JP4339457B2 - Interlayer film for laminated glass - Google Patents

Description

【００９４】
表１から明らかなように、本発明による実施例１〜３及び参考例１，２の中間膜を用いて作製した実施例１〜３及び参考例１，２の合わせガラスは、いずれも０℃〜３０℃の広い温度範囲において優れた遮音性能を発揮した。
【００９５】
これに対し、曇り点（Ｔａｂ）と曇り点（Ｔｂａ）との差（Ｔａｂ−Ｔｂａ）が５０℃未満であった比較例１の中間膜を用いて作製した比較例１の合わせガラス、及び、曇り点（Ｔａａ）及び曇り点（Ｔｂｂ）のいずれもが５０℃を超えていた比較例２〜４の中間膜を用いて作製した比較例２〜４の合わせガラスは、いずれも低温側の温度範囲（０℃〜１０℃）における遮音性能が悪かった。
【００９６】
【発明の効果】
以上述べたように、本発明の合わせガラス用中間膜は、低温から高温までの広い温度範囲において優れた遮音性能を長期にわたって安定的に発揮し、且つ、透明性、耐候性、耐貫通性、衝撃エネルギー吸収性、ガラスと中間膜との適正な接着力等の合わせガラスとして必要な基本性能にも優れる合わせガラスを得るに適する。
【００９７】
又、上記中間膜を用いた本発明の合わせガラスは、低温から高温までの広い温度範囲において優れた遮音性能を長期にわたって安定的に発揮すると共に、合わせガラスとして必要な上記基本性能にも優れるので、特に高い遮音性能が要求される建築物や交通車両等の窓ガラス用遮音性合わせガラスとして好適に用いられる。
【００９８】
【図面の簡単な説明】
【図１】合わせガラスの遮音性能を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an interlayer film for laminated glass and a laminated glass using the interlayer film.
[0002]
[Prior art]
Laminated glass obtained by bonding at least a pair of glass plates with an interlayer film for laminated glass formed by forming a transparent and flexible resin such as polyvinyl acetal resin plasticized by adding a plasticizer is damaged. Since fragments are not scattered sometimes and are excellent in safety, they are widely used, for example, for window glass of traffic vehicles such as automobiles and window glass of buildings.
[0003]
Among such interlayer films, an interlayer film formed of a polyvinyl butyral resin plasticized by the addition of a plasticizer has an appropriate adhesive strength with glass, tough tensile strength, excellent transparency, etc. It has various performances, so it is particularly suitable for window glass for traffic vehicles. On the other hand, ordinary polyvinyl butyral resin-based interlayer film is not sufficient for sound insulation for building window glass. There is a problem.
[0004]
In general, the sound insulation performance is shown as a transmission loss corresponding to a change in frequency, as shown in FIG. In JIS A-4706 “Sash”, the transmission loss is defined as a constant value according to the sound insulation class in the region of frequency 500 Hz or higher, as indicated by a solid line in FIG.
[0005]
By the way, the sound insulation performance of the glass plate is significantly reduced due to the coincidence effect in a frequency region centered on 2000 Hz, as indicated by a broken line in FIG. That is, the trough portion of the broken line in FIG. 1 corresponds to a decrease in the sound insulation performance due to the coincidence effect, and indicates that the predetermined sound insulation performance is not maintained.
[0006]
The coincidence effect is a phenomenon in which when a sound wave is incident on a glass plate, a transverse wave propagates on the glass surface due to the rigidity and inertia of the glass plate, and this transverse wave and the incident sound resonate, resulting in sound transmission. To tell.
[0007]
Although conventional laminated glass is extremely superior in preventing shattering of broken pieces at the time of breakage, with regard to sound insulation performance, as with ordinary glass plates, avoiding the deterioration of sound insulation performance due to the above-mentioned coincidence effect in the frequency region centered on 2000 Hz. However, improvement of this point is demanded.
[0008]
In addition, it is known from the equal loudness curve that human hearing is very sensitive in the frequency range of 1000 to 6000 Hz compared to other frequency regions, and prevents a decrease in sound insulation performance due to the coincidence effect. This is extremely important for improving the sound insulation (sound insulation) of window glass and walls.
[0009]
The problem with respect to the decrease in the sound insulation performance due to the coincidence effect is the minimum part of the transmission loss in FIG. 1 caused by the coincidence effect (hereinafter, “the transmission loss (dB) of the minimum part” is referred to as “TL value”). In order to improve the sound insulation performance, it is necessary to alleviate the coincidence effect and prevent the TL value from decreasing.
[0010]
Conventionally, as a means for preventing a decrease in the TL value, various measures such as an increase in the mass of laminated glass, glass double layering, glass area subdivision, and improvement of glass plate supporting means have been adopted. None of these measures bring about a sufficient effect of preventing a decrease in the TL value, and there is a problem that the cost is not practical.
[0011]
On the other hand, the demand for sound insulation performance has been increasing recently. For example, in the case of a window glass for a building, it is required to exhibit excellent sound insulation performance near room temperature. That is, the temperature with the best sound insulation performance obtained by plotting the TL value against the temperature {maximum sound insulation performance temperature (TLmax temperature)} is near room temperature, and the maximum value of the sound insulation performance {maximum sound insulation performance}. Value (TLmax value)} itself is required to have excellent sound insulation performance.
[0012]
In the case of window glass for transportation vehicles, the situation is the same. For example, there is an increasing demand for high sound insulation performance against wind noise during high-speed traveling, vibration noise from the engine unit, and the like.
[0013]
In actual use, these laminated glasses are exposed to a wide range of environmental temperature changes from a low temperature range to a high temperature range. That is, it is required to exhibit excellent sound insulation performance not only in the vicinity of normal temperature but also in a wide temperature range from low temperature to high temperature. However, in the case of laminated glass using a plasticized polyvinyl butyral resin film, which is the most common intermediate film in the past, the maximum sound insulation performance temperature (TLmax temperature) is higher than room temperature, and the sound insulation performance near room temperature is not necessarily good. There is a problem.
[0014]
Various attempts have been made to deal with these problems. For example, in JP-A-2-229742, “a layer A mainly composed of a polymer substance having a glass transition temperature of 15 ° C. or less and plasticized polyvinyl There is disclosed a “sound insulating laminated glass” in which an acetal film B is laminated between glass plates.
[0015]
However, the sound-insulating laminated glass disclosed in the above disclosure does not exhibit a sound insulation performance exceeding the Ts-35 grade in the sound insulation class according to JIS A-4706, and also has a problem that the temperature range in which good sound insulation performance is exhibited is narrow. There is.
[0016]
Further, in Japanese Patent Laid-Open No. 51-106190, “two or more types of resins having different glass transition temperatures are laminated, and a metal plate is bonded to one side or both sides, or a metal plate is placed between these two or more types of resins. A composite metal plate for vibration isolation characterized by being provided is disclosed.
[0017]
However, although the vibration-damping composite metal plate disclosed in the above disclosure is recognized to have improved vibration damping properties over a wide temperature range, sound insulation and transparency required for laminated glass, high impact energy absorption, glass It does not satisfy requirements such as scattering prevention property at the time of breakage, and is not used as a laminated glass.
[0018]
Further, in Japanese Patent Laid-Open No. 4-254444, “a laminated film composed of two types of resin films (A) and (B), wherein the resin film (A) is an acetal containing polyvinyl alcohol with an aldehyde having 6 to 10 carbon atoms. The resin film (B) is composed of a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde having 1 to 4 carbon atoms and a plasticizer. An interlayer film for sound insulating laminated glass is disclosed.
[0019]
However, the sound insulating interlayer disclosed in the above disclosure certainly has an effect of improving the sound insulating performance, and the fluctuation of the sound insulating performance due to temperature change is not large, but these improvements are considered when considering practical aspects under severe conditions. The effect is still not enough.
[0020]
As described above, an interlayer film for laminated glass suitable for obtaining a laminated glass that has excellent basic performance required as a laminated glass and that stably exhibits excellent sound insulation performance in a wide temperature range over a long period of time has not yet been put into practical use. is the current situation.
[0021]
[Problems to be solved by the invention]
In view of the above problems, the object of the present invention is to stably exhibit excellent sound insulation performance over a long period of time in a wide temperature range from low temperature to high temperature, and to have transparency, weather resistance, penetration resistance, impact energy absorption To provide an interlayer film for laminated glass suitable for obtaining a laminated glass excellent in basic performance necessary as a laminated glass such as an appropriate adhesive strength between the glass and the interlayer film, and a laminated glass using the interlayer film is there.
[0022]
[Means for Solving the Problems]
In the interlayer film for laminated glass of the present invention, the resin layer (A) comprising the polyvinyl acetal resin (a) and the plasticizer (a) and the polyvinyl acetal are used in order to make the sound insulation performance of the laminated glass excellent in a wide temperature range. The resin layers (B) made of the resin (b) and the plasticizer (b) are alternately laminated.
[0023]
By alternately laminating the resin layer (A) and the resin layer (B), the temperature dependency of the sound insulation performance of the resin layer (A) and the temperature dependency of the sound insulation performance of the resin layer (B) are overlapped. The laminated glass produced using the laminated film (interlayer film for laminated glass) can exhibit excellent sound insulation performance in a wide temperature range.
[0024]
In general, in order to improve the sound insulation performance on the lower temperature side by using the laminated film, for example, a method of shifting the sound insulation performance of one resin layer constituting the laminated film to the lower temperature side is employed. Specifically, this is a method of increasing the glass transition temperature (Tg) of the resin layer by increasing the amount of plasticizer added in one resin layer.
[0025]
However, in the case of the above method, depending on the type and configuration of the resin layer constituting the laminated film, the plasticizer moves from one resin layer to the other resin layer with an increased amount of plasticizer, and the desired glass transition temperature is lowered. Therefore, the sound insulation performance on the low temperature side of the laminated film is not improved, and therefore, it may not be possible to realize excellent sound insulation performance in a wide temperature range. That is, there is a problem that the temperature dependency of the sound insulation performance imparted to one resin layer is not necessarily expressed in the laminated film.
[0026]
As a result of intensive investigations that the temperature dependence of the sound insulation performance imparted to each resin layer constituting the laminated film does not change even after the inventors have made the laminated film, the present inventors have found that the polyvinyl acetal contained in each resin layer The inventors have found that the above problems can be solved by controlling the compatibility between the resin and the plasticizer and the compatibility between the one resin layer and the other resin layer, and the present invention has been completed.
[0027]
That is, the interlayer film for laminated glass according to claim 1 comprises a polyvinyl acetal resin (a) and , At least one of triethylene glycol di-2-ethylhexanoate and triethylene glycol di-n-heptanoate Plasticizer (a )When A resin layer (A) comprising a polyvinyl acetal resin (b) , At least one of triethylene glycol di-2-ethylhexanoate and triethylene glycol di-n-heptanoate Plasticizer (b )When The resin layer (B) is composed of alternating layers, and the cloud point (Tab) of the mixed solution of the polyvinyl acetal resin (a) and the plasticizer (b), the polyvinyl acetal resin (b) and the plasticizer The absolute value (| Tab−Tba |) of the difference from the cloud point (Tba) of the mixed solution with (a) is 50 ° C. or more, and the polyvinyl acetal resin (a) and the plasticizer (a) The cloud point (Taa) of the mixed solution and / or the cloud point (Tbb) of the mixed solution of the polyvinyl acetal resin (b) and the plasticizer (b) is 50 ° C. or less.
[0029]
The present invention The laminated glass is characterized by being formed by interposing the interlayer film for laminated glass according to claim 1 between at least a pair of glasses.
[0030]
The cloud point referred to in the present invention is a cloud point measured according to JIS K-2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”, specifically, 100 weight of plasticizer. When a mixed solution in which 8 parts by weight of the polyvinyl acetal resin is dissolved to 150 parts by weight is heated to 150 ° C. or higher and then left to stand in an atmosphere of 10 to 30 ° C. to lower the temperature, a part of the mixed solution becomes cloudy. It means the temperature at which it begins to occur. It can be said that the lower the cloud point, the better the compatibility between the polyvinyl acetal resin and the plasticizer.
[0031]
Examples of the method for measuring the cloud point include a method of visually observing the appearance of the mixed solution, a method of measuring the haze value of the mixed solution with a haze meter, and preparing a multi-stage limit sample regarding the degree of cloudiness in advance. And a method of judging cloudiness in contrast to this limit sample.
[0032]
In the interlayer film for laminated glass of the present invention (hereinafter simply referred to as “interlayer film”), the polyvinyl acetal resin (a) used for the resin layer (A) and the plasticizer (b) used for the resin layer (B) And the cloud point (Tba) of the mixed solution of the polyvinyl acetal resin (b) used for the resin layer (B) and the plasticizer (a) used for the resin layer (A). The absolute value of the difference (| Tab−Tba |) must be 50 ° C. or higher, preferably 70 ° C. or higher.
[0033]
The cloud point (Tab) represents the ease of transfer of the plasticizer (b) from the resin layer (B) to the resin layer (A), and the cloud point (Tba) is from the resin layer (A) to the resin layer ( It represents the ease of transfer of the plasticizer (a) to B). Therefore, by setting the absolute value (| Tab-Tba |) of the difference between the cloud point (Tab) and the cloud point (Tba) to 50 ° C. or higher, in other words, Tab-Tba or Tba-Tab is set to 50 ° C. or higher. By doing so, the migration of the plasticizer between the resin layer (A) and the resin layer (B) can be controlled in one direction.
[0034]
For example, when Tab is 100 ° C. and Tba is 20 ° C., the compatibility between the polyvinyl acetal resin (b) and the plasticizer (a) is more compatible with the polyvinyl acetal resin (a) and the plasticizer (b). Since it is superior to the compatibility, and Tab-Tba is 50 ° C. or higher, the migration of the plasticizer (a) from the resin layer (A) toward the resin layer (B) occurs preferentially.
[0035]
In this case, for example, in order to improve the sound insulation performance on the low temperature side of the intermediate film, the addition amount of the plasticizer (b) in the resin layer (B) may be increased. As described above, the migration of the plasticizer (a) in the direction from the resin layer (A) to the resin layer (B) occurs preferentially, so the plasticizer (b) in the resin layer (B) is the resin layer ( It does not shift in the A) direction, and the properties of the resin layer (B) imparted with flexibility by adding a large amount of the plasticizer (b) are maintained in the intermediate film. Therefore, the sound insulation performance on the low temperature side of the intermediate film is improved as originally designed.
[0036]
However, the absolute value (| Tab−Tba) of the difference between the cloud point (Tab) and the cloud point (Tba) is less than 50 ° C., in other words, Tab-Tba or Tba-Tab is less than 50 ° C. The migration of the plasticizer between the resin layer (A) and the resin layer (B) does not stop in one direction but occurs in both directions.
[0037]
For example, when Tab is 100 ° C., Tba is 60 ° C., and Tab-Tba is less than 50 ° C., the plasticizer (b) in the resin layer (B) also moves in the resin layer (A) direction. The properties of the resin layer (B) given flexibility by adding a large amount of the plasticizer (b) are lost in the interlayer film. Accordingly, the sound insulation performance on the low temperature side of the intermediate film is not improved as originally designed.
[0038]
Moreover, in the intermediate film of the present invention, it is used for the cloud point (Taa) and / or the resin layer (B) of the mixed solution of the polyvinyl acetal resin (a) and the plasticizer (a) used for the resin layer (A). The cloud point (Tbb) of the polyvinyl acetal resin (b) and the plasticizer (b) to be obtained needs to be 50 ° C. or lower, preferably 20 ° C. or lower.
[0039]
The cloud point (Taa) represents the compatibility between the polyvinyl acetal resin (a) and the plasticizer (a), and the cloud point (Tbb) is the phase of the polyvinyl acetal resin (b) and the plasticizer (b). Represents solubility. Therefore, by setting the cloud point (Taa) and / or the cloud point (Tbb) to 50 ° C. or less, the respective polyvinyl acetal resins and the respective plasticizers used for the resin layer (A) or the resin layer (B). The compatibility with is extremely excellent.
[0040]
As a result, even if the addition amount of the plasticizer (a) or the plasticizer (b) in the resin layer (A) or the resin layer (B) is small, the polyvinyl acetal resin (a) or the polyvinyl acetal resin (b) On the other hand, it exhibits an excellent plasticizing effect and also suppresses the migration of the plasticizer to the adjacent resin layer when the intermediate film is formed.
[0041]
However, when both the cloud point (Taa) and the cloud point (Tbb) exceed 50 ° C., the respective polyvinyl acetal resins used for the resin layer (A) or the resin layer (B) and the respective plasticizers The compatibility deteriorates, and it is necessary to increase the amount of each plasticizer in order to obtain a sufficient plasticizing effect for each polyvinyl acetal resin.
[0042]
As a result, the plasticizer may easily migrate to the adjacent resin layer when the interlayer film is formed, and long-term weather resistance and durability may be insufficient when the laminated glass is formed.
[0043]
As a preparation method of the polyvinyl acetal resin used for the resin layer (A) and the resin layer (B) constituting the interlayer film of the present invention, for example, an aqueous solution in which polyvinyl alcohol (PVA) is dissolved in warm water is set at a predetermined temperature (for example, 0 to 95 ° C.), the required aldehyde and acid catalyst are added, the acetalization reaction proceeds with stirring, the reaction temperature is then raised to ripen, and then the reaction is completed. A method of obtaining a polyvinyl acetal resin by performing summation, washing with water and drying is mentioned.
[0044]
Although PVA used for preparation of the said polyvinyl acetal resin is not specifically limited, A thing with an average degree of polymerization of 500-5000 is preferable, More preferably, it is 1000-3000. When the average degree of polymerization of PVA is less than 500, the strength of the resin layer and the interlayer film becomes too weak, and the penetration resistance and impact energy absorption when used as laminated glass may be insufficient. When the average degree of polymerization of PVA exceeds 5000, molding of the resin layer may be difficult, and the strength of the resin layer and the intermediate film becomes too strong, and penetration resistance and shock energy absorption when laminated glass is used. May be insufficient. The PVA is not particularly limited, but preferably has a saponification degree of 70 mol% or more. When the degree of saponification of PVA is less than 70 mol%, the transparency and heat resistance of the polyvinyl acetal resin may be lowered or the reactivity may be lowered.
[0045]
Examples of the aldehyde used for the preparation of the polyvinyl acetal resin include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, benzaldehyde, cinnamaldehyde and the like. It is done.
[0046]
Among the various polyvinyl acetal resins thus obtained, a polyvinyl formal resin obtained by reacting PVA and formaldehyde, a narrowly defined polyvinyl acetal resin obtained by reacting PVA and acetaldehyde, and a reaction between PVA and n-butyraldehyde. Polyvinyl butyral resin (PVB) or the like obtained by the above process is preferably used, and PVB is particularly preferably used. By using PVB as the polyvinyl acetal resin, the transparency and weather resistance of the resin layer and the intermediate film, and the adhesive force to glass are excellent.
[0047]
Although the said polyvinyl acetal resin is not specifically limited, A thing with an average acetalization degree of 40-75 mol% is preferable. If the average degree of acetalization of the polyvinyl acetal resin is less than 40 mol%, the compatibility with the plasticizer described later may be reduced. Conversely, in order to obtain a polyvinyl acetal resin having an average acetalization degree exceeding 75 mol% May require a long reaction, which is not preferable in terms of the process.
[0048]
The said polyvinyl acetal resin may be used independently and 2 or more types may be used together. Moreover, the polyvinyl acetal resin (a) used for the resin layer (A) and the polyvinyl acetal resin (b) used for the resin layer (B) may be the same or different. good.
[0049]
Examples of the plasticizer used for the resin layer (A) and the resin layer (B) constituting the interlayer film of the present invention include, for example, ester plasticizers such as monobasic acid esters and polybasic acid esters, and organic phosphorus Examples include acid-based and organic phosphorous acid-based phosphoric acid plasticizers.
[0050]
Examples of monobasic ester plasticizers include glycols such as triethylene glycol, tripropylene glycol, and tetraethylene glycol, and organic compounds such as butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, and 2-ethylhexylic acid. Examples thereof include glycol esters obtained by reaction with an acid.
[0051]
Examples of the polybasic ester plasticizer include esters obtained by reacting linear or branched alcohols having 4 to 8 carbon atoms with organic acids such as adipic acid, sebacic acid, and azelaic acid. .
[0052]
Examples of the phosphoric acid plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, and the like.
[0053]
Among the various plasticizers, for example, triethylene glycol di-2-ethylbutyrate (3GH), triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-n-heptanoate (3G7), triethylene Glycol dicaprylate, triethylene glycol di n-octoate, tetraethylene glycol di 2-ethylbutyrate, tetraethylene glycol di n-heptanoate, dihexyl adipate, dibenzyl phthalate, etc. are preferably used, and particularly preferably used It is 3GH, 3GO, 3G7, etc.
[0054]
The said plasticizer may be used independently and 2 or more types may be used together. Moreover, the plasticizer (a) used for the resin layer (A) and the plasticizer (b) used for the resin layer (B) may be the same or different.
[0055]
The amount of the plasticizer added to the polyvinyl acetal resin is not particularly limited, but in the resin layer serving as the outer layer of the intermediate film, that is, the resin layer bonded to glass, the plasticizer is added to 100 parts by weight of the polyvinyl acetal resin. It is preferable that it is 20-60 weight part of agents, More preferably, it is 30-50 weight part.
[0056]
When the addition amount of the plasticizer relative to 100 parts by weight of the polyvinyl acetal resin is less than 20 parts by weight, the plasticization of the polyvinyl acetal resin may be insufficient, and conversely, when it exceeds 60 parts by weight, the resin layer and the intermediate film Strength and adhesion to glass may be insufficient.
[0057]
Among the combinations of the polyvinyl acetal resin and the plasticizer, a combination using a polyvinyl butyral resin as the polyvinyl acetal resin and using at least one selected from the group consisting of 3GH, 3GO and 3G7 as the plasticizer is particularly preferable.
[0058]
The intermediate film composed of the resin layer (A) and the resin layer (B) by the above combination has not only sound insulation performance but also transparency, weather resistance, penetration resistance, impact energy absorption, and proper adhesion between the glass and the intermediate film. It is suitable for obtaining laminated glass that is superior in basic performance such as strength.
[0059]
In the resin layer (A) and / or the resin layer (B), in addition to the polyvinyl acetal resin and the plasticizer, an ultraviolet absorber, a light stabilizer, an oxidation agent may be used as long as the object of the present invention is not impaired. One kind or two or more kinds of various additives such as an inhibitor, an adhesion adjusting agent, a surfactant, and a colorant may be added.
[0060]
The intermediate film of the present invention needs to be an alternate laminate of the resin layer (A) and the resin layer (B).
[0061]
In the above alternate laminate, for example, when the resin layer (B) has a larger amount of added plasticizer and is more flexible than the resin layer (A), the resin layer (A) is an outer layer, that is, a contact layer with glass. The resin layer (B) is preferably an inner layer, that is, a non-contact layer with glass.
[0062]
By using the resin layer (A) as an outer layer, the handleability and mechanical strength of the intermediate film are improved. On the contrary, when the resin layer (B) is an outer layer, the flexibility of the intermediate film is deteriorated due to its flexibility.
[0063]
Further, the configuration of the alternate laminate is not particularly limited. For example, a three-layer laminate or a resin layer (A) composed of resin layer (A) / resin layer (B) / resin layer (A). A five-layer laminate comprising: / resin layer (B) / resin layer (A) / resin layer (B) / resin layer (A) is preferred.
[0064]
Although the thickness of the interlayer film of the present invention is not particularly limited, it is preferably 0.3 to 1.6 mm as with a normal interlayer film. The sound insulation performance itself becomes better as the thickness of the intermediate film becomes thicker, but if the thickness of the intermediate film becomes too thick, the penetration resistance and impact energy absorption when used as laminated glass may decrease, so the above A thickness in the range is preferred.
[0065]
Examples of the method for producing the interlayer film of the present invention include, for example, a method in which the resin layer (A) and the resin layer (B) are separately formed (film formation) and then alternately laminated, or a multilayer molding machine is used. And a method of integrally forming the resin layer (A) and the resin layer (B) so as to be alternately laminated.
[0066]
Next, the laminated glass of the present invention is produced by interposing and integrating the above-described intermediate film of the present invention between at least a pair of glasses.
[0067]
The glass includes not only normal inorganic transparent glass but also organic transparent glass such as polycarbonate plate and polymethyl methacrylate plate.
[0068]
The type of the glass is not particularly limited, but various inorganic glasses such as, for example, float plate glass, polished plate glass, flat glass, curved plate glass, parallel plate glass, type plate glass, wire mesh type plate glass, and colored glass And one or more of these are preferably used. The thickness of the glass is not particularly limited as long as it is appropriately selected depending on the application and purpose.
[0069]
The manufacturing method of the said laminated glass is not a special thing, The manufacturing method similar to the case of a normal laminated glass is employ | adopted. For example, the interlayer film of the present invention is sandwiched between two transparent glass plates, put in a rubber bag, pre-adhered at a temperature of about 70 to 110 ° C. while sucking and degassing under reduced pressure, and then subjected to an autoclave or press. Used, temperature about 120-150 ° C, pressure 10-15kg / cm ² A desired laminated glass can be obtained by carrying out the main adhesion by heating and pressing under the conditions of about.
[0070]
[Action]
The intermediate film of the present invention comprises a resin layer (A) composed of a polyvinyl acetal resin (a) and a plasticizer (a), and a resin layer (B) composed of a polyvinyl acetal resin (b) and a plasticizer (b). Of the mixed solution of the polyvinyl acetal resin (a) and the plasticizer (b), the cloud point (Tab) of the mixed solution of the polyvinyl acetal resin (a) and the plasticizer (b), and the plasticizer (a). The cloud point of the mixed solution of the polyvinyl acetal resin (a) and the plasticizer (a) is set so that the absolute value (| Tab−Tba |) of the difference from the cloud point (Tba) is not less than a specific value. Since the cloud point (Tbb) of the mixed solution of (Taa) and / or polyvinyl acetal resin (b) and the plasticizer (b) is set to a specific value or less, a wide temperature range from low temperature to high temperature Excellent sound insulation performance in With long-term stability exhibited, transparency, weather resistance, penetration resistance, impact energy absorption, suitable for obtaining a laminated glass excellent in basic performances such proper adhesion between the glass and the intermediate film.
[0071]
Moreover, the performance can be further improved by using a polyvinyl butyral resin as the polyvinyl acetal resin and at least one selected from the group consisting of 3GH, 3GO and 3G7 as the plasticizer.
[0072]
Since the laminated glass of the present invention is produced using the interlayer film of the present invention, it exhibits excellent sound insulation performance in a wide temperature range from low temperature to high temperature for a long period of time, and transparency, weather resistance, It also excels in basic performance such as penetration resistance, impact energy absorption, and proper adhesion between glass and interlayer.
[0073]
DETAILED DESCRIPTION OF THE INVENTION
In order to describe the present invention in more detail, examples are given below, but the present invention is not limited to these examples. In the examples, “part” means “part by weight”.
[0074]
( reference Example 1)
[0075]
(1) Preparation of resin layer (A)
Polyvinyl glycol as a plasticizer (a) with respect to 100 parts of polyvinyl butyral resin {PVB-a (degree of butyralization: 65.9 mol%, acetyl group content: 0.9 mol%)} as polyvinyl acetal resin (a) After adding 40 parts of di-2-ethylbutyrate (3GH) and sufficiently kneading with a mixing roll, the kneaded product was press-molded at 150 ° C. for 30 minutes using a press molding machine, and a resin having a film thickness of 0.2 mm Layer (A) was prepared.
[0076]
(2) Preparation of resin layer (B)
Polyvinyl butyral resin {PVB-b (degree of butyralization: 57.3 mol%, acetyl group content: 13.0 mol%)} 100 parts as polyvinyl acetal resin (b), and 3 parts by weight of 3GH as plasticizer (b) After adding and kneading sufficiently with a mixing roll, the kneaded product was press-molded at 150 ° C. for 30 minutes using a press molding machine to prepare a resin layer (B) having a thickness of 0.4 mm.
[0077]
(3) Cloud point measurement
The cloud point (Taa) of the mixed solution of PVB-a and 3GH used above and the cloud point (Tbb) of the mixed solution of PVB-b and 3GH were measured by the following methods. The results are shown in Table 1. still, reference In Example 1, since the plasticizer for the resin layer (A) and the plasticizer for the resin layer (B) were the same (3GH), the cloud point (Tab) was equal to the cloud point (Taa), and the cloud point ( Tba) was equal to the cloud point (Tbb).
[Measurement of Cloud Point] 100 parts of a plasticizer and 8 parts of PVB were placed in a glass test tube and heated to 170 ° C. to dissolve PVB in the plasticizer to obtain a PVB-plasticizer solution. Next, the solution was stirred and cooled while measuring the temperature of the solution with a thermocouple, the temperature at which a part of the solution began to cloud was read, and this temperature was taken as the cloud point.
[0078]
(4) Production of interlayer film and laminated glass
Using the resin layer (A) and resin layer (B) obtained above, the laminate structure is laminated so that the layer structure is resin layer (A) / resin layer (B) / resin layer (A). A membrane was obtained. Next, the interlayer film was sandwiched between two transparent float glasses (length 30 cm × width 30 cm × thickness 3 mm), placed in a rubber bag, deaerated at a vacuum of 20 torr for 20 minutes, and then deaerated. In the state as it was, it moved to 90 degreeC oven, and it hold | maintained at 90 degreeC for 30 minutes, and pre-adhered the laminated glass with the vacuum press.
[0079]
Next, the pre-bonded laminated glass is put in an autoclave, and the temperature is 135 ° C. and the pressure is 12 kg / cm. ² This bonding was performed for 20 minutes under the conditions described above to produce a transparent laminated glass.
[0080]
(5) Evaluation
The sound insulation of the laminated glass obtained above was evaluated by the following method. The results are shown in Table 1.
[0081]
Evaluation method of sound insulation: A specimen is cut out from the laminated glass obtained above, and this specimen is vibrated with a vibration generator for vibration test (trade name “G21-005D”, manufactured by Shinken Co., Ltd.). The vibration characteristics obtained from the above are amplified by a mechanical impedance amplifier (trade name “XG-81”, manufactured by Rion), and the vibration spectrum is FFT analyzer (trade name “FFT spectrum analyzer HP-3582AA”, Yokogawa Hewlett-Packard Company). Manufactured). A graph showing the relationship between the frequency (Hz) and the transmission loss (dB) is created from the loss coefficient thus obtained and the ratio of the resonance frequency with the glass, and the minimum transmission loss {TL value ( dB)}. In addition, the measurement was performed at each temperature of 0 ° C., 10 ° C., 20 ° C., and 30 ° C., and the sound insulation property acceptance standard was set to a TL value (dB) of 30 or more.
[0082]
(Example 1 ) 100 parts of polyvinyl butyral resin {PVB-c (degree of butyralization: 68.9 mol%, acetyl group content: 0.9 mol%)} as polyvinyl acetal resin (a), triethylene as plasticizer (a) Except for adding 39 parts of glycol di-2-ethylhexanoate (3GO) reference In the same manner as in Example 1, a resin layer (A) having a thickness of 0.2 mm was produced. Further, as a polyvinyl acetal resin (b), 100 parts of polyvinyl butyral resin {PVB-d (degree of butyralization: 63.6 mol%, acetyl group content: 13.0 mol%)} is used as 3GO65 as a plasticizer (b). Except that part was added reference In the same manner as in Example 1, a resin layer (B) having a thickness of 0.4 mm was produced.
[0083]
(Example 2 )Example 1 The resin layer (A) prepared in (1) was used as the resin layer (A) as it was. Further, as a polyvinyl acetal resin (b), 100 parts of polyvinyl butyral resin {PVB-e (degree of butyralization: 64.5 mol%, acetyl group content: 13.0 mol%)} is used as a plasticizer (b). Except that part was added reference In the same manner as in Example 1, a resin layer (B) having a thickness of 0.4 mm was produced.
[0084]
(Example 3 ) As a polyvinyl acetal resin (a) reference Except for adding 40 parts of triethylene glycol di-n-heptanoate (3G7) as a plasticizer (a) to 100 parts of PVB-a used in Example 1 reference In the same manner as in Example 1, a resin layer (A) having a thickness of 0.1 mm was produced. Moreover, as polyvinyl acetal resin (b) reference Except for adding 3G765 parts as a plasticizer (b) to 100 parts of PVB-b used in Example 1. reference In the same manner as in Example 1, a resin layer (B) having a thickness of 0.2 mm was produced.
[0085]
( reference Example 2 ) Example as polyvinyl acetal resin (a) 1 Except for adding 40 parts of 3GH as a plasticizer (a) to 100 parts of PVB-c used in reference In the same manner as in Example 1, a resin layer (A) having a thickness of 0.2 mm was produced. Moreover, as polyvinyl acetal resin (b) reference Except for adding 70 parts of 3GH as a plasticizer (b) to 100 parts of PVB-b used in Example 1. reference In the same manner as in Example 1, a resin layer (B) having a thickness of 0.4 mm was produced.
[0086]
Comparative Example 1 Example 1 The resin layer (A) prepared in (1) was used as the resin layer (A) as it was. Moreover, as polyvinyl acetal resin (b) reference Except for adding 3G770 parts as a plasticizer (b) to 100 parts of PVB-b used in Example 1. reference In the same manner as in Example 1, a resin layer (B) having a thickness of 0.4 mm was produced.
[0087]
(Comparative Example 2) As a polyvinyl acetal resin (a) reference Except for adding 40 parts of 3GO as a plasticizer (a) to 100 parts of PVB-a used in Example 1. reference In the same manner as in Example 1, a resin layer (A) having a thickness of 0.2 mm was produced. Moreover, as polyvinyl acetal resin (b) reference Except for adding 3 parts of GO as plasticizer (b) to 100 parts of PVB-b used in Example 1. reference In the same manner as in Example 1, a resin layer (B) having a thickness of 0.4 mm was produced.
[0088]
Comparative Example 3 Example 1 The resin layer (A) prepared in (1) was used as the resin layer (A) as it was. Further, the resin layer (B) produced in Comparative Example 2 was used as it is as the resin layer (B).
[0089]
Comparative Example 4 Example 1 The resin layer (A) prepared in (1) was used as the resin layer (A) as it was. Moreover, as polyvinyl acetal resin (b) reference Except for adding 80 parts of 3GO as a plasticizer (b) to 100 parts of PVB-b used in Example 1. reference In the same manner as in Example 1, a resin layer (B) having a thickness of 0.4 mm was produced.
[0090]
Example 1 ~ 3. Reference example 2 And each polyvinyl acetal resin (a), each plasticizer (a), each polyvinyl acetal resin (b) and each plasticizer (b) used in Comparative Examples 1 to 4, reference In the same manner as in Example 1, the cloud point (Tab), cloud point (Tba), cloud point (Taa), and cloud point (Tbb) were measured. The results are shown in Table 1.
[0091]
Example 1, 2, Reference Example 2 And using each resin layer (A) and each resin layer (B) produced in Comparative Examples 1 to 4, reference In the same manner as in Example 1, a three-layer interlayer film and a laminated glass were produced. Examples 3 Were laminated such that the laminated structure was resin layer (A) / resin layer (B) / resin layer (A) / resin layer (B) / resin layer (A) to produce a five-layer interlayer film. . Other than using the above interlayer film reference A laminated glass was produced in the same manner as in Example 1.
[0092]
Example 1 ~ 3. Reference example 2 And the sound insulation performance of the laminated glass obtained in Comparative Examples 1 to 4 reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
[0093]
[Table 1]

[0094]
As is clear from Table 1, Examples 1 to 1 according to the present invention 3 and Reference Examples 1 and 2 Examples 1 to 3 prepared using the intermediate film of 3 and Reference Examples 1 and 2 All of the laminated glasses exhibited excellent sound insulation performance in a wide temperature range of 0 ° C to 30 ° C.
[0095]
On the other hand, the laminated glass of Comparative Example 1 produced using the interlayer film of Comparative Example 1 in which the difference (Tab−Tba) between the cloud point (Tab) and the cloud point (Tba) was less than 50 ° C., and As for the laminated glass of Comparative Examples 2-4 produced using the intermediate film of Comparative Examples 2-4 in which both the cloud point (Taa) and the cloud point (Tbb) exceeded 50 ° C, the temperature on the low temperature side was used. The sound insulation performance in the range (0 ° C. to 10 ° C.) was poor.
[0096]
【The invention's effect】
As described above, the interlayer film for laminated glass of the present invention stably exhibits excellent sound insulation performance over a long period of time in a wide temperature range from low temperature to high temperature, and has transparency, weather resistance, penetration resistance, It is suitable for obtaining laminated glass excellent in basic performance required as laminated glass, such as impact energy absorption and appropriate adhesion between glass and interlayer film.
[0097]
In addition, the laminated glass of the present invention using the intermediate film stably exhibits excellent sound insulation performance in a wide temperature range from low temperature to high temperature over a long period of time, and also excellent in the basic performance required as a laminated glass. In particular, it is suitably used as a sound insulating laminated glass for window glass of buildings and traffic vehicles that require particularly high sound insulation performance.
[0098]
[Brief description of the drawings]
FIG. 1 is a graph showing the sound insulation performance of laminated glass.

Claims (1)

A resin layer (A) comprising a polyvinyl acetal resin (a) and a plasticizer (a ) which is at least one of triethylene glycol di-2-ethylhexanoate and triethylene glycol di n-heptanoate ;
Alternating lamination of a polyvinyl acetal resin (b) and a resin layer (B) comprising a plasticizer (b ) which is at least one of triethylene glycol di-2-ethylhexanoate and triethylene glycol di n-heptanoate Body,
Difference between the cloud point (Tab) of the mixed solution of the polyvinyl acetal resin (a) and the plasticizer (b) and the cloud point (Tba) of the mixed solution of the polyvinyl acetal resin (b) and the plasticizer (a). The absolute value (| Tab-Tba |) is 50 ° C. or more, and the cloud point (Taa) of the mixed solution of the polyvinyl acetal resin (a) and the plasticizer (a) and / or the polyvinyl acetal resin ( An interlayer film for laminated glass, wherein a cloud point (Tbb) of a mixed solution of b) and a plasticizer (b) is 50 ° C or lower.

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