JPH0365543A - Intermediate film composition for vinyl chloride-based safety glass, intermediate film for safety glass using same composition and safety glass using same intermediate film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an interlayer film composition for laminated glass, an interlayer film for laminated glass formed into a sheet shape using this interlayer film Mikaimono, and an interlayer film composition for laminated glass. It relates to safety laminated glass used in automobiles, architecture, etc., which is produced by sandwiching a film between two sheets of glass.

(Prior Art) The use of plasticized polyvinyl butyral as an interlayer film composition for safety laminated glass is widely known, and plasticized polyvinyl butyral films have excellent penetration resistance and light resistance, so they are used in automobiles, Widely used for safety laminated glass for aircraft and architecture. However, since the plasticized polyvinyl butyral film has too strong adhesiveness on the film surface at room temperature, it has the disadvantage of poor adhesion processability with glass.

As an interlayer film for laminated glass that eliminates the drawbacks of plasticized polyvinyl butyral films, we have developed a technology for creating an interlayer film from an interlayer film composition containing a vinyl chloride resin and sandwiching this interlayer film between two glass plates. A technique for producing laminated glass by heat-pressing has been proposed. (Unexamined Japanese Patent Publication No. 55-162
451, JP-A-56-37252) (Problems to be Solved by the Invention) The above-mentioned vinyl chloride resin contains glycidyl methacrylate or glycidyl acrylate as a component imparting adhesiveness,
This thermoplastic resin is a copolymer of vinyl chloride and at least one monomer selected from ethylene hydrocarbons, fatty acid vinyl, acrylic ester, vinyl ether, etc. as a component that imparts flexibility, but this resin has light resistance. It also has the disadvantage of poor thermal stability, that is, it yellows when exposed to light or heat.

Therefore, an interlayer film formed from this interlayer film composition is easily colored by heat during film formation and during processing when attached to glass.

Furthermore, JP-A-60-27630 discloses an interlayer film for laminated glass using an interlayer film composition containing a vinyl chloride-ethylene-glycidyl methacrylate ternary copolymer and a vinyl chloride-ethylene copolymer. Techniques have also been proposed to create .

However, this interlayer film also has poor light resistance, making it difficult to use it as safety glass for long-term use in buildings and the like. Furthermore, this interlayer film was inferior in thermal stability compared to the general vinyl chloride resin interlayer film described above. Addition of a heat stabilizer may be considered to suppress discoloration due to heating, but no improvement in heat stability is seen even with the addition of a fatty acid alkyltin compound, which is a heat stabilizer conventionally used. Additionally, adding a fatty acid alkyltin-containing sulfur compound containing a large amount of sulfur component, which is relatively hard to thermal stability, improved thermal stability, but the resulting interlayer film had poor light resistance. .

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an interlayer film composition for laminated glass, an interlayer film for laminated glass, and laminated glass that are excellent in both light resistance and heat resistance.

(Means for Solving the Problems) That is, the interlayer film composition for vinyl chloride laminated glass of the first invention contains at least one monomer selected from the group consisting of ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers. , a vinyl chloride copolymer obtained by copolymerizing vinyl chloride, at least one monomer selected from the group consisting of glycidyl methacrylate and glycidyl acrylate, a plasticizer, and a heat stabilizer. In the polyvinyl chloride-based interlayer film composition for laminated glass, the thermal stabilizer has a bonding ratio S/Sn of sulfur S and tin that satisfies Q, 5<S/Sn<1.5, and sulfur is It is characterized by being an alkyltin-containing sulfur compound that forms a cyclic bond or in which tin is bonded to oxygen forming an ester bond.

The interlayer film for laminated glass of the second invention is produced using the above composition. Moreover, the laminated glass of the third invention is formed by sandwiching the above 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,
Preferably, the vinyl chloride copolymer contains 1% by weight to 1O
It is contained in an amount of % by weight. If it is less than 1% by weight, when the composition containing the obtained copolymer is used as an interlayer film for laminated glass, the adhesion between the interlayer film and glass will be insufficient. If it exceeds 10% by weight, the resulting composition containing the copolymer will become very hard and its softening temperature will become high.

Therefore, it becomes difficult to bond an interlayer film using this composition to glass.

At least one monomer selected from the group consisting of ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers is preferably added to the vinyl chloride copolymer in an amount of 0.5% to 10% by weight. Contained in If it is less than 0.5% by weight, when a composition containing the obtained copolymer is used as an interlayer film for laminated glass, the penetration resistance of laminated glass will be insufficient. If it exceeds 10% by weight, the yield of the copolymer after copolymerizing this monomer will decrease, and the transparency of the composition containing this copolymer will deteriorate.

Ethylene-based hydrocarbons used include ethylene, propylene, isobutylene, and the like. Examples of vinyl fatty acids include vinyl acetate, vinyl caproate, vinyl pelargonate, vinyl laurate, vinyl myristate, vinyl balmitate, and the like. Acrylic acid esters include
Methyl acrylate, ethyl acrylate, acrylic acid-2
-Ethylhexyl, 2-hydroxyethyl acrylate, etc. Vinyl ethers include 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 because it yields a copolymer with excellent thermal stability and is economical.

The vinyl chloride interlayer film composition for laminated glass of the present invention includes:
Furthermore, it contains a plasticizer. As the plasticizer, any plasticizer generally used for vinyl chloride resins can be used. For example, this plasticizer includes dioctyl phthalate (
DOP).

This plasticizer is preferably vinyl chloride copolymer 10
It is used in a proportion of 20 to 60 parts by weight relative to 0 parts by weight. If the amount of plasticizer is too large, the mechanical strength (for example, penetration resistance)' of the interlayer film will decrease when the resulting composition is used as an interlayer film for laminated glass. If the amount of plasticizer is too small, the light resistance and plasticity of this interlayer film will decrease.

A heat stabilizer is further added to the vinyl chloride interlayer film composition for laminated glass of the present invention. Generally, when forming an interlayer film of laminated glass, and when bonding the interlayer film to a glass glass and processing the interlayer film, the interlayer film is exposed to high temperatures for a long period of time.

Therefore, a thermal stabilizer is added to the composition in order to improve the thermal stability of the interlayer. The heat stabilizer is preferably used in an amount of 1 part by weight per 100 parts by weight of the vinyl chloride copolymer.
It is used in a proportion of 2 to 4 parts by weight, more preferably 2 to 4 parts by weight. When a heat stabilizer containing a relatively large amount of sulfur component is added, the resulting composition has excellent heat resistance, but its light resistance decreases. In other words, 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, M
Since the light resistance of i-Kaimono is poor, heat stabilizers include, for example,
The ratio S/Sn of sulfur S and tin Sn as represented by the following formulas (1), (II), and (I[I) is 0.5<S/Sn<
An alkyltin-containing sulfur compound satisfying S/Sn=1.5 is used, and a compound with S/Sn=1 is particularly preferably used. Even if this compound is added in a small amount to the vinyl chloride copolymer, it is sufficiently effective in terms of the heat resistance and light resistance. Specific examples of the heat stabilizer used in the present invention are as follows: Integer from 1 to 20, m
is an integer from 2 to 20. ).

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

The polyvinyl chloride interlayer film composition for laminated glass of the present invention may contain ultraviolet absorbers, antioxidants, colorants, etc., if necessary, and may be formed using known molding methods such as calender roll method, extrusion sheet molding method, etc. It is formed into an interlayer film by a method such as a molding method, an inflation method, or a casting method. The obtained interlayer film is sandwiched between two pieces of glass, and is then thermally melted and bonded under heat and pressure to form a safety laminated glass. Heating temperature is 80°C ~ 200″C
1 Preferably, the temperature is 100°C to 180°C. The pressure is the pressure necessary to bring the interlayer film and glass into close contact and to remove air bubbles at the interface between the two and within the interlayer film.

This pressure is preferably between 5 and 15 Kg/aa.

To pressurize this interlayer film, a bonding device used to press conventional plasticized polyvinyl butyral films to glass is used.

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

The structural formula of the heat stabilizer used in the present examples and comparative examples is as follows.

R: CaHq R: C, H9 R: C, H9 R: C, H9 Actual 10 (1) Preparation of interlayer film for vinyl chloride laminated glass 90% by weight of vinyl chloride, 8% by weight of ethylene and methacrylic A vinyl chloride copolymer was prepared by copolymerizing 2% by weight of glycidyl acid. This vinyl chloride copolymer 100
Add 3 parts by weight of heat stabilizer A, 1 part by weight of 40 parts of dioctyl phthalate (DOP), and 0.3 parts by weight of benzotriazole ultraviolet absorber to the parts by weight, and heat at 120°C for 6 parts by weight.
A vinyl chloride interlayer film composition for laminated glass was prepared by kneading with two inch rolls. This composition was heated at 170°C at 1100 kg/c using a hydraulic press device.
By heating and pressurizing at T1 for 5 minutes, a 0.5-thick vinyl chloride interlayer film for laminated glass was produced.

(2) Measurement of physical properties of vinyl chloride-based interlayer film for laminated glass 1
A piece of the interlayer film for laminated glass with a thickness of 0.5 aun (no initial coloration was observed) prepared in , Thermal Stability (1) was placed in a gear oven at an ambient temperature of 190°C and left for 60 minutes. After that, it was 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 A piece of the 0.5 mm thick interlayer film for laminated glass prepared in (1) was sandwiched between 2.5 mm thick Pyrex glass and temporary glass, and heated to 150°C and 12 kg/cJ. A laminated glass was produced by applying heat and pressure. For the Pyrex glass side of this laminated glass, 25 cm from the glass.
Light was irradiated using a Toshiba high-pressure mercury lamp H-400F at a distance of 500 hours. After irradiation,
This laminated glass was pasted on a white standard plate, and the yellowness of Suga Color Computer 5M-4 was measured and expressed as the yellowness difference ΔN between this white standard plate and the laminated glass.

The yellowness difference ΔN of this laminated glass was 18.7. The results are shown in Table 1.

3. A piece of the interlayer film with a thickness of 0.5 mm prepared using bleed property (1),
After being left in an atmosphere of 95% RH and 70°C for 48 hours, the film was taken out and the presence or absence of stickiness on the film surface and transparency were observed. The results are shown in Table 1.

(3) Production of laminated glass The interlayer film obtained in (1) was
30C111X 15c for 20 minutes at
A laminated glass was produced by bonding between the Pyrex glass of No. m and a plate glass, and between this temporary glass and another plate glass.

1. An interlayer film composition for vinyl chloride laminated glass was prepared in the same manner as in Example 1, except that 3 parts by weight of the heavy heat stabilizer B was used in place of the monomeric heat stabilizer A. was prepared. Using this composition, a vinyl chloride interlayer film for laminated glass was prepared in the same manner as in Example 1, and its physical properties were measured. As a result, the thermal stability of this intermediate film was good.

The yellowness difference ΔN of the laminated glass obtained from this interlayer film was 12.8, and no bleeding was observed.

These results are shown in Table 1.

Example 1 PVC 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 containing no sulfur S were used. An interlayer film composition was prepared. Using this composition, a vinyl chloride interlayer film for laminated glass was prepared in the same manner as in Example 1, and its physical properties were measured. As a result, the thermal stability of this intermediate film was good. The yellowness difference ΔN of the laminated glass obtained from this interlayer film was 11.2, and no bleeding was observed. These results are shown in Table 1.

PVC laminated glass was prepared in the same manner as in Example 1, except that 2 parts by weight of heat stabilizer A used in Example 1 and 1 part by weight of heat stabilizer C, which does not contain sulfur S, were used. An interlayer film composition was prepared. Using this composition, a vinyl chloride interlayer film for laminated glass was prepared in the same manner as in Example 1, and its physical properties were measured. As a result, the thermal stability of this intermediate film was good. The yellowness difference ΔN of the laminated glass obtained from this interlayer film was 10.5, and no bleeding was observed. These results are shown in Table 1.

A vinyl chloride combination 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 B which does not contain sulfur S were used. An interlayer film composition for glass was prepared. Using this composition, a vinyl chloride interlayer film for laminated glass was prepared in the same manner as in Example 1, and its physical properties were measured. As a result, the thermal stability of this intermediate film was good. The yellowness difference ΔN of the laminated glass obtained from this interlayer film was 10.8, and no bleeding was observed. These results are shown in Table 1.

Example 1041 For vinyl chloride laminated glass in the same manner as in Example 1 except that 2 parts by weight of heat stabilizer B used in Example 2 and 1 part by weight of heat stabilizer E not containing sulfur S were used. An interlayer film composition was prepared. Using this M1 product, a vinyl chloride interlayer film for laminated glass was prepared in the same manner as in Example 1, and its physical properties were measured. As a result, the thermal stability of this intermediate film was good. The yellowness difference ΔN of the laminated glass obtained from this interlayer film was 10.3, and no bleeding was observed. These results are shown in Table 1.

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 comparative dish heat stabilizer C was used. Using this composition, a vinyl chloride interlayer film for laminated glass was prepared in the same manner as in Example 1, and its physical properties were measured. As a result, although the thermal stability of this interlayer film was good, the yellowness difference ΔN of the laminated glass obtained from this interlayer film was 41.6. No bleeding was observed. These results are shown in Table 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 a heat stabilizer containing no main sulfur S was used. Using this composition, a vinyl chloride interlayer film for laminated glass was prepared in the same manner as in Example 1, and its physical properties were measured. As a result, the thermal stability of this intermediate film was insufficient and yellow coloring was observed. The yellowness difference ΔN of the laminated glass obtained from this interlayer film is 1
1.3, and no bleeding was observed. These results are shown in Table 1.

Northern Flame 1 A vinyl chloride-based laminated glass layer interlayer film Ijl was prepared in the same manner as in Example 1, except that 3 parts by weight of heat stabilizer E not containing sulfur S was used. Using this composition, a vinyl chloride interlayer film for laminated glass was prepared in the same manner as in Example 1, and its physical properties were measured. As a result, the thermal stability of this intermediate film was insufficient and yellow coloring was observed. Yellowness difference ΔN of laminated glass obtained from this interlayer film
was 9.6, and bleeding was observed. These results are shown in Table 1.

(The following is a blank space) (Effects of the invention) The vinyl chloride interlayer film composition for laminated glass of the present invention has the following properties:
As described above, it has excellent light resistance, thermal stability, film formability, adhesion to glass, adhesive processability, and sound insulation properties. An interlayer film obtained using this composition has excellent light resistance and thermal stability. In addition, laminated glass made from this interlayer film shows no bleeding even after being left for a long time.
Transparency can be maintained. Therefore, the interlayer film composition of the present invention is useful as an interlayer film for laminated glass, and wood laminated glass can be used in fields where long-term light resistance and heat resistance are required for laminated architectural glass.

that's all

Claims (1)

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