JPH06191902A - Laminated glass - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a laminated glass having excellent optical characteristics and sound insulation. [Structure] An acrylic syrup consisting of a mixture of specific monomers and a specific copolymer is cured between two sheets of glass. Particularly, it is preferable to use a specific catalyst system. [Effect] A laminated glass having excellent optical characteristics and sound insulation can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated glass having excellent optical properties such as transparency, sound insulation, impact resistance and weather resistance, which are used for automobiles, buildings and shops, and other constructions.

[0002]

2. Description of the Related Art Laminated glass is used for automobiles and construction. Conventionally, as a laminated glass, one in which a thermoplastic polyvinyl butyral film is sandwiched between two pieces of glass is generally known. This laminated glass improved the risk of the glass breaking easily into sharp pieces. However, since its production requires an autoclave, which is a large-scale device, it is difficult to produce a large-sized laminated glass, the high-temperature physical properties are deteriorated by sandwiching a thermoplastic resin, and the sound insulation is insufficient. Has been pointed out.

Further, a method is known in which an acrylic syrup is injected between two pieces of glass and cured using a peroxide as a catalyst to produce a laminated glass. It can be said that this method overcomes the drawbacks of laminated glass that sandwiches a film, such that laminated glass can be produced by a simple method, and that the resin sandwiched is a curable resin, which has excellent physical properties at high temperatures. However, there is a drawback that heating is required to proceed the curing reaction, and the amount of the catalyst that achieves a practically short curing time causes coloring and impairs transparency.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is a laminated glass obtained by injecting and curing a resin composition which is curable at substantially room temperature, and having optical characteristics such as transparency, sound insulation,
It is to provide a laminated glass method having excellent impact resistance and weather resistance.

[0005]

The present inventors have found that a specific acrylic syrup is room temperature curable, and by pouring it into a plate of which at least one is glass, it is cured to obtain optical properties such as transparency. The present invention succeeded in obtaining a laminated glass excellent in physical properties, sound insulation, impact resistance, and weather resistance, and further found out that a laminated glass having further excellent properties can be obtained by using a specific curing catalyst. Reached

That is, the present invention is a laminated glass in which the following room temperature curable acrylic syrup (A-1) or (A-2) is cured between two plates, at least one of which is a glass plate. (A-1) Following (a-1) (b-
A syrup containing 1). (A-1) (Meth) having 1 to 20 carbon atoms of the alkyl group
10 to 90% by weight of a monomer mixture containing two or more acrylic ester monomers, and (b-1) two (meth) acrylic ester monomers having 1 to 20 carbon atoms of the alkyl group Copolymer containing 5 to 40% by weight. (A-2) A syrup containing the following (a-2) and (b-2). (A-2) (meth) having 1 to 20 carbon atoms of the alkyl group
Monomer Mixtures 10-9 Containing One or Two or More Acrylic Ester Monomers and One or Two or More Other α, β-Ethylenically Unsaturated Monomers Copolymerizable with These
0% by weight, (b-2) alkyl group having 1 to 20 carbon atoms
(Meth) acrylic acid ester monomer of 1 type or 2 types or more and other α, β-ethylenically unsaturated monomer copolymerizable therewith, or a monomer containing 1 type or 2 types or more 5 to 40% by weight of the copolymer of the mixture, and the present invention will be described in detail below.

At least one of the laminated glasses of the present invention is a glass plate, and the thickness and size thereof are not particularly limited. Other plates include FRP plates, polycarbonate plates, synthetic resin plates such as polymethylmethacrylate plates, iron plates, copper plates, metal plates such as stainless plates, paper, resin-impregnated paper,
Examples include wood and tiles. It is also possible to print these plates to give them designability. Further, these plates include not only flat ones but also curved ones.

The acrylic syrup (A-1) or (A-2) is a specific monomer mixture (a-1) or (a-).
2) and the specific copolymer (b-1) or (b-2).

As the monomer mixture, a monomer mixture containing two or more (meth) acrylic acid ester monomers having an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. It is a monomer mixture containing one or more of 20 (meth) acrylic acid ester monomers and another α, β-ethylenically unsaturated monomer copolymerizable therewith.

The copolymer has 1 to 2 carbon atoms in the alkyl group.
A copolymer containing two or more kinds of (meth) acrylic acid ester monomers of 0 or an alkyl group having 1 carbon atom
~ 20 (meth) acrylic acid ester monomer 1 or 2
It is a copolymer of a monomer mixture containing one or more and other α, β-ethylenically unsaturated monomers copolymerizable therewith. Here, the (meth) acrylic acid ester is an acrylic acid ester and a methacrylic acid ester,
Hereinafter, the same expression will be applied.

Examples of the (meth) acrylic acid ester having 1 to 20 carbon atoms include (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Examples thereof include lauryl acrylate and stearyl (meth) acrylate.

Other α, β-ethylenically unsaturated monomers copolymerizable with the (meth) acrylic acid ester monomer include glycidyl (meth) acrylate, allyl glycidyl ether, and 2-hydroxy (meth) acrylate. ,
Examples thereof include (meth) acrylic acid, fumaric acid and its esters, maleic acid and its esters, styrene, vinyltoluene, α-methylstyrene, vinyl acetate, (meth) acrylamide, and (meth) acrylonitrile. In addition, ethylene glycol di (meth) acrylate,
It is also possible to use polyfunctional monomers such as trimethylolpropane trimethacrylate. Such other α, β
-When an ethylenically unsaturated monomer is used, it is usually 1 to 50% by weight in both the monomer mixture and the copolymer.

The syrup of the present invention comprises, for example, a (meth) acrylic acid ester monomer having an alkyl group having 1 to 20 carbon atoms, and optionally an α, β-ethylenically unsaturated monomer copolymerizable therewith. Stirring the monomer mixture consisting of the body,
Stirring and mixing in a reaction tank equipped with heating and cooling equipment, for example, azo compounds such as azobisisobutyronitrile, or polymerization catalysts such as benzoyl peroxide, peroxides such as t-butylperoxyoctanoate, And a chain transfer agent such as n-dodecyl mercaptan to obtain a copolymerization reaction at a temperature of 50 to 130 ° C. for 3 to 24 hours. At this time, the proportion of the copolymer is 5 to 40% by weight. If it is less than 5% by weight, the volume shrinkage upon curing is large and the surface of the molded article becomes glossy, and if it exceeds 40% by weight, the syrup becomes highly viscous and the workability is extremely deteriorated. The proportion of the monomer mixture is 10 to 90% by weight. If it is less than 10% by weight, the syrup has a high viscosity and the workability is extremely deteriorated. If it exceeds 90% by weight, the volume shrinkage upon curing is large and the surface of the molded article becomes glossy. If necessary, additional monomers may be added after the copolymerization reaction.

In the present invention, it is preferable to use a redox catalyst as the curing catalyst. As the oxidizing agent, peroxides such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate and peroxyester are usually used. Among these, hydroperoxide is preferable in that the curing time is short,
Further, cumene hydroperoxide is preferable. The peroxide is 0.5 to 100 parts by weight of acrylic syrup.
1.5 parts by weight is preferred. If it is less than 0.5 part by weight, the curing time will be long, and if it exceeds 1.5 parts by weight, the cured product will be colored. As the reducing agent, metal salts, tertiary amines, 4
Examples thereof include primary ammonium salts and mercaptans, and vanadium compounds such as vanadium octoate and vanadium acetylacetonate are particularly preferable. The amount of the vanadium compound was 0.10 with respect to 100 parts by weight of acrylic syrup.
01 to 2 parts by weight is preferred. Below 0.01 parts by weight,
It takes a long time to cure, and if it exceeds 2 parts by weight, the cured product is colored. In the present invention, it is preferable to use pyruvic acid or ascorbic acid in order to shorten the curing time. The amount of pyruvic acid or ascorbic acid is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of acrylic syrup. If it is less than 0.01 part by weight, the curing time will be long, and if it exceeds 2 parts by weight, the cured product will be colored.

In the present invention, it is possible to use an ultraviolet absorber together. The ultraviolet absorber is effective in preventing discoloration of indoor products and furniture and improving weather resistance of laminated glass by blocking ultraviolet rays. Further, when an ultraviolet absorber that absorbs 370 nm or less is used, it has an effect of preventing flying insects such as larvae that are attracted by the indoor light leak, especially at night in summer. As the ultraviolet absorber, salicylic acid ester-based, benzophenone-based benzotriazole-based,
Examples thereof include cyanoacrylate type and oxalic acid anilide type. The amount of the ultraviolet absorber is preferably 0.05 to 5 parts by weight. If it is less than 0.05 parts by weight, the effect of absorbing ultraviolet rays is poor,
If it exceeds 5 parts by weight, the compatibility with the resin is poor.

Further, in the present invention, it is possible to use a coupling agent in order to improve the adhesion between the cured resin and the glass. Examples of the coupling agent include silane coupling agents such as vinylsilane, acrylsilane, and epoxysilane. The amount of the coupling agent is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of acrylic syrup. If it is less than 0.01 part by weight, the improvement of the adhesion to glass is not always sufficient, and if it exceeds 10 parts by weight, the compatibility with the resin is deteriorated and separation and white turbidity occur.

To produce a laminated glass using the room temperature curable resin composition of the present invention, for example, the following may be carried out. A curing catalyst and, if necessary, pyruvic acid or ascorbic acid are added to the acrylic syrup, and further, an ultraviolet absorber, a coupling agent, a pigment, a coloring agent, an antioxidant, resin beads, and resin powder are added and mixed as desired. A double-sided tape of appropriate thickness such as butyl rubber or silicon rubber is attached to the end surface between two glass plates to form an intermediate space.
At this time, a part is opened and a predetermined amount of the resin composition is injected from here. After defoaming, seal with butyl rubber, silicone rubber, etc. Glass plate encapsulating resin is 10-30 ° C
The curing reaction proceeds while standing for 1 to 10 hours under the environment.

[0018]

The present invention will be described in more detail with reference to examples. The physical properties of the cured products obtained in the examples were measured by the following methods. All parts in the examples are parts by weight. (1) Weather resistance A color difference (ΔE = (ΔL ² + Δa ² ) after 100 hours using an eye super (SUW-13 type manufactured by Iwasaki Electric) was used.
+ Δb ² ) ^1/2 ) with a color difference meter (ND-10 manufactured by Nippon Denshoku Industries Co., Ltd.)
1D type). (2) Light transmittance Using a spectrophotometer (ND-101D type, manufactured by Nippon Denshoku Industries Co., Ltd.), the transmittance of a flat plate having a thickness of 3 mm was measured by light having a wavelength of 550 nm. (3) Tensile strength A jig was put on the front and back of the laminated glass to measure the tensile strength of the laminated glass with a tensile tester. (4) Impact resistance (ball drop test) The impact resistance was measured according to JIS R 3205 (laminated glass). In this test, a steel ball having a diameter of 63.5 mm (1045 g) was freely dropped from a height of 150 cm, and the falling ball impact peeling property of the test piece was examined when the plate glass was broken. (5) Sound insulation The laminated glass was attached to the opening between the sound source reverberation room and the sound receiving reverberation room according to actual usage conditions, and parts other than the laminated glass were covered with a material with sufficiently large transmission loss. The sound source is octave band noise centered on the following values. 125, 250, 500, 1000, 2000, 40
The measurement frequency at 00 Hz is the following value in the 1/3 octave band. 100, 125, 160, 200, 250, 315, 4
00,500,630,800,1000,1250,
1600, 2000, 2500, 3150, 4000,
For 5000 Hz measurement, the sound pressure level difference between the rooms is set to 5 points and the reverberation time is set to 2 points for each frequency, and the transmission loss is calculated using the arithmetic mean value thereof. Sound transmission loss is calculated according to JIS A 1416.
The sound absorption force of the sound source reverberation room and the sound receiving reverberation room was measured according to the “method of measuring sound transmission loss in a laboratory” and calculated by the following formula. TL = D + 10 log (S / A) A = (55.3 / c) ・ V ・ (1 / T) c = 331.5 + 0.61t TL: Transmission loss (dB) D: Room sound pressure level difference (dB) S: Area of sound transmission part of the specimen (m ² ) A: Sound absorption capacity of the reverberation room (m ² ) T: Reverberation time of the sound reception room (sec) V: Reverberation room volume for the sound reception (m ³⁾ ) C: speed of sound in air (m / sec) t: temperature of air (° C)

Production Example 1 (Production of Syrup A) A flask having a stirrer was charged with the following composition comprising a monomer, a polymerization initiator and a chain transfer agent, and the mixture was heated to 100 to 105.
The reaction was carried out at ℃ for 7 hours to obtain a syrup (A) having a polymerization rate of 20% and a viscosity of 180 centipoise. The polymerization rate was calculated from the refractive index using an Abbe refractometer, including the following production examples. Methyl methacrylate 40.0 parts Styrene 15.0 parts 2-Ethylhexyl methacrylate 16.6 parts Isobutyl acrylate 25.0 parts Trimethylolpropane 3.0 parts Trimethacrylate t-dodecyl mercaptan 0.1 parts Azobisisobutyronitrile 0. 3 copies ────────────────────────── Total 100.0 copies

Production Example 2 (Production of Syrup B) The same flask as in Production Example 1 was charged with the following composition consisting of a monomer, a polymerization initiator and a chain transfer agent, and 100 to 10 was charged.
The reaction was carried out at 5 ° C for 4 hours to obtain a syrup (B) having a polymerization rate of 9% and a viscosity of 22 centipoise. Methyl methacrylate 30.0 parts Styrene 11.0 parts 2-Ethylhexyl acrylate 28.0 parts n-Butyl methacrylate 28.0 parts Ethylene glycol dimethacrylate 2.4 parts n-Dodecyl mercaptan 0.5 parts Azobisisobutyronitrile 0 １ copy ────────────────────────── Total 100.0 copies

Production Example 3 (Production of syrup C) The same flask as in Production Example 1 was charged with the following composition comprising a monomer, a polymerization initiator and a chain transfer agent, and 100 to 10 was charged.
The reaction was carried out at 5 ° C. for 7 hours to obtain Syrup C having a polymerization rate of 230 centipoise. Methyl methacrylate 35.0 parts Styrene 10.0 parts 2-Ethylhexyl methacrylate 26.6 parts Isobutyl acrylate 25.0 parts Trimethylolpropane 3.0 parts Trimethacrylate t-dodecyl mercaptan 0.1 parts Azobisisobutyronitrile 0. 3 copies ────────────────────────── Total 100.0 copies

Production Example 4 (Production of Syrup D) The same flask as in Production Example 1 was charged with the following composition consisting of a monomer, a polymerization initiator and a chain transfer agent, and the amount was 100 to 10:
The reaction was carried out at 5 ° C for 4 hours to obtain syrup D having a polymerization rate of 38 centipoise. Methyl methacrylate 36.0 parts Styrene 11.0 parts 2-Ethylhexyl acrylate 25.0 parts n-Butyl methacrylate 25.0 parts Ethylene glycol dimethacrylate 2.4 parts n-Dodecyl mercaptan 0.5 parts Azobisisobutyronitrile 0 １ copy ────────────────────────── Total 100.0 copies

Production Example 5 (Production of syrup E) The same flask as in Production Example 1 was charged with the following composition consisting of a monomer, a polymerization initiator and a chain transfer agent, and 100 to 10 was charged.
The reaction was carried out at 5 ° C for 7 hours to obtain syrup E having a polymerization rate of 25% and a viscosity of 235 centipoise. Methyl methacrylate 35.0 parts Styrene 16.0 parts 2-Ethylhexyl methacrylate 16.6 parts Isobutyl acrylate 25.0 parts Methacrylic acid 4.0 parts Trimethylolpropane 3.0 parts Trimethacrylate t-dodecyl mercaptan 0.1 parts Azobis Isobutyronitrile 0.3 parts ────────────────────────── Total 100.0 parts

Production Example 6 (Production of Syrup F) The same flask as in Production Example 1 was charged with the following composition comprising a monomer, a polymerization initiator and a chain transfer agent, and the amount was 100 to 10:
The reaction was carried out at 5 ° C for 3 hours to obtain syrup F having a polymerization rate of 8% and a viscosity of 20 centipoise. Methyl methacrylate 27.0 parts Styrene 10.0 parts 2-Ethylhexyl acrylate 30.0 parts n-Butyl methacrylate 30.0 parts Ethylene glycol dimethacrylate 2.4 parts n-Dodecyl mercaptan 0.5 parts Azobisisobutyronitrile 0 １ copy ────────────────────────── Total 100.0 copies

Examples 1 and 2 The following experiments were conducted for the purpose of examining the effects of peroxides, vanadium compounds, pyruvic acid or ascorbic acid. Laminated glass was prepared using the acrylic syrup obtained in Production Example and cured under the conditions shown in Tables 1 and 4 to obtain transparent laminated glass. The properties of the obtained laminated glass were measured and tested. The results are shown in Tables 2, 3 and 5, 6. The laminated glass was prepared as follows. 6
A sheet of glass having a thickness of 1 mm and a width of 5 mm is used as a sealing material between two sheets of sheet glass having a size of 10 mm × 610 mm × 3 mm to fit the sheet glass. Further, in order to form an intermediate film, the acrylic syrup, the peroxide, and the mixture of the curing accelerator of the above-described production example are poured and cured into a laminated glass. Examples 3 and 4 Experiments were performed according to Example 1 in order to see the effect of the ultraviolet absorber. The experimental conditions and results are shown in Tables 7-12. Examples 5 and 6 Experiments were performed according to Example 1 in order to see the effect of the coupling agent. Experimental conditions and results are shown in Tables 13-18.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

[0031]

[Table 6]

[0032]

[Table 7]

[0033]

[Table 8]

[0034]

[Table 9]

[0035]

[Table 10]

[0036]

[Table 11]

[0037]

[Table 12]

[0038]

[Table 13]

[0039]

[Table 14]

[0040]

[Table 15]

[0041]

[Table 16]

[0042]

[Table 17]

[0043]

[Table 18]

[0044]

INDUSTRIAL APPLICABILITY The laminated glass of the present invention has a transparent cured resin layer as an intermediate layer and has excellent optical characteristics, sound insulation, impact resistance and weather resistance. In addition, since it is sufficient to cure the cured resin layer at room temperature within a practical period of several hours, the laminated glass is characterized in that it can be manufactured at room temperature in a short period of time.

Claims (4)

[Claims] 1. A room temperature curable acrylic syrup (A-1) described below between two plates, at least one of which is a glass plate.
Alternatively, a laminated glass obtained by curing (A-2). (A-1) A syrup containing the following (a-1) and (b-1). (A-1) (Meth) having 1 to 20 carbon atoms of the alkyl group
10 to 90% by weight of a monomer mixture containing two or more acrylic ester monomers, and (b-1) two (meth) acrylic ester monomers having 1 to 20 carbon atoms of the alkyl group Copolymer containing 5 to 40% by weight. (A-2) A syrup containing the following (a-2) and (b-2). (A-2) (meth) having 1 to 20 carbon atoms of the alkyl group
Monomer Mixtures 10-9 Containing One or Two or More Acrylic Ester Monomers and One or Two or More Other α, β-Ethylenically Unsaturated Monomers Copolymerizable with These
0% by weight, (b-2) alkyl group having 1 to 20 carbon atoms
(Meth) acrylic acid ester monomer of 1 type or 2 types or more and other α, β-ethylenically unsaturated monomer copolymerizable therewith, or a monomer containing 1 type or 2 types or more Copolymer 5-40% by weight of the mixture. 2. 100 parts by weight of the acrylic syrup (A-1) or (A-2) according to claim 1 and 0.01 to 1 of a coupling agent between two plates, at least one of which is a glass plate.
A laminated glass obtained by curing a resin composition containing 0 part by weight. 3. Acrylic syrup (A-1) or (A-2) 100 parts by weight and an ultraviolet absorber 0.05 to 5 parts by weight between two plates, at least one of which is a glass plate. % Laminated glass obtained by curing a resin composition containing 100%. 4. 100 parts by weight of the acrylic syrup (A-1) or (A-2) according to claim 1 between two plates, at least one of which is a glass plate, and a peroxide of 0.5 to 1.5. A laminated glass formed by curing a resin composition containing 0.01 part by weight, 0.01-2 parts by weight of a vanadium compound, and 0.01-2 parts by weight of pyruvic acid or ascorbic acid.