JPH03170351A - Vinyl chloride-based interlayer composition for laminated glass - Google Patents

Abstract

PURPOSE:To improve light resistance, film-forming properties, adhesion to glass, etc., by blending a vinyl chloride copolymer, composed of vinyl chloride, a glycidyl ester and vinyl monomer with a polyvinyl acetal resin, plasticizer and heat stabilizer. CONSTITUTION:A interlayer composition for laminated glass formed by containing (A) a vinyl chloride copolymer containing vinyl chloride, at least one glycidyl ester selected from glycidyl methacrylate and glycidyl acrylate and at least one vinyl monomer selected from ethylenically unsaturated hydrocarbons, vinyl esters of fatty acids, acrylic esters and vinyl ethers as monomer components with (B) a polyvinyl acetal resin, (C) a plasticizer and (D) a heat stabilizer. The polyvinyl acetal resin is contained in an amount of about 1-10 pts.wt. based on 100 pts.wt. vinyl chloride copolymer.

Description

[Detailed description of the invention] (Industrial application field) The present invention has excellent heat stability and light resistance, and also has excellent film shapeability, adhesion to glass, adhesive processability, and sound insulation properties. This invention relates to a vinyl chloride interlayer film assembly for laminated glass.

(Prior art) Conventionally, laminated glass using a plasticized polyvinyl butyral film as an interlayer film has been widely used in automobiles, aircraft, buildings, etc. because the interlayer film deteriorates in penetration resistance and light resistance. It is being

However, the plasticized polyvinyl butyral film has a drawback that the film surface has strong adhesiveness at room temperature and is poor in adhesion processability with glass.

Therefore, as an interlayer film that has excellent adhesion processability to glass and excellent sound insulation properties, at least one compound selected from vinyl chloride and glycidyl meccrylate, ethylenically unsaturated hydrocarbons, vinyl fatty acids, and vinyl ethers is used.
For example, a vinyl chloride interlayer film made of a vinyl chloride copolymer mixed with a plasticizer, a heat stabilizer, an ultraviolet absorber, etc.
JP-A-55-162451, JP-A-56-372
This method has already been proposed in Japanese Patent Application Laid-open No. 52, Japanese Patent Application Laid-Open No. 60-27360, and the like. However, interlayer films containing such vinyl chloride resins, on the other hand, have poor light resistance and stain, making them difficult to apply to applications that will be used for long periods of time, such as in architectural applications. There is.

Conventionally, it has been generally known that it is effective to add a polyol to a vinyl chloride resin in order to improve its light resistance and thermal stability. However, polyols
Because polyols are inherently hydrophilic, they have poor compatibility with resins or plasticizers. Therefore, when kneading polyols as they are with vinyl chloride resins, the polyols are poorly dispersed and may deteriorate the impact strength of the product. , or the polyol may bleed out.

(Problems to be Solved by the Invention) The present invention has been made in order to solve the above-mentioned problems in conventional vinyl chloride interlayer film assemblies for laminated glass. A further object of the present invention is to provide a vinyl chloride-based interlayer film assembly for laminated glass that has excellent film shapeability, adhesion to glass, adhesion workability, and sound insulation properties.

(Means for Solving the Problems) The vinyl chloride-based interlayer film composite for laminated glass according to the present invention comprises: (A) at least one member selected from (a) vinyl chloride, (b) glycidyl methacrylate and glycidyl acrylate; glycidyl ester of
and (C) a vinyl chloride copolymer containing at least one vinyl monomer selected from ethylenically unsaturated hydrocarbons, fatty acid vinyls, acrylic esters, and vinyl ethers, and (B) polyvinyl acetal. It is characterized by consisting of a resin, (C) a plasticizer, and (D) a heat stabilizer.

In the present invention, the content of the glycidyl ester monomer component in the vinyl chloride copolymer is preferably in the range of 1 to 10% by weight. When the glycidyl ester monomer content in the vinyl chloride copolymer is less than 1% by weight, the resulting interlayer film has poor adhesion to glass. On the other hand,
When the amount is more than 10%, the resulting interlayer is hard;
It also has a high softening temperature and has poor bonding properties with glass.

As the vinyl monomer in the vinyl chloride copolymer, at least one selected from ethylenically unsaturated hydrocarbons, vinyl fatty acids, acrinoleic acid esters, and vinyl ethers is used. Examples of ethylenically unsaturated hydrocarbons include ethylene, propylene, and isobutylene; examples of vinyl include vinyl acetate, vinyl caproate, vinyl pelargonate, vinyl laurate, vinyl myristate, and vinyl valmitate. Examples of acrylic esters include methyl acrylate,
Examples of the vinyl ether include ethyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and the like. Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, and cetyl vinyl ether.

The content of these vinyl monomers in the vinyl chloride copolymer is preferably in the range of 0.5 to 10% by weight.

When the content of the vinyl monomer component in the vinyl chloride copolymer is less than 0.5% by weight, the resulting interlayer film has poor penetration resistance. However, when more than 10% by weight is used, the yield during copolymer production may decrease, or the transparency of the resulting copolymer may decrease.

The above-mentioned vinyl chloride copolymer can be produced by copolymerization of vinyl chloride, glycidyl ester, and vinyl monomer by suspension polymerization, emulsion polymerization, solution polymerization, etc., but the thermal stability of the resulting vinyl chloride copolymer From the aspects of gender and economic efficiency,
Preference is given to suspension polymerization.

The polyvinyl acetal resin used in the present invention includes polyvinyl formal, polyvinyl acetal in a narrow sense (acetalized with acetaldehyde),
Examples include polyvinyl butyral, and polyvinyl butyral and polyvinyl acetal in a narrow sense are preferably used.

It is preferable that such a polyvinyl acetal resin has an acetalization degree of 50 to 75 mol % and a polymerization degree of 300 to 3000.

The vinyl chloride interlayer film assembly according to the present invention preferably contains such a polyvinyl acetal resin in an amount of 1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride copolymer. In the vinyl chloride interlayer film composition,
When the content of polyvinyl acetal phase resin is less than 1 part by weight with respect to 100 parts by weight of vinyl chloride copolymer,
The resulting interlayer film still has insufficient light resistance and thermal stability, and on the other hand, when the amount exceeds 10 parts by weight, the compatibility with the vinyl chloride copolymer becomes poor and the resulting interlayer film becomes cloudy. So I don't like it.

The vinyl chloride interlayer film composition according to the present invention includes a heat stabilizer,
Preferably, it contains an organic tin-based heat stabilizer. Examples of such organotin heat stabilizers include alkylated tin compounds of fatty acids such as butyltin laurate, butyltin maleate, and octyltin laurate, dibutyltin bis(3-mercaptopropionic acid ester) salts, and Alkyltin-containing sulfur compounds such as di-n-octyltin bis(isooctylthioglycolic acid ester) salt are preferably used. Such an organic tin-based heat stabilizer is usually used in an amount of 0.5 to 100 parts by weight of the vinyl chloride copolymer.
It is contained in a range of 5 parts by weight.

Furthermore, the vinyl chloride interlayer film assembly according to the present invention contains a plasticizer. As the plasticizer, any plasticizer that is used for ordinary vinyl chloride resins can be used. Examples of such plasticizers include esters of phthalic acid, adipic acid, and sepatic acid, epoxy resin derivatives, and polyester derivatives. Specifically, examples of phthalate esters include dioctyl phthalate dibutyl phthalate, diisobutyl phthalate, and examples of adipate esters include di-2-ethylhexyl adipate, diisodecyl adipate, and the like. . In addition, examples of epoxy resin derivatives include epoxidized soybean oil,
Examples include epoxy fatty acid monoester.

The blending amount of such a plasticizer is 10% of the vinyl chloride copolymer.
A range of 20 to 60 parts by weight is usually suitable for 0 parts by weight. The amount of plasticizer blended is vinyl chloride copolymer 100%
If it is less than 20 parts by weight, the resulting interlayer film will have poor plasticity and light resistance, while if it exceeds 60 parts by weight, the resulting interlayer film will have poor S mechanical strength such as penetration resistance. decreases.

The interlayer film according to the present invention comprises the above-mentioned vinyl chloride copolymer,
In addition to the acetal resin, heat stabilizer, and plasticizer, it may further contain an ultraviolet absorber, an antioxidant, a coloring agent, a lubricant, a filler, etc., if necessary.

Among the above additives, for example, penzotriazole-based additives are preferably used as ultraviolet absorbers. Specific examples include 2-(2'-hydroxy-5''-methylphenyl)penzotriazole, 92-(2'-hydroxy-3'-L-butyl-5'-methylphenyl)-5-chlorobenzotriazole , 2-
Examples include (2'-hydroxy-3'',5'-di-t-butylphenyl)-5-chloropenzotriazole and 2(2'-hydroxy-4'-octoxyphenyl)penzotriazole.

Furthermore, as the antioxidant, phenolic ones are preferably used. Specific examples include 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4.
4”-butylidenebis(3-methyl-6-t-butylphenol), 4.4”-thiobis(3-methyl-6-t
-butylphenol), 4,4'-isopropylidene bis(phenol), and the like.

The interlayer film according to the present invention comprises the above-mentioned vinyl chloride copolymer,
By forming a film using a polyvinyl acetal resin, a heat stabilizer, and a plasticizer together with the above-mentioned additives, if necessary, by a known method such as a calender roll method, an extrusion method, an inflation method, or a casting method. Obtainable.

In order to manufacture laminated glass using such a film as an interlayer film, the interlayer film is sandwiched between glasses according to the conventional method, the interlayer film is melted under pressure and heat, and the glasses are bonded together. good. The heating temperature is 80 to 200°C, usually
A temperature range of 100 to 180°C is preferred. The pressure may be any pressure that can bring the interlayer film and glass into close contact and remove air bubbles at the interface between the interlayer film and glass and within the interlayer film, and is usually 5 to 5.
A range of 15 kg/cIil is preferred. For such heat-compression bonding, the same bonding equipment as conventionally used for manufacturing laminated glass using a plasticized polyvinyl butyral interlayer film is used, such as a heated press or a press roll with a heating furnace, or a hydraulic or pneumatic autoclave. can be used.

(Effects of the Invention) According to the interlayer film of the present invention, a vinyl chloride copolymer containing vinyl chloride, glycidyl ester, and vinyl monomer as monomers, and also as a resin component and as a type of polyol, Polyvinyl chloride copolymer resin is added to plasticize it, and a heat stabilizer is added to it to obtain a vinyl chloride interlayer film assembly for laminated glass. Alternatively, as a result of preventing the vinyl chloride copolymer from being colored due to the heat stabilizer blended into the copolymer, light resistance can be improved while ensuring thermal stability.

That is, according to the present invention, the above-mentioned problems caused by using a vinyl chloride copolymer can be solved while taking advantage of the advantages such as penetration resistance and excellent adhesion to glass as an interlayer film using a polyvinyl acetal resin. As a result, it is possible to obtain a vinyl chloride-based interlayer film assembly for laminated glass which has excellent film formability, adhesion to glass, adhesion workability, and sound insulation properties.

(Example) The present invention will be specifically described below with reference to Examples.

Examples 1 to 5 A vinyl chloride copolymer consisting of 10 moles of vinyl chloride, 20 moles of ethylene, and 1 mole of glycidyl methacrylate was mixed with the components shown in Table 1 to 12
It was kneaded at 0°C with two 6-inch rolls, and then kneaded using a hydraulic press at 170°C and 100 kg/cffl to a thickness of 0. A 5 mm interlayer film was prepared.

This interlayer film was sandwiched between 30cm x 15cm Pyrex glass and float glass, and the temperature was 113kg at 140°C.
A laminated glass was produced by autoclaving under a pressure of /cfl.

Table 1 shows the physical properties of the laminated glass thus obtained.

Comparative Example 1 An interlayer film containing no acetal resin was prepared in the same manner as in the example, and a laminated glass was manufactured using this in the same manner as in the example. Its physical properties are shown in Table 1.

Comparative Example 2 An interlayer film was prepared in the same manner as in Example 1, except that polyvinyl alcohol was used instead of the acetal resin, and a laminated glass was manufactured using this in the same manner as in Example. Its physical properties 13 are shown in Table 1.

In Table 1, thermal stability, light resistance and bleedability are as follows:
Evaluation was made as follows.

Thermal stability thickness 0. A 5 mm thick interlayer film was used as a test piece, and after being left in a gear oven at an ambient temperature of 190''C for 1 hour, it was taken out, and the presence or absence of coloring and the degree of coloring were visually evaluated.

Light resistance thickness 0. A 5 mm interlayer film was used as a test piece, and the thickness was 2.5 mm. A laminated glass was produced by sandwiching the glass between a 5 mm Pyrex glass and a float glass, heating the glass under pressure, and bonding them together.

A light resistance test of this laminated glass was conducted in accordance with JIS R 3205, with the Virex glass side as the irradiation side. After 300 hours of irradiation, the sample was attached to a standard white plate, and the yellow color difference ΔN with the standard white plate was measured using a multi-light source spectrophotometer (MS (-2 model) manufactured by Suga Test Instruments).

Bleedability 14 Thickness 0. A 5 mm thick interlayer film was used as a test piece, and after being left in an atmosphere with a relative humidity of 95% and a temperature of 70°C for one week, the presence or absence of stickiness and spots on the film surface was checked by touch and visual inspection.

Claims (1)

[Claims] (1) (A) (a) vinyl chloride, (b) at least one glycidyl ester selected from glycidyl methacrylate and glycidyl acrylate;
and (c) a vinyl chloride copolymer whose monomer component is at least one vinyl monomer selected from ethylenically unsaturated hydrocarbons, fatty acid vinyls, acrylic esters, and vinyl ethers; and (B) polyvinyl acetal resin. A vinyl chloride interlayer film composition for laminated glass, comprising: (C) a plasticizer; and (D) a heat stabilizer.