JPH0386744A - Vinyl chloride copolymer-derived glass laminate interlayer composition and glass laminate interlayer - Google Patents

Abstract

PURPOSE:To prepare a glass laminate interlayer compsn. excellent in the light resistance, thermal stability, film-forming properties, adhesion to glass, processability in adhesion, and sound insulating properties by compounding a specific vinyl chloride copolymer, a hydroxycarboxylic acid, and a plasticizer. CONSTITUTION:At least one monomer (e.g. ethylene) selected from the group consisting of an ethylenically unsatd. hydrocarbon, a vinyl ester of a fatty acid, an acrylate ester, and a vinyl ether is copolymerized with vinyl chloride and glycidyl methacrylate to give a vinyl chloride copolymer, which is compounded with a hydroxycarboxylic acid (e.g. citric acid) and a plasticizer (e.g. dioctyl phthalate).

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a vinyl chloride laminated glass having excellent light resistance, thermal stability, film formability, adhesion to glass, adhesive processability, and sound insulation properties. The present invention relates to an interlayer film composition for laminated glass, and an interlayer film for laminated glass created using the composition.

(Prior Art) A plasticized polyvinyl butyral film is conventionally known as an interlayer film for laminated glass. This membrane is puncture resistant,
Due to its excellent light resistance, it is widely used as an interlayer film for safety glass for automobiles, aircraft, and buildings.

However, plasticized polyvinyl butyral films are difficult to handle because the film surface is too sticky at room temperature, and the adhesion processability to safety glass is not sufficient.

As an interlayer film for laminated glass that eliminates the drawbacks of plasticized polyvinyl butyral films, a technique has been proposed in which an interlayer film is made from an interlayer film composition containing a vinyl chloride resin (Japanese Patent Application Laid-Open No. 162451/1983). , Japanese Patent Publication No. 56-37
Publication No. 252).

(Problems to be Solved by the Invention) The above-mentioned vinyl chloride resin contains glycidyl methacrylate as a component that imparts adhesiveness, and ethylene hydrocarbon, fatty acid vinyl, acrylic ester, vinyl ether, etc. as a component that imparts flexibility. It is a thermoplastic resin copolymerized with at least one monomer: vinyl chloride, but this resin has the drawback of poor light resistance and 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. To suppress discoloration caused by heating,
It may be possible to add a large amount of a heat stabilizer (for example, a sulfur-based stabilizer containing fatty acid alkyltin) to the above-mentioned interlayer film composition, but increasing the amount of the heat stabilizer added may cause a decrease in light resistance. .

JP-A No. 60-27630 discloses that an interlayer film for laminated glass is prepared using an interlayer film composition containing a vinyl chloride-ethylene-glycidyl methacrylate ternary copolymer and a vinyl chloride-ethylene copolymer. Techniques to do this have also been proposed.

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.

The present invention was made in view of the above-mentioned problems, and its purpose is not only to provide excellent adhesion to glass, adhesion processability, and penetration resistance, but also to provide an intermediate layer of laminated glass for architectural use. An object of the present invention is to provide an interlayer film composition for laminated glass that has excellent light resistance and heat resistance required for films, etc., and an interlayer film for laminated glass using the interlayer film composition.

(Means for Solving the Problems) The present invention provides an interlayer film composition for vinyl chloride laminated glass that has excellent light resistance and thermal stability by adding hydroxycarboxylic acid to a specific vinyl chloride copolymer. This was completed based on the inventors' knowledge that the following could be obtained.

The vinyl chloride interlayer film composition for laminated glass of the present invention includes:
A vinyl chloride copolymer obtained by copolymerizing at least one monomer selected from the group consisting of ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers, vinyl chloride, and glycidyl methacrylate; It contains a hydroxycarboxylic acid and a plasticizer, thereby achieving the above object.

The interlayer film for laminated glass of the present invention is created using the above composition.

Glycidyl methacrylate is preferably contained in the vinyl chloride copolymer in an amount of 1% to 10% by weight. 1
If it is less than % 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 an IFI 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. Contains. If it is less than 0.5 flfffi%, when a composition containing the obtained copolymer is used as an interlayer film of a laminated glass, the penetration resistance of the 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 hydrocarbons used include ethylene, propylene, imbutylene, and the like. As fatty acid vinyl,
Vinyl acetate, vinyl caproate, vinyl pelargonate,
Examples include vinyl laurate, vinyl myristate, vinyl palmitate, and the like.

Examples of acrylic esters include methyl acrylate, ethyl acrylate, 2-ethyl acrylate, bovine silyl acrylate, and 2-hydrocytodiethyl acrylate. Vinyl ethers include methyl vinyl ether, ethyl vinyl ether, inbutyl 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 hydroxycarboxylic acid used in the present invention is 0.02 to 0.7ji per 100 parts by weight of the vinyl chloride copolymer.
It is preferable to use the range of J1m. If the amount is less than 0.02 parts by weight, the resulting composition will not have sufficient light resistance. If it exceeds 0.7 parts by weight, the thermal stability and light resistance of the resulting composition will deteriorate. Therefore, when an interlayer film for laminated glass is created using this composition, and when a laminated glass is created using this interlayer film, the interlayer film and the laminated glass tend to discolor to yellow. Also,
If the amount of hydroxycarboxylic acid added is too large, bleeding of the hydroxycarboxylic acid is likely to occur.

Hydroxycarboxylic acids used in the present invention include, for example, tartaric acid, citric acid, tartronic acid, malic acid, α-methylmalic acid, tetrahydroxysuccinic acid, and 1,2-dihydroxy-1,1,2-ethanetricarboxylic acid. etc.

The vinyl chloride interlayer film composition for laminated glass of the present invention includes:
Furthermore, it contains a plasticizer. As the plasticizer, a wide variety of plasticizers commonly used in vinyl chloride resins can be used. For example, examples of the plasticizer include esters of phthalic acid, adipic acid, and sepatic acid, epoxy derivatives, and polyester derivatives. Specific examples include dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate,
Examples include di-2-ethyl adipate, bovine sil, diisodecyl adipate, and the like. This plasticizer is preferably used in an amount of 20 to 60 parts by weight based on 100 parts by weight of the vinyl chloride copolymer. If the amount of plasticizer is too large, when the resulting composition is used as an interlayer for laminated glass,
The mechanical strength (for example, penetration resistance) of this interlayer film is reduced. 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, if necessary. Generally, when forming an interlayer film of laminated glass, and when adhering this interlayer film to glass and processing it, the interlayer film is exposed to high temperatures for a relatively long period of time. Therefore, a thermal stabilizer is added to the composition in order to improve the thermal stability of the interlayer.

As the heat stabilizer, sulfur compounds containing alkyltin of fatty acids, alkyltin laurates of fatty acids, alkyltin malates of fatty acids, metal soaps, etc. are used.

In particular, sulfur compounds containing fatty acid alkyltin, which are effective in small amounts, are preferably used.

Examples of the alkyltin-containing sulfur compounds of the above fatty acids include dimethyltin bisisooctyl glycolate,
Dibutyltin bisisooctylthioglycolic acid ester, dioctyltin bisisooctylthioglycolic acid ester, dimethyltin mercaptoethanol trimethyl hequininate, dibutyltin mercaptoethanol trimethyl hequininate, dioctyltin mercaptoethanol trimethyl hequininate Examples include salt. An example of alkyltin laurate of fatty acid is dibutyltin laurate. Examples of alkyltin malates of fatty acids include dibutyltin maleate and dioctyltin maleate. These heat stabilizers are preferably used in an amount of 1 to 5 parts by weight based on ioo parts by weight of the vinyl chloride copolymer.

If necessary, an ultraviolet absorber, an antioxidant, a coloring agent, etc. may be added to the vinyl chloride interlayer film composition for laminated glass of the present invention. As the ultraviolet absorber, benzotriazole etc. are used.
-Methylphenyl〉benzotriazole, (2°-hydroboxy3゛-t-butyl-5°-methylphenyl)-
5-ria-lobenzotriazole, 2(2'-hydroxy-4'-octo-bovine diphenyl)benzotriazole and the like are preferably used.

and a known molding method, such as a calender roll method,
It is formed into an interlayer film by an extrusion sheet method, an inflation method, a casting method, etc.

When creating an interlayer film composition, the effect of improving the light resistance of the resulting interlayer film changes somewhat depending on the timing of addition of the hydroxycarboxylic acid. The timing of adding hydroxycarboxylic acid is when blending with other stabilizers, plasticizers, etc., immediately after producing the vinyl chloride copolymer, or when forming the interlayer film (for example, when forming the bottom using the calender roll method described above). (when kneading the composition with rolls), etc.
In order to improve the light resistance effect by adding a small amount, it is preferable to add the hydroxycarboxylic acid when the vinyl chloride copolymer is in a slurry or cake state. That is,
It is preferable to add the hydroxycarboxylic acid in the form of a slurry or cake after producing the vinyl chloride copolymer, or after dispersing the dried vinyl chloride copolymer in water to form a slurry or cake. Hydroxycarboxylic acid may be added as an aqueous solution.

In order to create safety laminated glass using the interlayer film obtained in this way, it is sufficient to sandwich the interlayer film between two glass plates, heat-melt it under heat and pressure, and press-bond it. Application devices used for polyvinyl butyral membranes can be used. In this case, the heating temperature is 80~2
00°C, usually 100 to 180°C. The pressure may be as long as it is necessary for adhesion between the interlayer film and the glass plate and for removing air bubbles that may exist at the interface and within the interlayer film, and may be 5 to 50%.
15 Kg/am2 is preferred.

The interlayer film for laminated glass obtained in this way is composed of an interlayer film composition in which hydroxycarboxylic acid is added to a specific vinyl chloride copolymer, so it has excellent film formability, adhesion to glass, and adhesive processability. It also has excellent light resistance and thermal stability. For example, when measuring the light resistance of an interlayer film obtained by adding 0.1 part by weight of hydroxycarboxylic acid, it was found that after 150 hours of ultraviolet irradiation, the yellowness difference ΔN (described later) was almost O, whereas hydroxycarboxylic acid In the intermediate film that does not contain acid, the chromaticity difference ΔN after the UV irradiation tSOS opening time is 1O. Furthermore, when laminated glass is made using this interlayer film, it has excellent penetration resistance and sound insulation properties.

(Example) The present invention will be explained below based on examples.

Note that "parts" below refer to parts by weight, and the physical properties of the obtained interlayer film for laminated glass and laminated glass were measured by the following method.

Physical property measurement method (a) Thermal stability: A piece of interlayer film with a thickness of 0.5111 m (no initial coloration was observed) was heated at an ambient temperature of 19
It was placed in a gear oven at 0° C., left for 60 minutes, and then taken out, and the degree of coloring of the interlayer film was visually judged.

(b) Light resistance: A 0.5 mm thick interlayer film with a thickness of 2.5 mm.
It was sandwiched between 5 mm Pyrex glass and plate glass, and heated and pressed to create a laminated glass. Toshiba high pressure mercury lamp H
Using a -400F lamp, place the laminated glass 25cm from the lamp with the Pyrex glass side in the irradiation direction, and after irradiating it for 500 hours, attach it to a white standard plate using Suga Color Fun Viewer 5M-4. measure,
It was expressed as the difference in yellowness ΔN from the white standard plate.

(C) Bleeding property: A piece of interlayer film for laminated glass with a thickness of 0.5 mm was left in an atmosphere of 95% RH and 75°C for 48 hours, and then taken out and the surface of the film remained sticky. and transparency were observed.

A cake-like vinyl chloride copolymer was obtained by copolymerizing 90% by weight of vinyl chloride with 8% by weight of ethylene and 2% by weight of glycidyl methacrylate. To 100 parts (solid content) of this cake-like vinyl chloride copolymer, 0.02 parts of citric acid was added as a hydroxycarboxylic acid, mixed well, and then dried at 45°C for 24 hours.

Next, 40 parts of dioctyl phthalate (DOP), 3 parts of a dimethyltin mercapto heat stabilizer, and 0.3 parts of a benzotriazole UV absorber are further added, and the mixture is kneaded at 120'C with two 6-inch rolls. As a result, a vinyl chloride-based interlayer film composition for laminated glass was obtained.

This composition was heated at 170'C, 10
By heating and pressurizing at 0 kg/cm2 for 5 minutes, a 0.5-thick vinyl chloride-based interlayer film for laminated glass was prepared.

One piece of the interlayer film for laminated glass with a thickness of 0.5 mm obtained above was replaced with Pyrex glass (thickness 2.5 mm).

30 cm x 15 am) and plate glass (2.5 m thick)
30 parts m x 15 cm) and heated at 150°C.
, 12 kg/am2 for 20 minutes to produce a laminated glass.

The physical properties of the vinyl chloride interlayer film for laminated glass and the laminated glass thus obtained were measured.

The results are shown in Table 1.

An interlayer film composition for laminated glass was obtained in the same manner as in Example 1, except that the amounts of citric acid shown in Table 1 were used. Using this composition, an interlayer film for laminated glass and a laminated glass were prepared in the same manner as in Example 1, and the physical properties thereof were measured.

The results are shown in Table 1.

Toouen L An interlayer film composition for laminated glass was obtained in the same manner as in Example 1, except that 0.03 parts of tartaric acid was used in place of citric acid. Using this composition, an interlayer film for laminated glass and a laminated glass were fabricated in the same manner as in Example 1, and the physical properties thereof were measured. The results are shown in Table 1.

An interlayer film composition for laminated glass was obtained in the same manner as in Example 7, except that the amounts of tartaric acid shown in Table 1 were used. Using this composition, an interlayer film for laminated glass and a laminated glass were prepared in the same manner as in Example 1, and the physical properties thereof were measured. The results are shown in Table 1.

A slurry-like copolymer was prepared using the same vinyl chloride copolymer composition as in Example 1. An interlayer film composition for laminated glass was obtained in the same manner as in Example 1, except that 0.02 parts of citric acid was added to 100 parts (solid content) of this slurry-like vinyl chloride copolymer. Implemented using fP+
An interlayer film for laminated glass and a laminated glass were prepared by the same method as in Example 1, and the physical properties thereof were measured. The results are shown in Table 1.

and 0.1 part of Kudan citric acid, dioctyl phthalate (DOP)
An interlayer film composition for laminated glass was obtained in the same manner as in Example 1, except that 40 parts of dimethyltinmercapto heat stabilizer, 3 parts of dimethyltin mercapto-based heat stabilizer, and 0.3 WJ of benzotriazole-based ultraviolet absorber were added to the copolymer. Using this composition, an interlayer film for laminated glass and a laminated glass were prepared in the same manner as in Example 1, and the physical properties thereof were measured. The results are shown in Table 1.

Example 12 except that the amount of citric acid added was 0.13 parts.
An interlayer film composition for laminated glass was obtained in the same manner as above. Using this composition, an interlayer film for laminated glass and a laminated glass were prepared in the same manner as in Example 1, and the physical properties thereof were measured. The results are shown in Table 1.

An interlayer film composition for laminated glass was obtained in the same manner as in Example 1, except that hydrocarbon dicarboxylic acid was not added.

Using this composition, an interlayer film for laminated glass and a laminated glass were prepared in the same manner as in Example 1, and the physical properties thereof were measured. The results are shown in Table 1.

(Left below) As is clear from the Examples and Comparative Examples, the interlayer film for laminated glass obtained from the vinyl chloride interlayer film composition for laminated glass of the present invention has excellent thermal stability. The laminated glass made from this interlayer film has a small yellowness difference ΔN and excellent light resistance, and no bleeding is observed. Although the interlayer film for laminated glass obtained from the vinyl chloride-based interlayer film composition for laminated glass that does not contain hydroxycarboxylic acid has excellent thermal stability, the laminated glass made with this interlayer film has a yellowness difference ΔN. is large and the light resistance is poor.

(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, the 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 of the present invention has long-term light resistance,
It is useful as an interlayer film for laminated glass that requires heat resistance.

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Claims (1)

[Claims] 1. Obtained by copolymerizing vinyl chloride and glycidyl methacrylate with at least one monomer selected from the group consisting of ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers. An interlayer film composition for vinyl chloride-based laminated glass, comprising a vinyl chloride copolymer, a hydroxycarboxylic acid, and a plasticizer. 2. An interlayer film for laminated glass formed from the composition according to claim 1.