium carbonate I was 10.8.

(Calcium carbonate J)
Calcium carbonate was obtained in the same manner as calcium carbonate G, except that an aqueous sodium hydroxide solution was added so that the alkali metal content contained in the mixture of calcium carbonate and sodium hydroxide would be 2500 μg / g.

The BET specific surface area of the obtained mixture of calcium carbonate and sodium hydroxide (hereinafter referred to as “calcium carbonate J”) was 2.6 m ² / g. The pH of calcium carbonate J was 11.2.

The BET specific surface area, alkali metal content and pH value of each of the obtained calcium carbonates are shown in Table 1.

<Synthesis of Talc K and L>
(Talc K)
A talc K having a BET specific surface area of 8.1 m ² / g was used. The pH was 9.7.

(Talc L)
Water was added to 1000 g of talc having a BET specific surface area of 8.1 m ² / g so that the solid content was 10% by mass, to prepare a slurry of talc. Next, to this slurry of talc, an aqueous solution of sodium hydroxide having a concentration of 2.5 mol / l was added and stirred. Thereafter, the obtained slurry was dewatered to obtain a cake having a solid content of 60% by mass. The resulting cake was dried in a drier to obtain talc. The addition amount of the sodium hydroxide aqueous solution was adjusted so that the alkali metal content contained in the mixture of talc and sodium hydroxide after dehydration and drying was 2500 μg / g.

The BET specific surface area of the resulting mixture of talc and sodium hydroxide (hereinafter referred to as “talc L”) was 7.0 m ² / g. The pH of talc L was 10.6.

The BET specific surface area, alkali metal content and pH value of each of the obtained talcs are shown in Table 1.

<Production of polyurethane resin composition>
(Examples 1 to 8 and Comparative Examples 1 to 2)
Using calcium carbonate shown in Table 1, polyurethane resin compositions of Examples 1 to 8 and Comparative Examples 1 to 2 were produced. Specifically, 222 parts by mass of calcium carbonate, 100 parts by mass of hydroxyl-terminated liquid polybutadiene (Poly-BD (R-45HT) manufactured by Idemitsu Kosan Co., Ltd.), 48 parts by mass of diisononyl phthalate (DINP), heavy calcium carbonate 132 parts by weight of Whiteton P30 manufactured by Shiroishi Kogyo Co., Ltd., 1.6 parts by weight of an ultraviolet absorber (SEESORB 703 manufactured by Shipro Kasei Co., Ltd.), amine catalyst (1,4-Diazabicycle [2,2,2] octane) 0 .021 parts by mass and 0.006 parts by mass of tin catalyst (Neostann U-100 manufactured by Nitto Kasei Co., Ltd.) were mixed to obtain a paste of a precursor of a polyurethane resin composition.

Next, 4.5 parts by mass of MDI based isocyanate (Cosmonate M200 manufactured by Mitsui Chemicals, Inc.), 11.5 parts by mass of diisononyl phthalate (DINP), and 2 parts by mass of carbon black were mixed to obtain an isocyanate mixture.

Next, the above precursor and an isocyanate mixture were mixed in a mass ratio of 200 to 18 to obtain a polyurethane resin composition.

(Example 9 and Comparative Example 3)
Using talc shown in Table 1, polyurethane resin compositions of Example 9 and Comparative Example 3 were produced. Specifically, 100 parts by mass of talc, 100 parts by mass of hydroxyl-terminated liquid polybutadiene (Poly-BD (R-45 HT) manufactured by Idemitsu Kosan Co., Ltd.), 48 parts by mass of diisononyl phthalate (DINP), heavy calcium carbonate 253 parts by mass of Whiteton P30 manufactured by Kogyo Co., Ltd., 1.6 parts by mass of ultraviolet absorber (SEESORB 703 manufactured by Cipro Chemical Co., Ltd.), amine catalyst (1,4-Diazabicycle [2,2,2] octane) 0. A paste of a precursor of a polyurethane resin composition was obtained by mixing 021 parts by mass and 0.006 parts by mass of tin catalyst (Neostann U-100 manufactured by Nitto Kasei Co., Ltd.).

[Evaluation of curability]
With respect to the obtained polyurethane resin composition, Shore A (Shore A) hardness is measured and cured after 1 hour after mixing the two solutions, up to 5 hours every hour, up to 7 hours if necessary, and finally 24 hours. The sex was evaluated.

[Evaluation of tensile strength, elongation and adhesion]
The tensile strength and elongation of the cured product of the resulting polyurethane resin composition were measured as follows. Polyurethane resin composition obtained by using a 50 × 50 × 5 mm glass plate specified in JIS A 1439 and combining spacers to make a space of 12 × 12 × 50 mm and preventing air bubbles from entering in the space The product paste was filled and aged at 23 ° C. for 14 days and then at 30 ° C. for 14 days to obtain a test piece consisting of a cured product of the polyurethane resin composition. After leaving the obtained test piece to stand at 23 ° C. for one day or more, a tensile test was performed by an autograph at a tensile speed of 50 mm / min to measure the tensile strength and the elongation.

The adhesion was visually confirmed with respect to the degree of peeling of the sealing material after the tensile test was performed on the test piece.

○: The adherend and the sealing material are firmly bonded, and the sealing material is cohesively broken.
X: Peeling off at the interface between the adherend and the sealing material. (Interface peeling)

Table 2 shows the results of measurement of the change with time in Shore A hardness, tensile strength, elongation, and adhesion in Examples 1 to 8 and Comparative Examples 1 and 2.

Further, FIG. 2 shows time-dependent changes in Shore A hardness in Examples 1 to 4 and Comparative Example 1, and FIG. 3 shows time-based changes in Shore A hardness in Examples 5 to 8 and Comparative Example 2.

Table 3 shows the measurement results of the change with time of the Shore A hardness, the tensile strength, the elongation, and the adhesiveness in Example 9 and Comparative Example 3.

Moreover, the time-dependent change of the Shore A hardness in Example 9 and Comparative Example 3 is shown in FIG.

From the results shown in Table 2 and Table 3 and FIGS. 2 to 4, the polyurethane resin compositions of Examples 1 to 9 having an alkali metal content within the scope of the present invention have lower alkali metal contents than those within the scope of the present invention. It can be seen that the curing rate is faster than the polyurethane resin composition of Comparative Example 1, 2 or 3 which has. Further, it is found that the tensile strength, the elongation and the adhesion of the cured products of the polyurethane resin compositions of Examples 1 to 9 are comparable to those of the polyurethane resin compositions of Comparative Examples 1, 2 or 3. Therefore, by using the polyurethane resin composition of the present invention as a sealing material for double glazing, the glass plates can be sealed in a short time without decreasing the strength, elongation, etc. of the sealing material. It can be seen that the laminated glass can be produced efficiently.

In each of the above Examples and Comparative Examples, the alkali metal content is adjusted by adding an aqueous solution of sodium hydroxide to a slurry of calcium carbonate or talc, but the present invention is not limited to this. .

DESCRIPTION OF SYMBOLS 1 ...

Double layer glass

2, 3 ... Glass plate 4 ... Spacer 5 ... Adhesive agent 6 ... Interior space 7 ... Sealing material

Claims

A pair of glass plates provided at predetermined intervals;
A spacer disposed between the pair of glass plates to maintain the spacing at the periphery of the pair of glass plates and to form an inner space inside;
A sealing material provided along the outside of the spacer and sealing between the pair of glass plates;
The sealing material comprises an inorganic filler and is composed of a polyurethane resin composition containing an alkali metal in the range of 100 to 2000 μg / g.
The multilayer glass according to claim 1, wherein the inorganic filler is calcium carbonate.
The double glazing according to claim 1 or 2, wherein the alkali metal is contained as sodium hydroxide.
A method of producing a multi-layer glass according to any one of claims 1 to 3, comprising:
Disposing the spacer between the pair of glass plates to maintain the spacing at the periphery of the pair of glass plates and to form an inner space inside;
Applying the sealing material along the outer side of the spacer, and sealing the pair of glass plates together.