JPH0796456B2 - Vinyl chloride-based interlayer film composition for laminated glass, interlayer film for laminated glass using the composition, and laminated glass using the interlayer film - Google Patents

Description

TECHNICAL FIELD The present invention relates to an interlayer film composition for laminated glass, an interlayer film for laminated glass formed into a sheet by this interlayer film composition, and this interlayer film. The present invention relates to a safety laminated glass used for automobiles, constructions, etc., which is produced by sandwiching between two pieces of glass.

(Prior Art) It is widely known to use plasticized polyvinyl butyral as an interlayer film composition for safety laminated glass, and because the plasticized polyvinyl butyral film has excellent penetration resistance and light resistance, Widely used in safety laminated glass for aircraft and construction. However, the plasticized polyvinyl butyral film has a drawback that it is inferior in adhesive workability with glass because the tackiness of the film surface at room temperature is too strong.

As an interlayer film for laminated glass, which eliminates the drawbacks of a plasticized polyvinyl butyral film, a technique for forming an interlayer film with an interlayer film composition containing a vinyl chloride resin, and a method of sandwiching the interlayer film between two glass plates. A technique for producing a laminated glass by thermocompression bonding has been proposed. (JP-A-55-162451, JP-A-56-37252) (Problems to be solved by the invention) The vinyl chloride resin, glycidyl methacrylate or glycidyl acrylate as a component to impart adhesiveness ,
It is a thermoplastic resin obtained by copolymerizing vinyl chloride with at least one monomer selected from ethylene-based hydrocarbons, fatty acid vinyls, acrylic acid esters, vinyl ethers, etc. as a component that imparts flexibility. In addition, there is a drawback in that the thermal stability is poor, that is, yellowing occurs by light irradiation or heating.

Therefore, the intermediate film formed of this intermediate film composition is susceptible to coloring due to heat during the film formation and the process of sticking to glass.

Further, JP-A-60-27630 discloses an interlayer film composition for laminated glass, which comprises an interlayer film composition containing a terpolymer of vinyl chloride-ethylene-glycidyl methacrylate and a vinyl chloride-ethylene copolymer. Techniques for creating are also proposed.

However, even this interlayer film has poor light resistance, and it has been difficult to use it as a safety glass used for a long period of time such as for construction. Further, this intermediate film was also inferior in thermal stability to the above-mentioned general vinyl chloride resin-based intermediate film. A heat stabilizer may be added to suppress coloration due to heating, but improvement in heat stability is not observed even if a fatty acid alkyltin compound, which is a heat stabilizer that has been conventionally used, is added. Further, when a fatty acid alkyltin-containing sulfur compound containing a large amount of a sulfur component, which is relatively excellent in thermal stability, was added, the thermal stability was improved, but the obtained interlayer film was inferior in light resistance.

The present invention has been made in view of such circumstances, and a light stabilizer can be obtained by adding a heat stabilizer satisfying the condition that the ratio S / Sn of sulfur S and tin Sn is 0.5 <S / Sn <1.5. It is an object to provide an interlayer film composition for laminated glass, an interlayer film for laminated glass, and a laminated glass which are excellent in both heat resistance and heat resistance.

(Means for Solving the Problem) That is, the interlayer film composition for vinyl chloride-based laminated glass according to the first invention is at least one selected from the group consisting of ethylene hydrocarbons, fatty acid vinyls, acrylates and vinyl ethers. A vinyl chloride-based copolymer obtained by copolymerizing a monomer, at least one monomer selected from the group consisting of glycidyl methacrylate and glycidyl acrylate, and vinyl chloride, a plasticizer, and a heat stabilizer. In a vinyl chloride-based interlayer glass composition for laminated glass, the heat stabilizer comprises sulfur S and tin.
Alkyltin-containing sulfur, in which the bond ratio S / Sn with Sn satisfies 0.5 <S / Sn <1.5 and sulfur is either a cyclic bond or tin is bonded to oxygen forming an ester bond. It is a compound.

The interlayer film for laminated glass of the second invention is produced using the above composition. Further, the laminated glass of the third invention is formed by sandwiching the interlayer film for laminated glass between two glass plates, thereby achieving the above object.

At least one monomer selected from the group consisting of glycidyl methacrylate and glycidyl acrylate is
Preferably, it is contained in the vinyl chloride-based copolymer in an amount of 1% by weight to 10% by weight. When it is less than 1% by weight, when the composition containing the obtained copolymer is used as an interlayer film for laminated glass, the adhesiveness between the interlayer film and glass becomes insufficient. When it exceeds 10% by weight, the composition containing the obtained copolymer becomes very hard and its softening temperature becomes high. Therefore, it becomes difficult to bond the interlayer film using this composition to glass.

At least one monomer selected from the group consisting of ethylene-based hydrocarbons, fatty acid vinyls, acrylic esters and vinyl ethers is preferably contained in the vinyl chloride-based copolymer in an amount of 0.5% by weight to 10% by weight. It 0.5
When the content is less than 10% by weight, when the composition containing the obtained copolymer is used as an interlayer film for laminated glass, the penetration resistance of the laminated glass is insufficient. When it exceeds 10% by weight, the yield of the copolymer after copolymerization of the monomer is lowered and the transparency of the composition containing the copolymer is deteriorated.

Ethylene hydrocarbons used include ethylene, propylene, isobutylene and the like. Examples of the fatty acid vinyl include vinyl acetate, vinyl caproate, vinyl pelargonate, vinyl laurate, vinyl myristate, vinyl palmitate and the like. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate. The vinyl ether includes methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, cetyl vinyl ether and the like.

A vinyl chloride copolymer can be obtained by copolymerizing these monomers by suspension polymerization, emulsion polymerization, solution polymerization, or the like. Suspension polymerization is preferably used from the viewpoint that a copolymer having excellent thermal stability can be obtained and that it is excellent in economic efficiency.

The interlayer film composition for a vinyl chloride-based laminated glass of the present invention,
Further, it contains a plasticizer. As the plasticizer, any plasticizer generally used for vinyl chloride resins is used. For example, the plasticizer includes dioctyl phthalate (DOP). This plasticizer is preferably used in a proportion of 20 to 60 parts by weight with respect to 100 parts by weight of the vinyl chloride copolymer. When the amount of the plasticizer is too large, the mechanical strength (for example, penetration resistance) of the obtained intermediate film is lowered when the obtained composition is used as an intermediate film of laminated glass. If the amount of the plasticizer is too small, the light resistance and plasticity of the interlayer film will be deteriorated.

A heat stabilizer is further added to the interlayer film composition for vinyl chloride laminated glass of the present invention. In general, when forming an interlayer film of laminated glass and when bonding and processing the interlayer film with a gasra, the interlayer film is exposed to high temperatures for a long time. Therefore, a thermal stabilizer is added to the composition to improve the thermal stability of the interlayer film. The heat stabilizer is preferably a vinyl chloride-based copolymer 10
0 to 5 parts by weight, more preferably 2 to 4 parts by weight
Used in proportions by weight. When a heat stabilizer containing a relatively large amount of a sulfur component is added, the resulting composition has excellent heat resistance, but light resistance decreases. That is, when the ratio S / Sn of sulfur S and tin contained in the heat stabilizer is 0.5 or less, the heat resistance of the composition is insufficient, and when the ratio S / Sn is 1.5 or more, the light resistance of the composition is inferior. Examples of the stabilizer include an alkyltin-containing sulfur compound having a ratio S / Sn of sulfur S and tin Sn represented by the following formulas (I), (II) and (III) satisfying 0.5 <S1Sn <1.5. With throat, S /
A compound with Sn = 1 is particularly preferably used. Even if a small amount of this compound is added to the vinyl chloride-based copolymer, it is sufficiently effective in terms of the above heat resistance and light resistance. Specific examples of the heat stabilizer used in the present invention are represented by the general formula: [R in the formulas (I), (II) and (III) is an alkyl group having 1 to 12 carbon atoms, n is an integer of 1 to 20 and m is 2 to
It is an integer of 20. ] There is one represented.

In the composition of the present invention, in addition to the heat stabilizer of the above formula, a conventional heat stabilizer may be used in combination within the range where the object of the present invention can be achieved. For example, the compounding ratio of the fatty acid dialkyl tin malate or the fatty acid dialkyl tin laurate is preferably in the range of 0 to 40% of the total heat stabilizer.

To the interlayer film composition for a vinyl chloride-based laminated glass of the present invention, an ultraviolet absorber, an antioxidant, a colorant, etc. are added, if necessary, and a known molding method, for example, a calendar roll method, an extruded sheet. Law, inflation law,
It is formed into an intermediate film by a casting method or the like. The obtained interlayer film is sandwiched between two pieces of glass, and is melted under heat and pressure to be pressure-bonded to obtain a safety laminated glass. The heating temperature is 80 ° C to 200 ° C, preferably 100 ° C to 180 ° C. The pressure is a pressure required to bring the interlayer film and the glass into close contact with each other and to remove bubbles at the interface between them and the interlayer film. This pressure is preferably 5 to 15 kg / cm ² . To pressurize this interlayer,
The laminating apparatus used to crimp a conventional plasticized polyvinyl butyral film to glass is used.

(Examples) Examples of the present invention will be described below.

The structural formulas of the heat stabilizers used in the examples and comparative examples are as follows.

Example 1 (1) Preparation of interlayer film for vinyl chloride-based laminated glass A vinyl chloride-based copolymer was prepared by copolymerizing 90% by weight of vinyl chloride with 8% by weight of ethylene and 2% by weight of glycidyl methacrylate. . This vinyl chloride copolymer 10
By adding 3 parts by weight of the heat stabilizer A, 40 parts by weight of dioctyl phthalate (DOP), and 0.3 parts by weight of a benzotriazole-based UV absorber to 0 parts by weight, and kneading with a 6-inch two-roll mill at 120 ° C. , An interlayer film composition for vinyl chloride laminated glass was prepared. This composition was heated and pressed at 170 ° C. and 100 kg / cm ² for 5 minutes in a hydraulic press machine to prepare a 0.5 mm thick interlayer film for vinyl chloride laminated glass.

(2) Measurement of physical properties of vinyl chloride-based interlayer film for laminated glass 1. Thermal stability One piece of the 0.5 mm-thick interlayer film for laminated glass (initial coloring was not observed) prepared in (1) was used. It was put in a gear oven with an ambient temperature of 190 ° C., left for 60 minutes, then taken out, and the degree of coloring was visually judged. As a result, no coloring of the interlayer film was observed and its thermal stability was good. The results are shown in Table 1.

2. Light resistance (1) A piece of 0.5 mm thick interlayer film for laminated glass was sandwiched between 2.5 mm thick Pyrex glass and sheet glass and heated at 150 ° C and 12 kg / cm ² . The pressure was applied to produce a laminated glass. The Pyrex glass side of this laminated glass was irradiated with light at a distance of 25 cm from the glass for 500 hours using a high pressure mercury lamp H-00F manufactured by Toshiba. After the irradiation, the laminated glass was attached to a white standard plate, the yellowness was measured using Suga Color Computer SM-4, and the yellowness difference ΔN between the white standard plate and the laminated glass was expressed. Yellowness difference ΔN of this laminated glass
Was 18.7. The results are shown in Table 1.

3. Bleedability A piece of the 0.5 mm thick interlayer film prepared in (1) was put under 95% RH.
-After being left in an atmosphere of 70 ° C for 48 hours, it was taken out and observed for stickiness on the film surface and the transparency. The results are shown in Table 1.

(3) Fabrication of laminated glass The interlayer film obtained in (1) was heated at 150 ° C and 12 kg / cm ² for 20
Laminated glass was prepared by laminating between 30 cm × 15 cm Pyrex glass and a plate glass and between this plate glass and another plate glass over a period of time.

Example 2 A vinyl chloride-based interlayer glass composition for laminated glass was prepared in the same manner as in Example 1 except that 3 parts by weight of the heat stabilizer B was used in place of the monomer heat stabilizer A. Prepared. Using this composition, an interlayer film for a vinyl chloride-based laminated glass was prepared by the same method as in Example 1, and its physical properties were measured. As a result, the thermal stability of this interlayer film was good.
The yellowness difference ΔN of the laminated glass obtained from this interlayer film is
12.8, and no bleed was noted. The results are shown in Table 1.

Example 3 A vinyl chloride-based laminated glass was prepared in the same manner as in Example 1 except that 2 parts by weight of the heat stabilizer A used in Example 1 and 1 part by weight of the heat stabilizer D containing no sulfur S were used in combination. An intermediate film composition for use was prepared. Using this composition, an interlayer film for a vinyl chloride-based laminated glass was prepared by the same method as in Example 1, and its physical properties were measured. As a result, the thermal stability of this interlayer film was good. The difference in yellowness ΔN of the laminated glass obtained from this interlayer film was 11.2, and no bleeding was observed. The results are shown in Table 1.

Example 4 A vinyl chloride-based laminated glass was prepared in the same manner as in Example 1 except that 2 parts by weight of the heat stabilizer A used in Example 1 and 1 part by weight of the heat stabilizer C containing no sulfur S were used in combination. An intermediate film composition for use was prepared. Using this composition, an interlayer film for a vinyl chloride-based laminated glass was prepared by the same method as in Example 1, and its physical properties were measured. As a result, the thermal stability of this interlayer film was good. The difference in yellowness ΔN of the laminated glass obtained from this interlayer film was 10.5, and no bleeding was observed. The results are shown in Table 1.

Example 5 A vinyl chloride-based laminated glass was prepared in the same manner as in Example 1 except that 2 parts by weight of the heat stabilizer B used in Example 2 and 1 part by weight of the heat stabilizer D containing no sulfur S were used in combination. An intermediate film composition was prepared. Using this composition, an interlayer film for a vinyl chloride-based laminated glass was prepared by the same method as in Example 1, and its physical properties were measured. As a result, the thermal stability of this interlayer film was good. The yellowness difference ΔN of the laminated glass obtained from this interlayer film was 10.8, and no bleeding was observed. The results are shown in Table 1.

Example 6 A vinyl chloride-based laminated glass was prepared in the same manner as in Example 1 except that 2 parts by weight of the heat stabilizer B used in Example 2 and 1 part by weight of the heat stabilizer E containing no sulfur S were used in combination. An intermediate film composition for use was prepared. Using this composition, an interlayer film for a vinyl chloride-based laminated glass was prepared by the same method as in Example 1, and its physical properties were measured. As a result, the thermal stability of this interlayer film was good. The yellow difference ΔN of the laminated glass obtained from this interlayer film was 10.3, and no bleeding was observed. The results are shown in Table 1.

Comparative Example 1 An interlayer film composition for vinyl chloride based laminated glass was prepared in the same manner as in Example 1 except that 3 parts by weight of the heat stabilizer C was used. Using this composition, an interlayer film for a vinyl chloride-based laminated glass was prepared by the same method as in Example 1, and its physical properties were measured. As a result, the thermal stability of this interlayer film was good, but the yellowness difference ΔN of the laminated glass obtained from this interlayer film was 41.6. No bleed was observed. The results are shown in Table 1.

Comparative Example 2 A vinyl chloride type interlayer film composition for laminated glass was prepared in the same manner as in Example 1 except that 3 parts by weight of the heat stabilizer D containing no sulfur S was used. Using this composition, an interlayer film for a vinyl chloride-based laminated glass was prepared by the same method as in Example 1, and its physical properties were measured. As a result, the thermal stability of this interlayer film was insufficient and yellow coloring was observed.
The yellowness difference ΔN of the laminated glass obtained from this interlayer film is
11.3, no bleed was observed. The results are shown in Table 1.

Comparative Example 3 A vinyl chloride-based interlayer film composition for laminated glass was prepared in the same manner as in Example 1 except that 3 parts by weight of a heat stabilizer E containing no sulfur S was used. Using this composition, an interlayer film for a vinyl chloride-based laminated glass was prepared by the same method as in Example 1, and its physical properties were measured. As a result, the thermal stability of this interlayer film was insufficient and yellow coloring was observed. The yellowness difference ΔN of the laminated glass obtained from this interlayer film was 9.6, and bleeding was recognized. The results are shown in Table 1.

(Effect of the invention) The interlayer film composition for a vinyl chloride-based laminated glass of the present invention is
Thus, it has excellent light resistance, thermal stability, film formability, adhesiveness with glass, adhesive workability, and sound insulation. The interlayer film obtained using this composition has excellent light resistance and thermal stability. In addition, the laminated glass produced from this interlayer film showed no bleeding even after being left for a long time,
The transparency can be maintained. Therefore, the interlayer film composition of the present invention is useful as an interlayer film for laminated glass, and the laminated glass of the present invention can be used in fields requiring long-term light resistance and heat resistance, including laminated glass for construction.

Claims (3)

[Claims] 1. At least one monomer selected from the group consisting of ethylene-based hydrocarbons, fatty acid vinyls, acrylic esters and vinyl ethers, and at least one monomer selected from the group consisting of glycidyl methacrylate and glycidyl acrylate. A vinyl chloride-based copolymer obtained by copolymerizing a monomer and vinyl chloride,
An interlayer film composition for a vinyl chloride-based laminated glass, comprising a plasticizer and a heat stabilizer, wherein the heat stabilizer has a bond ratio S / Sn of sulfur S and tin Sn of 0.5.
Vinyl chloride characterized in that it is an alkyltin-containing sulfur compound that satisfies <S / Sn <1.5, and that sulfur forms a cyclic bond or that tin is bonded to oxygen forming an ester bond. An interlayer film composition for laminated glass. 2. An interlayer film for laminated glass, which is formed from the vinyl chloride-based interlayer film composition for laminated glass according to claim 1. 3. An intermediate film for laminated glass according to claim 2
A laminated glass sandwiched between two glass plates.