JPWO2015152241A1 - Intermediate film for laminated glass, laminated glass, and intermediate film roll for laminated glass - Google Patents

Abstract

The present invention relates to an interlayer film for laminated glass that has high rigidity and can be wound around a roll-shaped body, and can be easily corrected in position after being laminated on a curved glass during the production of laminated glass, and the interlayer film for laminated glass An object is to provide a laminated glass using a glass and an intermediate film roll for laminated glass. The present invention is an interlayer film for laminated glass containing a polyvinyl acetal resin, a metal atom and a plasticizer, and has a storage elastic modulus G ′ (A) of 40 and 20 measured at 20 ° C. according to JISK-7128-3. Storage at 20 ° C. when the ratio (G ′ (B) / G ′ (A)) to the storage elastic modulus G ′ (B) at 0.1 ° C. is 0.1 or less and measured according to JISK-7128-3 The interlayer film for laminated glass has a ratio (G ′ (C) / G ′ (A)) of an elastic modulus G ′ (A) and a storage elastic modulus G ′ (C) at 60 ° C. of 0.01 or less.

Description

The present invention relates to an interlayer film for laminated glass that has high rigidity and can be wound around a roll-shaped body, and can be easily corrected in position after being laminated on a curved glass during the production of laminated glass, and the interlayer film for laminated glass The present invention relates to a laminated glass using, and an intermediate film roll for laminated glass.

Laminated glass is highly safe because glass fragments are less likely to scatter even if broken due to external impact. For this reason, it is widely used as a window glass for vehicles such as automobiles, aircraft, buildings, and the like. Examples of the laminated glass include laminated glass in which an interlayer film for laminated glass containing a polyvinyl acetal resin such as polyvinyl butyral resin and a plasticizer is interposed between at least a pair of glass plates, and laminated and integrated.

In recent years, in order to reduce the weight of laminated glass, it has been studied to reduce the thickness of the glass used for the laminated glass. If the thickness of the glass is reduced, there is a problem that the rigidity of the entire laminated glass is lowered.
On the other hand, it has been attempted to increase the rigidity of the entire laminated glass by employing a highly rigid interlayer film for laminated glass. As such an interlayer film for laminated glass having a high rigidity, for example, an interlayer film for laminated glass made of an ionomer of a terpolymer has been studied (Patent Document 1, etc.). However, laminated glass is usually manufactured by pulling out an interlayer film for laminated glass wound up in a roll and placing it between a pair of glass plates. An interlayer film for laminated glass with high rigidity employing an ionomer is a roll. It is difficult to wind up in the shape. Moreover, when laminated on curved glass during the production of laminated glass, it is difficult to follow the curved glass because of its high rigidity. The interlayer film for laminated glass that is difficult to follow the curved glass has a problem that the manufacturing efficiency is poor in the manufacturing process.

JP 2013-28486 A

The present invention relates to an interlayer film for laminated glass that has high rigidity and can be wound around a roll-shaped body, and can be easily corrected in position after being laminated on a curved glass during the production of laminated glass, and the interlayer film for laminated glass An object is to provide a laminated glass using a glass and an intermediate film roll for laminated glass.

The present invention is an interlayer film for laminated glass containing a polyvinyl acetal resin, a metal atom and a plasticizer, and has a storage elastic modulus G ′ (A) of 40 and 20 measured at 20 ° C. according to JISK-7128-3. Storage at 20 ° C. when the ratio (G ′ (B) / G ′ (A)) to the storage elastic modulus G ′ (B) at 0.1 ° C. is 0.1 or less and measured according to JISK-7128-3 The interlayer film for laminated glass has a ratio (G ′ (C) / G ′ (A)) of an elastic modulus G ′ (A) and a storage elastic modulus G ′ (C) at 60 ° C. of 0.01 or less.
The present invention is described in detail below.

The interlayer film for laminated glass of the present invention has a ratio (G of storage elastic modulus G ′ (A) at 20 ° C. and storage elastic modulus G ′ (B) at 40 ° C. measured according to JISK-7128-3. '(B) / G' (A)) (hereinafter also simply referred to as “ratio (G ′ (B) / G ′ (A))”) is 0.1 or less and conforms to JISK-7128-3 The ratio (G ′ (C) / G ′ (A)) between the storage elastic modulus G ′ (A) at 20 ° C. and the storage elastic modulus G ′ (C) at 60 ° C. (hereinafter simply referred to as “ratio” (Also referred to as “G ′ (C) / G ′ (A))”) is 0.01 or less. By adopting polyvinyl acetal resin as the binder resin and satisfying these parameters, the interlayer film for laminated glass of the present invention has high rigidity and can be wound on a roll-shaped body.

The interlayer film for laminated glass of the present invention has a ratio (G ′ (B) / G ′ (A)) of 0.1 or less and a ratio (G ′ (C) / G ′ (A)) of 0.01. It is as follows. Thereby, the interlayer film for laminated glass has high rigidity and can be wound up on a roll-shaped body.
The ratio (G ′ (B) / G ′ (A)) is preferably 0.05 or less, and the ratio (G ′ (C) / G ′ (A)) is preferably 0.01 or less.

While using the polyvinyl acetal resin, the ratio (G ′ (B) / G ′ (A)) is 0.1 or less and the ratio (G ′ (C) / G ′ (A)) is 0.01 or less. For this purpose, for example, a method of using a specific polyvinyl acetal resin, blending metal atoms, and sufficiently kneading the polyvinyl acetal resin and the raw material composition containing the metal atoms is conceivable. By adopting such a method, the side chain functional group (hydroxyl group) of the polyvinyl acetal resin and the metal atom form an ionic bond in the interlayer film for laminated glass to be obtained, and high rigidity can be exhibited. The flexibility which can be taken can also be exhibited.

The interlayer film for laminated glass of the present invention contains a polyvinyl acetal resin.
By containing the polyvinyl acetal resin, the interlayer film for laminated glass of the present invention can exhibit a rollable flexibility.

The polyvinyl acetal resin is not particularly limited as long as it is a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde, but a polyvinyl butyral resin is preferable. Moreover, you may use together 2 or more types of polyvinyl acetal resin as needed. In order to further increase the rigidity, it is preferable to use a polyvinyl acetal resin having a carboxyl group. For example, a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol having a structural unit modified with a carboxylic acid such as itaconic acid is preferred.

The minimum with the preferable amount of hydroxyl groups of the said polyvinyl acetal resin is 15 mol%. By using a polyvinyl acetal resin having a hydroxyl group content of 15 mol% or more, the hydroxyl group of the polyvinyl acetal resin and the metal atom form an ionic bond, and can exhibit high rigidity, and the ratio (B / A) is 0.7. This can be done. A more preferable lower limit of the amount of hydroxyl groups of the polyvinyl acetal resin is 20 mol%.
The upper limit with the preferable amount of hydroxyl groups of the said polyvinyl acetal resin is 40 mol%. Thereby, the interlayer film for laminated glass obtained does not become too hard. The upper limit with the more preferable amount of hydroxyl groups of the said polyvinyl acetal resin is 35 mol%.

The preferable lower limit of the degree of acetalization of the polyvinyl acetal resin is 50 mol%, and the preferable upper limit is 80 mol%. When the degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the degree of acetalization is less than or equal to the above upper limit, the production efficiency of the intermediate film is increased. The minimum with a more preferable acetalization degree of the said polyvinyl acetal resin is 60 mol%, and a more preferable upper limit is 70 mol%.
The degree of acetalization and the amount of hydroxyl groups can be measured by, for example, a method based on JIS K6728 “Testing method for polyvinyl butyral”.

The polyvinyl acetal resin can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
The polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol having a saponification degree of 80 to 99.8 mol% is generally used.
The preferable lower limit of the polymerization degree of the polyvinyl alcohol is 500, and the preferable upper limit is 4000. When the polymerization degree of the polyvinyl alcohol is less than 500, the penetration resistance of the obtained laminated glass may be lowered. When the polymerization degree of the polyvinyl alcohol exceeds 4000, it may be difficult to mold the interlayer film for laminated glass. The minimum with a more preferable polymerization degree of the said polyvinyl alcohol is 1000, and a more preferable upper limit is 3600.

The aldehyde is not particularly limited, but generally an aldehyde having 1 to 10 carbon atoms is preferably used. The aldehyde having 1 to 10 carbon atoms is not particularly limited. For example, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde N-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Of these, n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferable, and n-butyraldehyde is more preferable. These aldehydes may be used alone or in combination of two or more.

The interlayer film for laminated glass of the present invention contains a metal atom. By containing a metal atom, the hydroxyl group of the polyvinyl acetal resin and the metal atom form an ionic bond, and high rigidity can be exhibited.

Examples of the metal atom include alkali metals such as lithium, sodium, potassium, rubidium, cesium, and francium, alkaline earth metals such as calcium, strontium, barium, and radium, and zinc. Among these, sodium and zinc are preferable among alkali metals because they can be easily introduced into the resin.

The metal atoms can be blended in the interlayer film for laminated glass in the form of metal salts such as hydroxides, carbonates, bicarbonates, and fatty acid salts with metals.
In the interlayer film for laminated glass, generally, an alkali metal or alkaline earth metal salt is blended as an adhesive strength adjusting agent. You may mix | blend a part of said metal atoms as this adhesive force regulator.

A preferable lower limit of the amount of the metal atom is 50 ppm. By blending 50 ppm or more of metal atoms, the hydroxyl group of the polyvinyl acetal resin and the metal atoms form an ionic bond, and can exhibit high rigidity, and the ratio (B / A) can be 0.7 or more. . A more preferable lower limit of the compounding amount of the metal atoms is 100 ppm. Although the upper limit of the compounding amount of the metal atoms is not particularly limited, when it exceeds 2000 ppm, the moisture resistance of the interlayer film for laminated glass obtained may be lowered.

The interlayer film for laminated glass of the present invention contains a plasticizer. By containing a plasticizer, flexibility is imparted to the interlayer film for laminated glass, and winding becomes easier.
Examples of the plasticizer include triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, and triethylene glycol diester. -N-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl butyrate, 1 , 3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, 1,2-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate Rate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicapryate , Triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, triethylene glycol di-2-ethylbutyrate, dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, diisononyl adipate, heptylnonyl adipate , Dibutyl sebacate, oil-modified alkyd sebacate, a mixture of phosphate ester and adipic acid ester, adipic acid ester, alkyl alcohol having 4 to 9 carbon atoms and charcoal Number 4-9 mixed adipates made from cyclic alcohols, such as adipic acid ester having 6 to 8 carbon atoms such as adipic acid hexyl. Among the plasticizers, triethylene glycol-di-2-ethylhexanoate (3GO) is particularly preferably used.

Although content of the said plasticizer is not specifically limited, The preferable minimum with respect to 100 weight part of said thermoplastic resins is 10 weight part, and a preferable upper limit is 60 weight part. When the content of the plasticizer is not within this range, high handleability can be exhibited. The minimum with more preferable content of the said plasticizer is 15 weight part, and a more preferable upper limit is 45 weight part.

The interlayer film for laminated glass of the present invention may further contain additives such as an ultraviolet absorber, an antioxidant, a light stabilizer, an adhesive strength modifier, a pigment, a dye, and a fluorescent brightening agent, if necessary. Good.

The ultraviolet absorber is not particularly limited, and examples thereof include benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, hindered amine compounds, and the like.

The antioxidant is not particularly limited. For example, 2,2-bis [[[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] oxy] methyl] propane-1,3- Diol 1,3-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-3-methylphenol), 4,4 '-Dimethyl-6,6'-di (tert-butyl) [2,2'-methylenebis (phenol)], 2,6-di-t-butyl-p-cresol, 4,4'-butylidenebis- (6 -T-butyl-3-methylphenol) and the like.

The preferable lower limit of the thickness of the interlayer film for laminated glass of the present invention is 0.1 mm, and the preferable upper limit is 3 mm. When the thickness of the interlayer film for laminated glass is less than 0.1 mm, the penetration resistance of the obtained laminated glass may be lowered. When the thickness of the interlayer film for laminated glass exceeds 3 mm, the transparency of the interlayer film for laminated glass obtained may be lowered. The more preferable lower limit of the thickness of the interlayer film for laminated glass is 0.25 mm, and the more preferable upper limit is 2 mm.

The interlayer film for laminated glass of the present invention may be an interlayer film for laminated glass having a single layer structure formed by only one resin layer, or a laminated structure in which two or more resin layers are laminated. An interlayer film for glass may be used.

The method for producing the interlayer film for laminated glass according to the present invention includes, for example, mixing the plasticizer, the compound serving as the raw material of the metal atom, and the additive to be blended as necessary, and then sufficiently with the polyvinyl acetal resin. Examples thereof include a method of kneading and forming an interlayer film for laminated glass.
Here, in order to form a sufficient ionic bond between the side chain functional group (hydroxyl group) of the polyvinyl acetal resin and the metal atom, it is important that the polyvinyl acetal resin and the metal atom are sufficiently kneaded. . More specifically, kneading is performed using a mixing roll or a kneader.

The laminated glass in which the interlayer film for laminated glass of the present invention is laminated between a pair of glass plates is also one aspect of the present invention.
In the laminated glass of the present invention, since the interlayer film for laminated glass itself of the present invention has high rigidity, it is possible to employ a glass plate that is thinner than before.
The said glass plate can use the transparent plate glass generally used. Examples thereof include inorganic glass such as float plate glass, polished plate glass, template glass, netted glass, wire-containing plate glass, colored plate glass, heat ray absorbing glass, heat ray reflecting glass, and green glass. Further, an ultraviolet shielding glass having an ultraviolet shielding coating layer formed on the glass surface can also be used. Furthermore, organic glass plates such as polyethylene terephthalate, polycarbonate, and polyacrylate can be used as the glass plate.
Two or more types of glass plates may be used as the glass plate. For example, the laminated glass which laminated | stacked the intermediate film for laminated glasses of this invention between transparent float plate glass and colored glass plates like green glass is mentioned. Moreover, you may use the glass plate from which 2 or more types of thickness differs as said glass plate.

The interlayer film for laminated glass of the present invention has high rigidity and can be wound around a roll-shaped body.
The interlayer film roll for laminated glass obtained by winding the interlayer film for laminated glass of the present invention into a roll is also one aspect of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, it has high rigidity, and can be wound up in a roll-shaped body, and can correct | amend a position easily after the lamination | stacking to the curved glass at the time of laminated glass manufacture, The laminated film for this laminated glass A laminated glass using an intermediate film and an intermediate film roll for laminated glass can be provided.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
(1) Preparation of polyvinyl acetal resin Modified polyvinyl alcohol having a polymerization degree of 1900 (itaconic acid modification amount 1.2 mol%) was butyralized with n-butyraldehyde to obtain a polyvinyl butyral resin. The obtained polyvinyl butyral resin had a hydroxyl group content of 23 mol% and an acetalization degree of 13 mol%.

(2) Preparation of interlayer film for laminated glass With respect to 100 parts by weight of the obtained polyvinyl butyral resin, 40 parts by weight of triethylene glycol-2-ethylhexanoate (manufactured by Sekisui Chemical Co., Ltd.) as a plasticizer, and zinc acetate (Made by Wako Pure Chemical Industries, Ltd.) was blended so that the zinc concentration in the film would be 100 ppm, and mixed for 10 minutes using a mixing roll under the conditions of a rotation speed of 50 rpm and a set temperature of 150 ° C. to obtain a resin composition. .
The obtained resin composition was extruded by an extruder to obtain a single-layer interlayer film for laminated glass having a thickness of 0.5 mm.

(Example 2)
An interlayer film for laminated glass was obtained in the same manner as in Example 1 except that zinc acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was blended so that the zinc concentration in the film was 200 ppm.

(Example 3)
An interlayer film for laminated glass was obtained in the same manner as in Example 1 except that sodium hydrogen carbonate (manufactured by Tosoh Corporation) was used instead of zinc acetate so that the sodium concentration in the film was 100 ppm.

Example 4
An interlayer film for laminated glass was obtained in the same manner as in Example 1 except that sodium hydrogen carbonate (manufactured by Tosoh Corporation) was used in place of zinc acetate so that the sodium concentration in the film was 200 ppm.

(Comparative Example 1)
A commercially available ionomer (“1705” manufactured by DuPont) was mixed for 10 minutes using a mixing roll under the conditions of a rotation speed of 50 rpm and a set temperature of 150 ° C., and extruded by an extruder, and a single-layer laminated glass having a thickness of 0.5 mm An intermediate film for use was obtained.

(Comparative Example 2)
A commercially available ionomer (“3701” manufactured by DuPont) was mixed for 10 minutes using a mixing roll under the conditions of a rotation speed of 50 rpm and a set temperature of 150 ° C., and extruded by an extruder to form a single-layer laminated glass having a thickness of 0.5 mm. An intermediate film for use was obtained.

(Evaluation)
The interlayer films for laminated glass obtained in Examples and Comparative Examples were evaluated by the following methods.
The results are shown in Table 1.

(1) Measurement of break work amount Using the obtained interlayer film for laminated glass, a test piece sample according to JISK-7128-3 was prepared, and using a micrometer ("DIGIMATIC MICROMETER" manufactured by Mitutoyo) The thickness d (mm) was measured.
Using a universal material testing machine ("RTC-1350A" manufactured by A & D Co., Ltd.), the test piece after the thickness measurement is subjected to a tear test under the conditions of a load cell of 5 kN and a test speed of 500 mm / min. The value of the tear load F (N) with respect to each moving distance (mm) until tearing was obtained.
Next, from the obtained tear load F and thickness d, the stress S (N / mm ² ) at the moving distance is obtained by the following formula, and the integrated value of the stress S from the start of the test to the end of the test is calculated as the work of fracture E (J / Mm ² ).
S = F / (width of test sample x thickness d)
The measurement was performed immediately after leaving the test piece sample in a thermostatic chamber at -10 ° C, 20 ° C and 40 ° C for 10 minutes.

(2) Measurement of storage elastic modulus G ′ The obtained interlayer film for laminated glass was allowed to stand for 2 hours under conditions of a temperature of 25 ° C. and a relative humidity of 30%. Then, viscoelasticity was measured using “ARES-G2” manufactured by TAINSTRUMENTS, and storage elastic modulus G ′ at 20 ° C., 40 ° C. and 60 ° C. was calculated.
Note that a parallel plate having a diameter of 8 mm was used as a jig, and the measurement was performed under the conditions of decreasing the temperature from 100 ° C. to −10 ° C. at a temperature decreasing rate of 3 ° C./min, and under the conditions of frequency 1 Hz and strain 1%.

(3) Evaluation of bending hardness (rigidity) The interlayer film for laminated glass was cut into a width of 30 mm and a length of 200 mm to obtain a test sample. The test sample was stored at 23 ° C. × 50% atmosphere for 2 hours, and then the bending deformation rate was 0.5 cm ⁻ using a pure bending tester (manufactured by Kato Tech Co., Ltd., multipurpose strain tester “KES-FB2-S”). ^It was measured at ¹ / sec. The measurement was performed 3 times for each test sample, and the average value was defined as the bending hardness (gf · cm ² / cm).

(4) Evaluation of roll roll-up property 5 m in the longitudinal direction of the interlayer film for laminated glass was manually wound around a polypropylene core having a core size (outside diameter) of 3 inches.
With this method, when the roll can be wound without generating a gap, “○”, when the winding itself is impossible or when a gap is generated between the wound roll-like sheets Was evaluated as “×”.

(5) Evaluation of followability to curved glass An interlayer film for laminated glass is laminated in a curved glass (length 1 m x width 1 m) in a 23 ° C atmosphere, and the followability of the interlayer film for laminated glass to curved glass is confirmed. did. The case where two or more sides of the peripheral edge of the curved glass were in contact with the laminated glass interlayer film was evaluated as “◯”, and the case of one side or less was evaluated as “x”.

ADVANTAGE OF THE INVENTION According to this invention, it has high rigidity, and can be wound up in a roll-shaped body, and can correct | amend a position easily after the lamination | stacking to the curved glass at the time of laminated glass manufacture, The laminated film for this laminated glass A laminated glass using an intermediate film and an intermediate film roll for laminated glass can be provided.

Claims (5)

An interlayer film for laminated glass containing a polyvinyl acetal resin, a metal atom and a plasticizer,
Ratio of storage elastic modulus G ′ (A) at 20 ° C. and storage elastic modulus G ′ (B) at 40 ° C. measured according to JISK-7128-3 (G ′ (B) / G ′ (A) ) Is 0.1 or less, and the ratio (G ′) of the storage elastic modulus G ′ (A) at 20 ° C. and the storage elastic modulus G ′ (C) at 60 ° C. measured according to JISK-7128-3. (C) / G ′ (A)) is 0.01 or less, an interlayer film for laminated glass. The interlayer film for laminated glass according to claim 1, wherein the polyvinyl acetal resin has a hydroxyl group content of 15 mol% or more and contains 50 ppm or more of metal atoms. The interlayer film for laminated glass according to claim 1 or 2, wherein the metal atom is an alkali metal, an alkaline earth metal or zinc. A laminated glass, wherein the interlayer film for laminated glass according to claim 1, 2 or 3 is laminated between a pair of glass plates. An interlayer film roll for laminated glass, wherein the interlayer film for laminated glass according to claim 1, 2 or 3 is wound into a roll.