JP2001240435A - Laminated glass and intermediate membrane therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated glass with good antistaticity and an intermediate membrane suitable to obtain the laminated glass. SOLUTION: This intermediate membrane comprises a plasticized polyvinyl butyral resin having butyral content of 62 to 72 mol% which contains 0.05 to 3 pts.wt. of a compound expressed by the general formula (1) below, 0.05 to 3 pts.wt. of a compound expressed by the general formula (2) below and 0.005 to 0.5 pts.wt. of potassium salt of a carboxylic acid having 4 to 12 carbons, each based on 100 pts.wt. of the polyvinyl butyral resin. R1-O-(CH2CH2O)mH (1) wherein R1 represents a hydrocarbon group having 1 to 25 carbons and (m) is an integer of 1 to 20. R2-O-(CH2CH2CH2O)nH (2) wherein R2 represents a hydrocarbon group having 1 to 25 carbons and (n) is an integer of 1 to 20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interlayer film for laminated glass and a laminated glass using the same.

[0002]

2. Description of the Related Art Laminated glass in which an interlayer film is sandwiched between a pair of glass plates has excellent safety without breaking fragments when it is damaged by an impact. Widely used for window glass etc.

[0003] Among such interlayer films for laminated glass,
The interlayer made of polyvinyl butyral resin plasticized by the addition of a plasticizer has excellent adhesion to glass, tough tensile strength, and high transparency.The laminated glass obtained using this interlayer is In particular, it is suitable as a window glass for vehicles.

The interlayer film for laminated glass made of the above-mentioned plasticized polyvinyl butyral resin has a surface resistance of 10 ¹³ Ω /.
In general, it is hard to be charged at about ² cm ² , and since it is used by being sandwiched between glass plates, little consideration has been given to antistatic performance.

On the other hand, in recent years, requirements for quality have become strict, and adhesion of dust and foreign matter due to static electricity has become a problem, and an interlayer film for laminated glass having excellent antistatic performance has been demanded.

However, when an antistatic method, which is widely used in conventional transparent plastics, is applied to an interlayer film for laminated glass, the adhesiveness between the interlayer film for laminated glass and glass, transparency, durability, and the like are reduced. No suitable combination was found because it was damaged.

In order to solve the above problem, Japanese Patent Laid-Open No.
Japanese Patent No. 223849 discloses an interlayer film for laminated glass in which an antistatic agent is kneaded or coated, but may affect the basic physical properties of the film such as moisture resistance and adhesiveness. There was a problem of being large.

[0008]

SUMMARY OF THE INVENTION In view of the above, the present invention has been made, without impairing the basic properties required for laminated glass such as transparency, light resistance, weather resistance, impact resistance, and adhesiveness, and
To provide an interlayer film for laminated glass and a laminated glass suitable for obtaining a laminated glass having excellent antistatic properties, with little peeling or whitening at the periphery of the laminated glass even when placed in a humid atmosphere. With the goal.

[0009]

The present invention provides an interlayer film for laminated glass comprising a plasticized polyvinyl butyral resin having a butyralization degree of 62 to 72 mol%, wherein the plasticized polyvinyl butyral resin is a polyvinyl butyral resin. The compound represented by the following general formula (1) is used in an amount of 0.05 to 3 parts by weight, based on 100 parts by weight, of the following general formula (2)
A compound represented by the formula: 0.05 to 3 parts by weight and a carbon number of 4 to
This is an interlayer film for laminated glass obtained by adding 0.005 to 0.5 parts by weight of potassium salt of carboxylic acid No. 12. R ¹ —O— (CH ₂ CH ₂ O) mH (1) In the formula, R ¹ represents a hydrocarbon group having 1 to 25 carbon atoms;
Represents an integer of 1 to 20. R ² —O— (CH ₂ CH ₂ CH ₂ O) nH (2) In the formula, R ² represents a hydrocarbon group having 1 to 25 carbon atoms;
Represents an integer of 1 to 20. Hereinafter, the present invention will be described in detail.

The interlayer for laminated glass of the present invention comprises a plasticized polyvinyl butyral resin having a butyralization degree of 62 to 72 mol%. When the butyralization degree of the plasticized polyvinyl butyral resin is less than 62 mol%, the water absorption of the obtained interlayer film for laminated glass increases, and whitening easily occurs. If the content exceeds 72 mol%, the mechanical strength of the obtained interlayer film for laminated glass decreases, so that the penetration resistance of the laminated glass using the same decreases. The butyralization degree of the plasticized polyvinyl butyral resin is preferably 63.5 to 70 mol%.

The method for producing the polyvinyl butyral resin constituting the plasticized polyvinyl butyral resin is not particularly limited, and a known method can be employed.
For example, polyvinyl alcohol is dissolved in hot water, and the resulting aqueous solution is kept at 10 to 20 ° C., and butyl aldehyde and an acid catalyst are added thereto to progress acetalization. A method of obtaining a polyvinyl butyral resin powder through various steps of neutralization, washing with water, and drying after the temperature is raised to and maintained at a temperature.

The polyvinyl alcohol used as the raw material for the polyvinyl butyral resin is not particularly limited, but those having an average degree of polymerization of 1,000 to 2,500 are preferable.
When the average degree of polymerization of polyvinyl alcohol is less than 1,000, the strength of the obtained interlayer film for laminated glass is reduced, so that the penetration resistance and impact energy absorption of the laminated glass using the same may be reduced. Average degree of polymerization is 2
If it exceeds 500, the strength of the obtained interlayer film for laminated glass may be too strong, and the penetration resistance and impact energy absorption of the laminated glass may be insufficient.

The above polyvinyl alcohol is obtained by saponifying polyvinyl acetate. In order to improve the transparency, heat resistance and light resistance of the obtained interlayer film for laminated glass, the saponification degree of the polyvinyl alcohol is preferably 9
It is preferably at least 5 mol%.

In the interlayer film for laminated glass of the present invention,
The plasticized polyvinyl butyral resin is prepared by adding 0.05 to 3 parts by weight of the compound represented by the general formula (1) and 0.05 to 3 parts by weight of the compound represented by the general formula (2) to 100 parts by weight of the polyvinyl butyral resin. To 5 to 3 parts by weight and 0.005 to 0.5 parts by weight of a potassium salt of a carboxylic acid having 4 to 12 carbon atoms.

In the interlayer film for laminated glass of the present invention,
The compound represented by the general formula (1) has an effect of dispersing and conducting static electricity (charge) in a film and preventing chargeability. When the number of carbon atoms of the hydrocarbon group (R ¹ ) of the compound represented by the general formula (1) exceeds 25, an excessive bleed phenomenon occurs on the surface of the obtained interlayer film for laminated glass, which adversely affects the adhesive strength. And the antistatic effect is reduced. In the compound represented by the general formula (1), R ¹
Preferably has 4 to 20 carbon atoms. On the other hand, when the value of m exceeds 20, the moisture resistance of the obtained interlayer film for laminated glass decreases. The value of m is preferably 2-10.

The compound represented by the above general formula (1) includes, for example, dodecyloxydiethylene glycol, dodecyloxytriethylene glycol, methoxytetraethylene glycol, pentoxyhexaethylene glycol, 3,3-dipropylbutoxytetra Ethylene glycol, 2,2-diethylbutoxytetraethylene glycol, phenoxyhexaethylene glycol, 1,5-
And diethylphenoxyoctaethylene glycol. These may be used alone or in combination of two or more.

When the amount of the compound represented by the general formula (1) is less than 0.05 part by weight based on 100 parts by weight of the polyvinyl butyral resin, the antistatic effect is reduced. If the amount exceeds 3 parts by weight, the resulting interlayer film for laminated glass will have reduced moisture resistance. Preferably, it is 0.1 to 2 parts by weight based on 100 parts by weight of the polyvinyl butyral resin.

The compound represented by the general formula (2) interacts with the compound represented by the general formula (1) and plays a role in increasing the antistatic effect thereof. When the number of carbon atoms of the hydrocarbon group (R ² ) of the compound represented by the general formula (2) exceeds 25, an excessive bleeding phenomenon occurs on the surface of the obtained interlayer film for laminated glass, which adversely affects the adhesive strength. And the antistatic effect is reduced. In the compound represented by the general formula (2), R ² preferably has 4 to ² carbon atoms.
0. On the other hand, when the value of n exceeds 20, the moisture resistance of the obtained interlayer film for laminated glass decreases. The value of n is preferably 2-10.

The compound represented by the general formula (2) includes, for example, dodecyloxytripropylene glycol,
Methoxytetrapropylene glycol, pentoxyhexapropylene glycol, 3,3-dipropylbutoxytetrapropyleneglycol, 2,2-diethylbutoxytetrapropyleneglycol, phenoxyhexapropyleneglycol, 1,5-diethylphenoxyoctapropyleneglycol, and the like. . These may be used alone or in combination of two or more.

When the amount of the compound represented by the general formula (2) is less than 0.05 parts by weight based on 100 parts by weight of the polyvinyl butyral resin, the antistatic effect is reduced. If the amount exceeds 3 parts by weight, the resulting interlayer film for laminated glass will have reduced moisture resistance. Preferably, it is 0.1 to 2 parts by weight based on 100 parts by weight of the polyvinyl butyral resin.

The potassium salt of a carboxylic acid having 4 to 12 carbon atoms used in the interlayer film for laminated glass of the present invention is as follows:
It has the effect of dispersing and conducting static electricity (charge) in the film to prevent charging.

In the above-mentioned potassium carboxylate, if the carboxylic acid has less than 4 carbon atoms, particles will aggregate in the film, and the antistatic effect will be reduced. If it exceeds 12,
The potassium salt of the carboxylic acid is excessively segregated on the film surface, causing the adhesive force to change with time. The carboxylic acid preferably has 6 to 12 carbon atoms.

The potassium salt of a carboxylic acid having 4 to 12 carbon atoms includes, for example, potassium butanoate, potassium isobutyrate, potassium 2-ethylbutyrate, potassium hexanoate, potassium 2-ethylhexanoate, potassium octanoate, decane And potassium dodecylate, potassium oxalate, potassium malonate, potassium succinate, potassium glutarate, potassium adipate and the like. These may be used alone or in combination of two or more.

If the amount of the potassium salt of a carboxylic acid having 4 to 12 carbon atoms is less than 0.005 parts by weight based on 100 parts by weight of the polyvinyl butyral resin, the antistatic effect is reduced. If it exceeds 0.5 part by weight, the resulting interlayer film for laminated glass will have reduced moisture resistance. Preferably, 0.01 to 100 parts by weight of polyvinyl butyral resin
０．３0.3 parts by weight.

The plasticized polyvinyl butyral resin used in the interlayer film for laminated glass of the present invention is obtained by plasticizing a polyvinyl butyral resin with a plasticizer. The plasticizer is not particularly limited, and includes, for example, organic ester plasticizers such as monobasic acid ester and polybasic acid ester; and phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid. No.

The above-mentioned monobasic ester plasticizer is not particularly restricted but includes, for example, glycols such as triethylene glycol, tripropylene glycol and tetraethylene glycol and butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid and heptanoic acid. And glycol-based esters obtained by reaction with an organic acid such as 2-ethylhexylic acid.

The polybasic acid ester plasticizer is not particularly limited, and may be, for example, a reaction of a linear or branched alcohol having 4 to 8 carbon atoms with an organic acid such as adipic acid, sebacic acid or azelitic acid. The resulting ester and the like can be mentioned. The phosphoric acid plasticizer is not particularly limited,
For example, tributoxyethyl phosphate, isodecylphenyl phosphate and the like can be mentioned.

Among the above plasticizers, for example, triethylene glycol-di-2-ethylbutyrate (3G
H), triethylene glycol-di-2-ethylhexanoate (3GO), triethylene glycol-di-n
-Heptanoate (3G7), triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, tetraethylene glycol di-2-ethyl butyrate, tetraethylene glycol di-n-
Heptanoate, dihexyl adipate, dibenzyl phthalate and the like are preferred. More preferably, 3GH, 3G
O, 3G7 and the like. The above plasticizers may be used alone or two or more of them may be used in combination.

The amount of the plasticizer added to the polyvinyl butyral resin is not particularly limited, but is preferably 30 to 70 parts by weight of the plasticizer based on 100 parts by weight of the polyvinyl butyral resin. If it is less than 30 parts by weight,
Plasticization of the polyvinyl butyral resin may be insufficient. When the amount exceeds 70 parts by weight, the mechanical strength of the interlayer film for laminated glass is reduced, so that the impact resistance is poor, and the adhesive strength between the interlayer film for laminated glass and the glass may be insufficient.

The interlayer film for laminated glass of the present invention may further contain, if necessary, a stabilizer for preventing deterioration of the polyvinyl butyral resin, an antioxidant, an ultraviolet absorber, and an adhesion regulator. An agent may be added to the extent that the properties of the interlayer film for laminated glass of the present invention are not impaired.

The stabilizer is not particularly restricted but includes, for example, surfactants such as sodium lauryl sulfate and alkylbenzenesulfonic acid. The antioxidant is not particularly limited. For example, t-butylhydroxytoluene (BHT), tetrakis- [methylene-3-
(3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (manufactured by Ciba-Geigy, trade name: Irganox 1010).

The ultraviolet absorber is not particularly restricted but includes, for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (Ciba Geigy, trade name: Tinuvin P), 2- (2'- Hydroxy-3 ',
5′-di-t-butylphenyl) benzotriazole (trade name: Tinuvin 320, manufactured by Ciba Geigy), 2-
(2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole (manufactured by Ciba Geigy, trade name: Tinuvin 326), 2- (2′-hydroxy-3 ′, 5 ′) -Di-amylphenyl) benzotriazole (manufactured by Ciba Geigy, trade name: Tinuvin 32)
Benzotriazoles such as 8); hindered amines such as LA-57 manufactured by Adeka Argus Co., Ltd .;

In the interlayer film for laminated glass of the present invention,
The thickness of the entire film is preferably from 0.3 to 1.6 mm, which is the thickness of an ordinary interlayer film for laminated glass. The method for producing the interlayer film for laminated glass of the present invention is not particularly limited. For example, a polyvinyl butyral resin, a general formula (1)
The compound represented by the formula, a compound represented by the general formula (2), a metal salt of a carboxylic acid having 4 to 12 carbon atoms, a plasticizer, and an additive to be added as necessary are supplied to the mixing roll.
The kneaded product obtained by kneading is formed into a sheet by a press forming machine, a calender roll, an extruder, or the like, whereby an interlayer film for a laminated glass made of a plasticized polyvinyl butyral resin can be produced.

Further, a laminated glass can be manufactured by interposing and integrating the interlayer film for laminated glass of the present invention between at least a pair of glass plates. A laminated glass using the interlayer film for a laminated glass of the present invention is also one of the present invention.

The method for producing the laminated glass of the present invention is not particularly limited, and a conventionally used method can be employed. For example, the interlayer film for a laminated glass of the present invention is sandwiched between glass plates from both sides thereof. This sandwich is placed in a vacuum bag, and kept in a vacuum at 90 ° C. for 30 minutes.
The transparent laminated glass can be obtained by hot pressing at a pressure of 1.3 MPa and a temperature of 140.degree.

The glass plate is not particularly limited. For example, float glass, polished glass, template glass,
Netted glass, lined glass, heat absorbing glass,
Various inorganic glasses or organic glasses such as colored plate glass are exemplified. These may be used alone,
More than one species may be used in combination.

The interlayer film for a laminated glass of the present invention may be sandwiched between transparent members having high rigidity other than glass. Examples of the transparent body include those made of a polycarbonate resin. Such a structure is also a feature of the present invention.
One.

The interlayer film for a laminated glass and the laminated glass of the present invention having the above-mentioned constitutions provide the basic performance required for the laminated glass such as transparency, light resistance, weather resistance, impact resistance and adhesiveness. In addition, even when the laminated glass is placed in a humid atmosphere, peeling or whitening of the periphery of the laminated glass is less likely to occur, and the antistatic property is excellent.

[0039]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 (Synthesis of polyvinyl butyral resin) Deionized water 29
00 parts by weight, average degree of polymerization 1700, degree of saponification 99.2m
198% by weight of polyvinyl alcohol (equivalent to 4.5 mol of vinyl alcohol) was supplied to a reactor equipped with a stirrer, and dissolved by heating to 95 ° C. while stirring. The solution was cooled to 30 ° C., and 208 parts by weight (2.1 mol) of 35% by weight hydrochloric acid and 152 parts by weight (2.1 mol) of n-butyraldehyde were added. Then, the temperature of the solution was lowered to 2 ° C., and the temperature was lowered. After holding and holding the polyvinyl butyral resin, the liquid temperature was raised to 30 ° C. and held for 5 hours. After holding, 156 parts by weight of sodium bicarbonate (1.8 mo
l) was added to neutralize, washed with water and dried to obtain a polyvinyl butyral resin having a butyralization degree of 69 mol%.

(Preparation of interlayer for laminated glass) 100 parts by weight of the obtained polyvinyl butyral resin, 39 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, magnesium 2-ethylbutyrate ( C6Mg) and magnesium acetate (C
2Mg), 0.01 parts by weight, 0.03 parts by weight of potassium 2-ethylhexanoate, and 0.5 parts by weight of dodecyloxytriethylene glycol are supplied to a mixing roll,
The kneaded material obtained by kneading is 150 ° C. in a press molding machine,
Press molding was performed under a condition of 10 MPa for 30 minutes to obtain an interlayer film for laminated glass having a thickness of 0.8 mm and comprising a plasticized polyvinyl butyral resin. Using the interlayer film for laminated glass, the surface resistance of the film was measured by the following method. The results are shown in Table 3.

(Preparation of Laminated Glass) The obtained interlayer film for laminated glass was sandwiched from both sides with two float glass plates each having a square of 30 cm and a thickness of 2.5 mm, and the sandwich was evacuated. It was put in a bag, kept at a degree of vacuum of 2.7 kPa for 20 minutes, transferred to an oven at 90 ° C. in a vacuum state, and kept at this temperature for 30 minutes. The sandwiched body thus temporarily bonded by the vacuum press is thermocompression-bonded in an autoclave at a pressure of 1.3 MPa and a temperature of 150 ° C.
A transparent laminated glass was produced. About the obtained laminated glass, an adhesion test (Pummel test) is performed by the following method,
A moisture resistance (whitening resistance) test was performed. The results are shown in Table 3.

(1) Adhesion (Pummel) Test The adhesion of the interlayer for laminated glass to glass was evaluated by Pummel value. The laminated glass was allowed to stand at a temperature of -18 ± 0.6 ° C. for 16 hours, and the head was adjusted to 0.45 ° C.
The glass was ground with a hammer of kg until the particle size of the glass became 6 mm or less. As shown in Table 1, the degree of exposure of the interlayer film after the glass was partially peeled was determined by a preliminarily graded limit sample, and defined as a Pummel value. In addition, the Pummel value measured the initial value and the value after leaving a laminated glass at 50 degreeC for 4 weeks. The larger the Pummel value is,
The adhesiveness between the interlayer film for laminated glass and the glass is large, and the adhesive strength between the interlayer film for laminated glass and the glass is small as the Pummel value is small.

[0044]

[Table 1]

(2) Moisture resistance (whitening resistance) test The laminated glass was left in an environment of 80 ° C. and a relative humidity of 95% for 2 weeks, and immediately after being taken out, the whitening distance from the edge of the laminated glass (whitening was observed). Part distance) was measured.

(3) Measurement of Surface Resistance The obtained interlayer film for laminated glass was dried in a desiccator for 24 hours, and was subjected to a surface resistance measurement device (manufactured by Toa Denpa Kogyo KK,
DSM-8103).

Examples 2 to 3 and Comparative Examples 1 to 9 Interlayer films for laminated glass were prepared in the same manner as in Example 1 with the formulations shown in Table 2, and the surface resistance was measured. Also,
Using this interlayer film for laminated glass, a laminated glass was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0048]

[Table 2]

The description in Table 2 is as follows. PVB resin: polyvinyl butyral resin Bu degree: butyral degree 3GO: triethylene glycol-di-2-ethylhexanoate 4G7: tetraethylene glycol-di-n-heptanoate C6Mg: magnesium 2-ethylbutyrate C2Mg: magnesium acetate C2K : Potassium acetate Phe: phenyl group

[0050]

[Table 3]

From Table 3, it can be seen that the interlayer film for laminated glass produced in the examples is excellent in adhesion to glass and moisture resistance, so that a laminated glass excellent in impact resistance and moisture resistance can be produced. Was. Furthermore, since the surface resistance of the film was small, it was excellent in antistatic properties. On the other hand, the interlayer film for laminated glass produced in Comparative Example was not excellent in both moisture resistance and antistatic property.

[0052]

Since the interlayer film for laminated glass of the present invention has the above-mentioned structure, the adhesiveness is stable, the moisture resistance is excellent, and the antistatic property is excellent. Therefore, the interlayer film for laminated glass of the present invention is suitably used as an interlayer film for laminated glass for construction and vehicles.

Continued on the front page (51) Int.Cl. ⁷ Identification FI theme coat II (reference) (C08L 29/14 (C08L 29/14 71:02) 71:02) F term (reference) 4F071 AA30 AA47 AA80 AC05 AC09 AH19 BC01 BC02 BC12 CA01 CB06 CD01 4G061 AA04 AA29 BA02 CB03 CB19 CD18 4J002 BE061 CH022 ED036 EG027 EG057 4J040 DD071 EE012 HA08 HB15 MA05

Claims (2)

[Claims] 1. An interlayer for laminated glass comprising a plasticized polyvinyl butyral resin having a butyralization degree of 62 to 72 mol%, wherein the plasticized polyvinyl butyral resin is as follows based on 100 parts by weight of the polyvinyl butyral resin. The compound represented by the general formula (1)
3 parts by weight of a compound represented by the following general formula (2)
An interlayer for laminated glass, comprising 5 to 3 parts by weight and 0.005 to 0.5 part by weight of a potassium salt of a carboxylic acid having 4 to 12 carbon atoms. R ¹ —O— (CH ₂ CH ₂ O) mH (1) In the formula, R ¹ represents a hydrocarbon group having 1 to 25 carbon atoms;
Represents an integer of 1 to 20. R ² —O— (CH ₂ CH ₂ CH ₂ O) nH (2) In the formula, R ² represents a hydrocarbon group having 1 to 25 carbon atoms;
Represents an integer of 1 to 20. 2. A laminated glass comprising the interlayer film for laminated glass according to claim 1 interposed between at least a pair of glasses and integrated.