JP3197379B2 - Manufacturing method of laminated glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Laminated glass is used for automobiles and buildings. Conventionally, as a laminated glass, a laminated glass in which a thermoplastic polyvinyl butyral film is sandwiched between two glasses is generally known. This laminated glass improved the risk of the glass breaking easily and into sharp shards. However, its production requires a large-scale autoclave, which makes it difficult to produce large-sized laminated glass, sandwiches thermoplastic resin, lowers high-temperature physical properties, and lacks sound insulation. Shortcomings have been noted.

There is also known a method in which an acrylic syrup is poured between two glasses and cured using a peroxide as a catalyst to produce a laminated glass. According to this method, a laminated glass can be manufactured by a simple method, and since the sandwiched resin is a curable resin, it can be said that it overcomes the drawbacks of the laminated glass that sandwiches a film, such as having excellent high-temperature properties. However, the curing reaction requires heating, and the amount of the catalyst that achieves a practically short curing time has a disadvantage that coloring and transparency are impaired. Also, conventional acrylic syrup,
The viscosity is high and bubbles are involved during injection, and it takes a long time to remove bubbles. When the ratio of the amount of the acrylic monomer in the acrylic syrup was increased and the viscosity was reduced, there was a defect that shrinkage was severe upon curing and voids were generated.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminated glass obtained by injecting and curing an acrylic syrup that can be substantially cured at room temperature, and to provide optical properties such as transparency, sound insulation, and impact resistance. An object of the present invention is to provide a method for easily producing a laminated glass having excellent heat resistance and weather resistance.

[0005]

Means for Solving the Problems The present inventors have improved the optical characteristics such as transparency, sound insulation, impact resistance and weather resistance by injecting and curing an acrylic syrup having a specific viscosity range. We succeeded in obtaining a method that can easily manufacture laminated glass.

That is, the first aspect of the present invention is to provide at least one
10 to 90 wt. Of a monomer mixture containing (A) two or more (meth) acrylate monomers having 1 to 20 carbon atoms of an alkyl group between two plates, each of which is a glass plate %, (B) 5 to 40% by weight of a copolymer containing two or more (meth) acrylate monomers having 1 to 20 carbon atoms in the alkyl group, and (C) 5 to 30 plasticizers % By weight, and an acrylic syrup having a viscosity of 40 centipoise or less as a main component is injected, and substantially cured at room temperature.
Secondly, (A) one or more (meth) acrylic acid ester monomer having 1 to 20 carbon atoms of an alkyl group and at least one glass plate between at least two glass plates. 10 to 90% by weight of a monomer mixture containing one or two or more other α, β-ethylenically unsaturated monomers copolymerizable, (B) an alkyl group having 1 to 1 carbon atoms
Monomer containing 20 or more (meth) acrylate monomers and one or more other α, β-ethylenically unsaturated monomers copolymerizable therewith 5 to 40% by weight of a copolymer of a body mixture, (C) a plasticizer 5
30% by weight, and injecting an acrylic syrup having a viscosity of 40 centipoise or less, and curing at substantially normal temperature.

Hereinafter, the present invention will be described in detail. At least one laminated glass of the present invention is a glass plate. Other plates include FRP plate, polycarbonate plate, synthetic resin plate such as polymethyl methacrylate plate, iron plate, copper plate, metal plate such as stainless plate, paper, resin impregnated paper, wood,
Tile and the like can be exemplified. These plates can be printed to impart design properties. These plates include not only flat plates but also curved plates.

The acrylic syrup of the present invention comprises a specific monomer mixture (A), a specific copolymer (B) and a plasticizer (C). The monomer mixture may be a monomer mixture containing two or more (meth) acrylate monomers having 1 to 20 carbon atoms in the alkyl group or a (meth) acrylate having 1 to 20 carbon atoms in the alkyl group. A) A monomer mixture containing one or more acrylate monomers and other α, β-ethylenically unsaturated monomers copolymerizable therewith.

The copolymer has 1 to 2 carbon atoms in the alkyl group.
A copolymer comprising two or more (meth) acrylic acid ester monomers, or an alkyl group having 1 carbon atom
1 to 20 (meth) acrylate monomers or 2
It is a copolymer of a monomer mixture comprising at least one species and another α, β-ethylenically unsaturated monomer copolymerizable therewith. The molecular weight of the copolymer is preferably from 10,000 to 50,000. Here, the (meth) acrylate is
An acrylic acid ester and a methacrylic acid ester, which will be similarly described below.

The (meth) acrylate having 1 to 20 carbon atoms includes (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Lauryl acrylate, stearyl (meth) acrylate and the like can be mentioned.

Other α, β-ethylenically unsaturated monomers copolymerizable with the (meth) acrylic ester monomer include glycidyl (meth) acrylate, allyl glycidyl ether, 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. Also, ethylene glycol di (meth) acrylate,
Polyfunctional monomers such as trimethylolpropane trimethacrylate can also be used. 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 plasticizer is effective in reducing curing shrinkage and preventing the occurrence of voids during curing. Examples of the plasticizer include adipic acid ester, azelaic acid ester, sebacic acid ester, and alicyclic dibasic acid ester. The amount of the plasticizer is 5 to 30% by weight, and if less than 5% by weight, there is no shrinkage preventing effect. If it exceeds 30% by weight, resin curability and weather resistance are poor.

The syrup of the present invention is, for example, a (meth) acrylate monomer having 1 to 20 carbon atoms in the alkyl group, and an α, β-ethylenically unsaturated monomer copolymerizable therewith if necessary. Stirring the monomer mixture consisting of the body,
Heating, stirring and mixing in a reaction vessel equipped with a cooling facility, for example, an azo compound such as azobisisobutyronitrile, or a polymerization catalyst such as benzoyl peroxide, peroxide such as t-butylperoxyoctanoate, And a chain transfer agent such as n-dodecyl mercaptan and a copolymerization reaction at a temperature of 50 to 130 ° C. for 3 to 24 hours, and then a plasticizer is added. The plasticizer may be added prior to copolymerization.

At this time, the proportion of the copolymer is 5 to 40% by weight. If the amount is less than 5% by weight, the volume shrinkage at the time of curing is large, and the surface of the molded product becomes glossy. Becomes difficult. The ratio of the monomer mixture is 10 to 90% by weight. 10% by weight
If it is less than 3, the syrup has a high viscosity and the workability is extremely deteriorated. If it exceeds 90% by weight, the volume shrinkage at the time of curing is large, and the surface of the molded product becomes glossy. Incidentally, if necessary, additional monomers may be added after the copolymerization reaction.

[0015] The viscosity of the acrylic syrup is 40 centipoise (CPS) or less, preferably 1 CPS or more.
If it is less than 1 CPS, there is a disadvantage that voids are formed in the cured resin layer, which is the intermediate layer of the laminated glass, when cured. If it exceeds 40 CPS, there is a drawback that it is extremely difficult to remove bubbles entrained during injection. More preferably, 1-20 CPS,
Particularly preferred is 1 to 10 CPS. The viscosity can be adjusted by the molecular weight of the copolymer, the ratio between the copolymer and the monomers, and the amount of the plasticizer.

Acrylic syrup is accompanied by volume shrinkage upon curing. The volume shrinkage is preferably 15% or less. When the volumetric shrinkage ratio is large, there is a tendency that voids occur during curing. The volume shrinkage can be adjusted by the proportion of the copolymer in the syrup and the amount of the plasticizer.

As a curing catalyst for the acrylic syrup, a redox catalyst can be used. In particular, as an oxidizing agent of a redox catalyst system capable of curing at room temperature, peroxides such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, etc. Hydroperoxide is preferred in terms of short curing time, and cumene hydroperoxide is particularly preferred. Examples of the reducing agent include metal salts, tertiary amines, quaternary ammonium salts, and mercaptans. In particular, a vanadium compound is preferred in terms of coloring. Further, ascorbic acid or pyruvic acid can be used to promote curing.

In order to produce a laminated glass using the cold-setting resin composition of the present invention, for example, the following operation is performed. A catalyst is added to the acrylic syrup of the present invention, a pigment and a coloring agent are added if necessary, and further, an ultraviolet absorber, an antioxidant, resin beads and resin powder are added and mixed as necessary. A double-sided tape of an appropriate thickness such as butyl rubber or silicon rubber is attached to the end face between the two glass plates to create 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, silicon rubber or the like. The glass plate containing the resin
The curing reaction proceeds during standing for 1 hour to 10 hours in an environment of 30 ° C.

[0019]

The present invention will be described below in more detail with reference to examples and comparative examples. The physical properties of the cured products obtained in Examples and Comparative Examples were measured by the following methods. All parts in the examples are parts by weight. (1) Weather resistance Using an eye super (manufactured by Iwasaki Electric Co., SUW-13), the color difference (ΔE = (ΔL ² + Δa ² ) after 100 hours and at the initial stage
+ 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, manufactured by Nippon Denshoku Industries Co., Ltd.), the transmittance of a 3 mm-thick flat plate was measured with light having a wavelength of 550 nm. (3) Tensile strength A jig was attached to the front and back of the laminated glass, and the tensile strength of the laminated glass was measured by a tensile tester. (4) Impact resistance (falling ball test) This was performed 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 reverberation room for sound source and the reverberation room for sound reception according to the actual use condition, and the other parts were covered with a material having sufficiently large transmission loss. The sound source is octave band noise centered on the following values. 125, 250, 500, 1000, 2000, 40
00 Hz The measurement frequency is the following value in a 1/3 octave band. 100, 125, 160, 200, 250, 315, 4
00, 500, 630, 800, 1000, 1250,
1600, 2000, 2500, 3150, 4000,
In the 5000 Hz measurement, the transmission loss is calculated using the arithmetic mean value of five points of the inter-room sound pressure level difference and two points of the reverberation time for each frequency. Calculation of sound transmission loss is based on JIS A 1416
The sound absorption loss of the sound source reverberation room and the sound reception reverberation room was measured according to the “method of measuring sound transmission loss in a laboratory”, and calculated by the following equation. 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 the sound-transmitting portion of the specimen (m ² ) A: Sound-absorbing reverberation room sound absorption power (m ² ) T: Sound-receiving reverberation room reverberation time (sec) V: Sound-receiving reverberation room volume (m ³⁾ C) Sound velocity in air (m / sec) t: Temperature of air (° C) (6) Volume shrinkage The specific gravity of the resin and the specific gravity of the cured resin were measured and calculated by the following equation. ε (%) = 100 × (Sg (s) −Sg (l)) / Sg (s) Sg (S): Specific gravity of solid Sg (l): Specific gravity of liquid ε (%): Volumetric shrinkage

Production Example 1 (Production of Syrup A) The following composition comprising a monomer, a polymerization initiator and a chain transfer agent was charged into a flask having a stirrer, and 100-105
The reaction was carried out at 7 ° C. for 7 hours to obtain a syrup (A) having a polymerization rate of 19% and a viscosity of 86 centipoise. The polymerization rate was determined from the refractive index using Abbe refractometer including the following production examples. Methyl methacrylate 29.0 parts Styrene 19.0 parts 2-Ethylhexyl methacrylate 19.6 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 2 (Production of Syrup B) In the same flask as in Production Example 1, the following composition comprising a monomer, a polymerization initiator and a chain transfer agent was charged, and 100 to 10
The reaction was carried out at 5 ° C. for 3 hours to obtain a syrup (B) having a polymerization rate of 10% and a viscosity of 20 centipoise. Methyl methacrylate 25.0 parts Styrene 10.0 parts 2-Ethylhexyl acrylate 31.0 parts n-butyl methacrylate 31.0 parts Ethylene glycol dimethacrylate 2.4 parts n-dodecyl mercaptan 0.5 parts Azobisisobutyronitrile 0 1 copy ────────────────────────── Total 100.0 copy

Examples 1 to 7 The acrylic syrups obtained in the production examples were prepared in the production example of laminated glass and cured under the conditions shown in Table 1 to obtain a transparent laminated glass. The properties of the obtained laminated glass were measured and tested. The results are shown in Tables 2 and 3. In addition, the laminated glass was produced as follows. 610m
A plate glass is attached by using an acrylic tape having a thickness of 1 mm and a width of 5 mm as a sealing material between two plate glasses of m × 610 mm × 3 mm. Further, in order to form an intermediate film, a mixture of the acrylic syrup, the peroxide and the curing accelerator of the above-mentioned production example is injected and cured into a laminated glass. Comparative Examples 1 to 6 The acrylic syrups obtained in the production examples were prepared in the production example of laminated glass and cured under the conditions shown in Table 4 to obtain a transparent laminated glass. The properties of the obtained laminated glass were measured and tested. The results are shown in Tables 5 and 6.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

[0027]

[Table 5]

[0028]

[Table 6]

[0029]

The laminated glass manufactured by the method of the present invention has a transparent cured resin layer in the intermediate layer, does not generate voids, is excellent in optical properties, sound insulation and impact resistance, has no discoloration and has good weather resistance. It has excellent tensile strength of 10 kg / cm ² or more and excellent performance in practical adhesion to glass. Further, since the hardening time of the hardened resin layer within a few hours that is practical at room temperature is sufficient, the laminated glass is characterized in that the laminated glass can be manufactured at room temperature in a short time.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C03C 27/12 B32B 17/10 C08F 2/02

Claims (2)

(57) [Claims] 1. A method comprising (A) two or more (meth) acrylate monomers having 1 to 20 carbon atoms in an alkyl group between at least one glass plate and at least one glass plate. 10 to 90% by weight of a monomer mixture, and 5 to 40% by weight of a copolymer (B) containing two or more (meth) acrylate monomers having 1 to 20 carbon atoms in an alkyl group.
(C) A method for producing a laminated glass, comprising injecting an acrylic syrup having a viscosity of 40 centipoise or less and containing 5 to 30% by weight of a plasticizer as a main component, and curing at substantially normal temperature. 2. A method according to claim 1, wherein one or two or more (A) (meth) acrylic acid ester monomers having 1 to 20 carbon atoms in the alkyl group are interposed between two plates, at least one of which is a glass plate. 10 to 90% by weight of a monomer mixture containing one or two or more other α, β-ethylenically unsaturated monomers copolymerizable, (B) an alkyl group having 1 to 1 carbon atoms
Monomer containing 20 or more (meth) acrylate monomers and one or more other α, β-ethylenically unsaturated monomers copolymerizable therewith 5 to 40% by weight of a copolymer of a body mixture, (C) a plasticizer 5
A method for producing a laminated glass, comprising injecting an acrylic syrup having a viscosity of 40 centipoise or less and containing 30% by weight as a main component, and curing substantially at room temperature.