JP2001163640A - Intermediate film for laminated glass and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate film for laminated glass suitable for obtaining the laminated glass which has excellent basic performance necessary as the laminated glass including transparency, weatherability, adhesiveness, penetration resistance, etc., and lessens the occurrence of whitening at the peripheral edges of the sandwich glass even when the laminated glass is rested under an atmosphere of high humidity and the laminated glass formed by using the intermediate film. SOLUTION: The intermediate film for the laminated glass which consists of a plasticized polyvinyl acetal resin film and a polyester resin film and of which the outermost layer is the plasticized polyvinyl acetal resin film is 40 to 80 N/cm at 20 deg.C in 90 deg. peel adhesion between the glass and the plasticized polyvinyl acetal resin film in the laminated glass using the intermediate film described above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an interlayer film for laminated glass and a laminated glass using the interlayer film.

[0002]

2. Description of the Related Art Conventionally, laminated glass has been used for automobiles,
Widely used as window glass for buildings and the like. The laminated glass is manufactured by interposing a laminated glass intermediate film formed by forming a plasticized polyvinyl acetal resin such as a polyvinyl butyral resin plasticized by a plasticizer between at least a pair of glasses, and integrally forming the laminated glass. The one given is typical. Such laminated glass is transparent,
It has good weather resistance and adhesiveness, and also has excellent penetration resistance. That is, if an impact is applied to this, the glass is broken, but the interlayer film interposed between the glass is not easily broken, and the glass remains adhered to the interlayer film even after the breakage. The fragments are less likely to be scattered, and thus have a function of preventing a human body, for example, inside a car or a building from being injured by the fragments of glass.

However, when the laminated glass is left in a humid atmosphere, the periphery of the laminated glass
Usually, since the intermediate film is in direct contact with the environmental air, the problem of moisture resistance arises in that the intermediate film at the peripheral portion is liable to cause whitening due to moisture absorption. That is, with respect to the moisture resistance performance, not only the side glass of an automobile or the like whose peripheral edge is exposed, but also the windshield is required to have a high quality level due to the open edge and the like.

To cope with the above problems, for example, Japanese Patent Application Laid-Open No. 7-41340 discloses an intermediate for laminated glass comprising a polyvinyl acetal resin and a resin composition containing a plasticizer, a metal carboxylate and a linear fatty acid. Membrane "is disclosed. However, in the laminated glass using the interlayer film for a laminated glass, although the whitening of the peripheral portion after the moisture resistance test is reduced, it is still insufficient. Further, when the amount of the metal salt added is reduced, the whitening phenomenon is improved, but the penetration resistance is reduced. In particular, it has been considered that it is difficult to reduce the amount of metal salt to be added to windshields of automobiles and the like because it is essential to maintain a quality level of penetration resistance. Also, side glasses for automobiles and the like are required to have a considerable level of penetration resistance for the purpose of crime prevention and the like. The inventor of the present invention has found that, while maintaining the level of penetration resistance, by reducing the amount of metal salt added, the performance of laminated glass is stably excellent over a long period of time, and even when manufacturing a laminated glass, the interlayer film is also required. The present inventors have found a method capable of obtaining a stable adhesive force between the glass and glass and suppressing the foaming rate, thereby improving the yield.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems by providing excellent basic properties required for laminated glass such as transparency, weather resistance, adhesion and penetration resistance.
Also, to provide an interlayer film for a laminated glass suitable for obtaining a laminated glass which is less likely to cause a whitening phenomenon on a peripheral portion of the laminated glass even when left in an atmosphere having a high humidity, and a laminated glass using the intermediate film. As an issue.

[0006]

The interlayer for laminated glass according to the invention of claim 1 (hereinafter referred to as invention 1) comprises a plasticized polyvinyl acetal resin film and a polyester resin film, and the outermost layer is plasticized. An interlayer for laminated glass, which is a polyvinyl acetal resin film, wherein the laminated glass using the interlayer has a 90-degree peel adhesion between the glass and the plasticized polyvinyl acetal resin film of 20.
It is characterized by being 40 to 80 N / cm at ° C.

The interlayer film for laminated glass according to the invention of claim 2 (hereinafter referred to as invention 2) is the interlayer film for laminated glass according to the above invention 1, wherein the plasticized polyvinyl acetal resin film contains 40 ppm or less of magnesium, Further, it is a plasticized polyvinyl acetal resin film containing 100 ppm or less of potassium.

[0008] The interlayer film for laminated glass according to the invention described in claim 3 (hereinafter referred to as invention 3) is provided by the invention 1 or 2 described above.
Is characterized in that the polyvinyl acetal resin used in the interlayer film for laminated glass according to (1) is a polyvinyl butyral resin having a butyralization degree of 60 to 70 mol%.

The interlayer film for laminated glass according to the invention of claim 4 (hereinafter referred to as invention 4) is obtained by integrating the interlayer film for laminated glass according to any one of the inventions 1 to 3 between at least a pair of glasses. The whitened distance from the periphery of the laminated glass is 4 mm or less when the laminated glass thus obtained is left in an atmosphere of 50 ° C. and 95% relative humidity for 4 weeks.

In the laminated glass according to the invention described in claim 5 (hereinafter referred to as invention 5), an interlayer film for laminated glass according to any one of the inventions 1 to 4 described above is interposed between at least a pair of glasses and integrated. It is characterized by becoming. Hereinafter, the present invention will be described in detail.

In the interlayer film for a laminated glass according to the first aspect of the invention (hereinafter simply referred to as an interlayer film), the laminated glass using the interlayer film has a 90 ° peel adhesion between the glass and the plasticized polyvinyl acetal resin film of 20 ° C. Is required to be 40 to 80 N / cm. This is because the intermediate film of Invention 1 is composed of a plasticized polyvinyl acetal resin film and a polyester resin film having a higher tensile strength than the plasticized polyvinyl acetal resin film. 20 to 40 N / cm, which is the level of the 90-degree peel adhesion when a conventional intermediate film consisting of only an acetal resin film is used.
Is outside the range, the penetration resistance of the laminated glass obtained is reduced.

In the intermediate film according to the first aspect of the present invention, as the polyvinyl acetal resin used for the plasticized polyvinyl acetal resin film, a polyvinyl acetal resin generally used as a main component of an interlayer film for laminated glass can be used. Polyvinyl butyral resin having a degree of butyralization of 60 to 70 mol% (hereinafter referred to as PVB)
Is preferably used. If the butyralization degree is less than 60 mol%, the compatibility with the plasticizer described below may decrease, and if the butyralization degree exceeds 70 mol%, the PVB production process may require a long time. This degree of butyralization can be measured, for example, in accordance with JIS K 6728 “Testing method for polyvinyl butyral”.

The average polymerization degree of the PVB is 100
It is preferably from 0 to 2000. Average degree of polymerization is 10
If it is less than 00, the penetration resistance or the like of the obtained laminated glass may decrease, and if the average degree of polymerization exceeds 2,000,
The production of the intermediate film may be difficult. The average degree of polymerization can be measured, for example, according to JIS K 6728 "Testing method for polyvinyl butyral".

In the intermediate film according to the first aspect of the present invention, the plasticizer used for the plasticized polyvinyl acetal resin film includes:
There is no particular limitation, and those generally used for an intermediate film, for example, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethyl butyrate (3GH), dihexyl adipate (DH)
A), tetraethylene glycol diheptanoate (4
G7), tetraethylene glycol di-2-ethylhexanoate (4GO) and the like, and one or more of these are suitably used.

The amount of the plasticizer used in the plasticized polyvinyl acetal resin film is preferably 20 to 60 parts by weight based on 100 parts by weight of the polyvinyl acetal resin.

The polyester resin film used in the intermediate film according to Invention 1 is not particularly limited, and for example, a polyethylene terephthalate (PET) resin film is preferably used. In addition, the PET resin film may be provided with functionality such as vapor deposition of metal fine particles to impart heat insulation.

In the intermediate film according to the first aspect, the plasticized polyvinyl acetal resin film has magnesium (M
g) is preferably not more than 40 ppm, and potassium (K) is preferably not more than 100 ppm. Mg content exceeds 40 ppm or K content is 100 ppm
When it exceeds, the whitening distance from the periphery of the laminated glass in a high-humidity atmosphere may be large.

[0018] In the interlayer according to the first aspect of the present invention, the adhesion modifier contained in the plasticized polyvinyl acetal resin film is
40pp of Mg to plasticized polyvinyl acetal resin film
It is preferable to add K so as to contain not more than m and not more than 100 ppm of K. That is, since the polyester film is used in the intermediate film according to the first aspect of the invention, the amount of the adhesive force modifier added can be suppressed as described above while maintaining the level of penetration resistance.

The adhesive force adjuster is not particularly limited, and examples thereof include organic acid metal salts such as organic acid magnesium salts and organic acid potassium salts. Examples thereof include magnesium acetate, magnesium propionate, and 2-ethylbutane. Magnesium carboxylate such as magnesium silicate and magnesium 2-ethylhexanoate are preferred, and have 1 to 28 carbon atoms.
Is more preferable. One or more of these are preferably used.

The adhesive strength control agent may further include other known adhesive strength control agents (for example, Japanese Patent Application No. 49-2740).
No. 6) Modified silicone oil can also be used in combination. Examples of the modified silicone oil include ether-modified silicone oil, epoxy-modified silicone oil, ester-modified silicone oil, and amine-modified silicone oil. These are generally obtained by reacting a compound to be modified with polysiloxane. It is a silky liquid. The added amount of this modified silicone oil is 0.005 to 0.5
Part by weight is preferable, and 0.02 to 0.2 part by weight is more preferable.

In the interlayer according to the first aspect of the present invention, the plasticized polyvinyl acetal resin film may contain, if necessary, a stabilizer for preventing deterioration of the interlayer, within a range that does not hinder achievement of the object of the present invention. One or two of various additives such as an inhibitor, an ultraviolet absorber for improving weather resistance and light resistance.
More than one species may be contained.

Next, the interlayer according to the fourth aspect is the same as the first aspect.
The laminated glass edge obtained when the laminated glass obtained by interposing the interlayer film for laminated glass according to any one of (1) to (3) between at least a pair of glasses and being left under an atmosphere of 50 ° C. and a relative humidity of 95% for 4 weeks. 4m whitening distance from the part
m.

That is, in the intermediate film of the first aspect, by setting the 90 ° peel adhesive force to 40 to 80 N / cm at 20 ° C., the amount of the metal salt added as an adhesive force modifier can be reduced. The whitening distance can be reduced to 4 mm or less.

Further, the laminated glass according to the fifth aspect of the present invention is required to have the interlayer film for laminated glass according to any one of the first to fourth aspects interposed between at least a pair of glasses to be integrated.

The type of the above glass is not particularly limited, and includes, for example, various types of inorganic glass or organic glass such as float plate glass, polished plate glass, template glass, etc., and one or more of these are preferably used. . Further, the thickness of the glass is not particularly limited and may be appropriately selected depending on the application, but is practically 2.0 to 4.0 mm.
Is preferred.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example 1) (1) Production of interlayer film for laminated glass As a polyvinyl acetal resin, a butyralization degree of 6 was used.
8.5 mol%, 1 mol% of vinyl acetate component, PVB having a polymerization degree of 1700 were used, and 39 parts by weight of triethylene glycol di-2-ethylhexanoate were added to 100 parts by weight of this PVB.
ppm and 20 ppm of 2-ethylbutyrate are added, and after sufficiently melt-kneaded with a mixing roll, press-formed at 150 ° C. for 30 minutes using a press-forming machine.
An interlayer for laminated glass having an average thickness of 0.38 mm was obtained.

(2) Production of Laminated Glass The interlayer film obtained in (1) was adjusted so that the water content became 0.3 to 0.5%, and this was mixed with an interlayer film / PET (thickness of 75 μm).
m) / intermediate film in order, 2.4 transparent from both sides
After being sandwiched between float glass sheets having a thickness of 1 mm and placed in a rubber bag and degassed for 20 minutes at a degree of vacuum of 2.7 kPa, it was transferred to an oven at 90 ° C. while keeping the degassed state and held for 30 minutes. The laminated glass thus preliminarily bonded was hot-pressed in an air type autoclave at a temperature of 140 ° C. and a pressure of 1.3 MPa for 20 minutes to obtain a laminated glass.

(3) Evaluation The performance of the interlayer film obtained in (1) (Mg and K contents and 90 ° peel adhesion) and the performance of the laminated glass obtained in (2) (penetration resistance and moisture resistance) Was evaluated by the following method. The results were as shown in Table 1.

1. Mg and K contents The intermediate film obtained in (1) is thermally decomposed with sulfuric acid and nitric acid,
After the volume of this decomposed product is determined with ultrapure water, an ICP-AES device (manufactured by Nippon Jarrell Ash Co., Ltd., ICAP-575) is used.
Was used to measure the contents of Mg and K in the intermediate film by an ICP emission elemental analysis method (ICP-AES method).

2. Intermediate film (thickness 0.76 mm) obtained by 90-degree peel adhesion (1), PET
(Thickness: 100 μm) and glass (2.5 mm float glass) were laminated in the configuration shown in FIG. 1 to obtain a test piece for peel adhesion measurement having a width of 10 mm and a length of 100 mm. Using this test piece, a tensile test was performed by a method shown in FIG. 2 using a Tensilon tester at 20 ± 2 ° C. and a tensile speed of 500 mm / min, and a 90 ° peel adhesion was measured. In this exam,
The tensile test was performed so that the interlayer film and the glass were always perpendicular to each other. The greater the 90-degree peel adhesion, the better the adhesion between the interlayer and the glass, and the lower the 90-degree peel adhesion, the worse the adhesion between the interlayer and the glass.

3. Moisture resistance The laminated glass obtained in (2) was treated at 50 ° C. and a relative humidity of 9
After being left for 4 weeks in a 5% atmosphere, the whitening distance of the peripheral edge of the glass was measured immediately after being taken out. The smaller the whitening distance, the better the moisture resistance, and the larger the whitening distance, the poorer the moisture resistance. If the whitening distance is 2 mm or less, it is considered good,
Anything beyond that was considered bad.

4. Penetration resistance A steel ball having a mass of 2260 ± 20 g and a diameter of about 82 mm is dropped from above vertically onto the 300 mm × 300 mm laminated glass obtained in (2), and 50% of the specimens can prevent penetration of the steel ball. The falling ball height was measured. The higher the falling ball height, the better the penetration resistance, and the smaller the falling ball height, the poorer the penetration resistance. If the height of the falling ball was 5 m or more, it was judged as good, and if it was less than that, it was judged as bad.

Example 2 In the production of an interlayer film, 20 pp of magnesium 2-ethylbutyrate was used as an adhesive force regulator.
m instead of magnesium 2-ethylhexylate 30
An interlayer film and a laminated glass were obtained in the same manner as in Example 1 except that ppm was added.

(Example 3) In the production of an interlayer film, magnesium 2-ethylbutyrate was used as an adhesive force regulator in an amount of 20 p.
pm, 20 ppm of magnesium 2-ethylhexylate
Except for the addition, an intermediate film and a laminated glass were obtained in the same manner as in Example 1.

Example 4 In the production of an interlayer film, 20 pp of magnesium 2-ethylbutyrate was used as an adhesion regulator.
An interlayer film and a laminated glass were obtained in the same manner as in Example 1 except that 50 ppm of potassium hexanoate was added instead of m.

Comparative Example 1 A laminated glass was obtained in the same manner as in Example 1 except that two interlayer films were stacked without using PET in the production of the laminated glass.

(Comparative Example 2) In the production of the intermediate film, the addition amount of magnesium acetate was 25 pp as an adhesion regulator.
m and the addition amount of magnesium 2-ethylbutyrate are 25 pp
An intermediate film was obtained in the same manner as in Example 1 except that m was used. Next, in the production of the laminated glass, a laminated glass was obtained in the same manner as in Example 1, except that two interlayer films were stacked without using PET.

Comparative Example 3 An intermediate film and a laminated glass were obtained in the same manner as in Example 1 except that no adhesive force adjusting agent was used in the production of the intermediate film.

(Comparative Example 4) An interlayer film and a laminated glass were obtained in the same manner as in Example 1, except that 21 ppm of magnesium acetate and 143 ppm of potassium acetate were added as an adhesion regulator in the production of the interlayer film.

[0041]

[Table 1]

As is clear from Table 1, the interlayer film for laminated glass according to the embodiment of the present invention has excellent adhesion to glass, and the laminated glass according to the embodiment of the present invention has excellent penetration resistance. Also, it has excellent moisture resistance.

On the other hand, Comparative Example 1 using no PET
Is inferior in penetration resistance, and has improved penetration resistance without using PET, and has a 90 ° peel adhesive strength of 40 N / cm.
The intermediate film of Comparative Example 2 having less than the above has an inappropriate adhesive force and is inferior in moisture resistance. Further, Comparative Example 3 in which no adhesive force modifier was used
The intermediate film having a 90 degree peel adhesive force of more than 80 N / cm has an inappropriate adhesive force and is inferior in penetration resistance.

[0044]

As described above, the interlayer film for laminated glass of the present invention has excellent adhesion to glass, and the laminated glass using it has excellent penetration resistance and moisture resistance. Are better. Accordingly, the interlayer film for laminated glass and the laminated glass of the present invention are suitably used for window glass for automobiles, buildings, and the like.

[0045]

[Brief description of the drawings]

FIG. 1 shows the configuration of a test piece used in measuring a 90-degree peel adhesion.

FIG. 2 shows a method of a tensile test in measuring a 90-degree peel adhesion.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 29/14 C08L 29/14 C09J 129/14 C09J 129/14 167/00 167/00 F term (reference) 4F100 AB09C AB09H AG00A AG00D AK23C AK41B AK42 BA03 BA04 BA07 BA10A BA10C BA10D GB08 GB33 JB20C JK06C JL09 JL11 JN01 YY00C 4G061 AA10 AA25 BA01 BA02 CB05 CB16 CB19 CD02 EG01 020 MA05

Claims (5)

[Claims] 1. An interlayer film for laminated glass, comprising a plasticized polyvinyl acetal resin film and a polyester resin film, wherein the outermost layer is a plasticized polyvinyl acetal resin film. An intermediate film for laminated glass, wherein the 90-degree peel adhesion between the film and the plasticized polyvinyl acetal resin film is 40 to 80 N / cm at 20 ° C. 2. A plasticized polyvinyl acetal resin film,
The interlayer film for laminated glass according to claim 1, wherein the interlayer film is a plasticized polyvinyl acetal resin film containing 40 ppm or less of magnesium and 100 ppm or less of potassium. 3. The interlayer film for laminated glass according to claim 1, wherein the polyvinyl acetal resin used for the plasticized polyvinyl acetal resin film is a polyvinyl butyral resin having a butyralization degree of 60 to 70 mol%. . 4. The laminated film for laminated glass according to claim 1, wherein the laminated film is formed by interposing the intermediate film between at least a pair of glasses and integrating the laminated glass.
An interlayer film for laminated glass, wherein a whitening distance from a peripheral portion of the laminated glass is 4 mm or less when left in an atmosphere of 50 ° C. and a relative humidity of 95% for 4 weeks. 5. The method according to claim 1, wherein at least between the pair of glasses.
A laminated glass characterized by being integrated with an interlayer film for laminated glass according to any one of (1) to (4).