JP4528188B2 - Thermoplastic resin sheet and laminate - Google Patents

Description

  The present invention relates to a thermoplastic resin sheet having a structure in which a plurality of types of polyvinyl acetal resin layers are laminated, and a laminate using the thermoplastic resin sheet, and is suitably used for an interlayer film of laminated glass used for vehicles, for example. The present invention relates to a thermoplastic resin sheet and a laminate using the thermoplastic resin sheet.

  Laminated glass is widely used as a glass that can be attached to windows and the like in transportation such as automobiles, railway vehicles, and airplanes, and buildings. In laminated glass, a thermoplastic resin sheet is interposed as an intermediate film between a transparent first glass plate or resin plate and a transparent second glass plate or resin plate. By making a thermoplastic resin sheet exist in between, the laminated glass is made difficult to break.

  The following Patent Document 1 discloses a laminated glass in which two glass plates are laminated through a thermoplastic resin sheet made of PVB (polyvinyl butyral resin), particularly as an aircraft window glass. This thermoplastic resin sheet has a three-layer structure in which an inner layer made of PVB and a surface layer made of PVB and positioned on both surfaces of the inner layer are laminated. And the ratio of the plasticizer content in the surface layer and the plasticizer content in the inner layer is set to 1.2-3.

  In the laminated glass described in Patent Document 1, the elastic modulus of the surface layer is relatively lowered by making the plasticizer content of the surface layer higher than the plasticizer content of the inner layer. In this window glass, since the thermoplastic resin sheet is used, for example, it is said that the impact resistance is excellent even at a low temperature. In particular, when a chemically strengthened glass plate is used as the glass plate, the compression amount of the thickness is smaller than that of the thermally strengthened glass plate. On the other hand, it is said that by using the thermoplastic resin sheet, it is possible to suppress cracking of the glass plate even when a chemically strengthened glass plate is used.

  On the other hand, the following Patent Document 2 discloses a laminated glass using a thermoplastic resin sheet formed by laminating a plurality of resin layers made of PVB as a laminated glass used for a vehicle or the like, as in Patent Document 1. ing. In this thermoplastic resin sheet, the Tg is in the range of 35 to 60 ° C., and the Tg is in the range of 32 to 35 ° C. on both sides of the inner layer made of relatively hard PVB. An outer layer made of soft PVB is laminated.

And in patent document 2, it is supposed that the laminated glass which is excellent in mechanical strength and is stable can be provided by laminating | stacking an outer layer on both surfaces of the said inner layer.
Japanese Patent No. 3300402 WO03 / 097347 A1

  For example, laminated glass is widely used as safety glass for vehicles such as automobiles, but this type of laminated glass is strongly required to have high penetration resistance. For example, in Japan, a safety glass test method for automobiles is defined in JIS R 3212. In JIS R 3212, with respect to penetration resistance, a steel ball having a mass of 2260 ± 20 g and a diameter of about 82 mm was placed on a laminated glass sample having an area of about 300 × 300 mm stored in a room at 23 ± 2 ° C. for 4 hours or more. This is done by dropping from a height of 4 m onto the center of the sample. When this steel ball is dropped, it is required that the steel ball does not penetrate through the laminated glass.

  The penetration resistance is also important for preventing the theft of money due to vandalism. In other words, in the case of breaking on a car, a window glass is smashed using a hammer or the like to steal internal metal parts, but if the penetration resistance is low, the window glass can be easily broken. On the other hand, if the penetration resistance is high, the window glass is difficult to break even if the window glass is subjected to a considerable number of impacts using a hammer or the like. Therefore, there is a high possibility that the window glass breaking work due to the vandalization is heard by a third party or witnessed by the third party. Therefore, the vandalism is likely to give up if the window glass cannot be easily broken. Therefore, in order to reliably prevent theft due to vandalism, it is strongly desired that the window glass has high penetration resistance.

  On the other hand, for example, while traveling in a car, an object may be scattered or dropped from the front or above, and an impact may be applied to the window glass from the outside of the car, causing the window glass to be broken. In addition, the window glass may be broken due to a collision accident or the like. In such a case, there is a possibility that an occupant riding inside the vehicle may be seriously damaged by the glass pieces scattered by the impact. Therefore, in order to ensure the safety of passengers such as vehicles, it is required that the glass on the inner side of the vehicle does not peel or scatter when it is broken by impact.

  By the way, in the test method described above, evaluation is made at a temperature of 23 ± 2 ° C., but the actual laminated glass for vehicles is exposed to a relatively high temperature environment of 30 ° C. or more, for example, from a temperature range below freezing. It will be. Accordingly, there is a strong demand for excellent penetration resistance over such a wide temperature range.

  There is also a method to create laminated glass by laminating multiple types of resin films such as polyethylene terephthalate, polycarbonate, and ionomer to ensure penetration resistance. For this reason, not only is the work complicated, but if the interface of the laminated resin film is not smooth, the image transmitted through the laminated glass may be distorted due to the generated optical distortion, and depending on the type of resin, There was a problem that it did not adhere to the PVB resin.

  Increasing the thickness of the intermediate film is also effective for improving penetration resistance. However, this method increases the weight of the structure, and is not appropriate for reducing the weight of the vehicle required for improving fuel efficiency. Moreover, since it became thick, there existed a fault that it became difficult to handle a laminated glass.

  In addition, as another method of improving the penetration resistance, there is a method of increasing the thickness of the glass constituting the laminated glass. However, in this method, the weight of the structure increases, so that the weight of the vehicle can be reduced. Not suitable. As described above, with the conventional method, it has been very difficult to reduce the weight of the vehicle without reducing the penetration resistance.

  In the laminated glass described in Patent Document 1 and Patent Document 2, in the thermoplastic resin sheet in which the inner layer made of PVB and the outer layer made of PVB are laminated, the plasticizer content on the outer layer side is relatively increased. The strength of the inner layer was increased, thereby improving the mechanical strength of the laminated glass.

  However, in general, the thermoplastic resin sheet has temperature dependence, and at a low temperature, the maximum stress of the thermoplastic resin becomes large, but the elongation becomes small and becomes brittle. On the other hand, at a high temperature, the elongation of the thermoplastic resin is large, but the maximum stress is small and too soft. In either case, the impact resistance is small. The laminated glass configurations described in Patent Document 1 and Patent Document 2 have a drawback that the impact resistance of the thermoplastic resin sheet is not sufficient particularly in a low temperature range.

  In Patent Documents 1 and 2, the resins constituting the inner layer and the outer layer are the same PVB, and the mechanical strength of the inner layer is relatively increased by simply varying the plasticizer content. It wasn't too much.

  On the other hand, at the time of producing laminated glass, an autoclave process in which treatment is performed under high temperature and high pressure is usually used to produce laminated glass having a good appearance. In the autoclave process, as described in Patent Documents 1 and 2, when a multilayer film thermoplastic resin sheet composed of the same PVB is used, if the resin composition of the inner layer and the outer layer is the same, a high temperature / high pressure treatment is performed. Thus, a single layer thermoplastic resin sheet with a small number of plasticizer parts is obtained. That is, the plasticizer on the outer layer side is transferred to the inner layer, so that a single-layer thermoplastic resin sheet having a small plasticizer content as a whole is obtained. The thermoplastic resin sheet composed of a single-layer PVB sheet with a low plasticizer content increases the penetration resistance at high temperatures, but the penetration resistance at low temperatures is inevitably reduced. There was a drawback that penetration resistance performance could not be ensured in all temperature ranges up to.

  Further, if the high-temperature and high-pressure treatment in the autoclave process is moderated, the plasticizer hardly migrates, but in that case, it may be difficult to sufficiently adhere the inner layer and the outer layer.

  Moreover, in the laminated glass of patent document 1, 2, only PVB was used as resin which comprises the said thermoplastic resin sheet. Therefore, in order to make the physical properties of the inner layer and the outer layer different, PVA having a large amount of acetyl groups present in the raw material polyvinyl alcohol (hereinafter abbreviated as PVA) is used. It was necessary to use a PVB resin having a large amount of acetyl groups.

  PVB with a low degree of butyralization becomes hard when the plasticizer content is the same, and it is possible to improve penetration resistance. However, when the degree of butyralization of PVB is lowered, the amount of plasticizer that can be contained decreases, and even if an attempt is made to contain a plasticizer that is more than the amount that can be contained, bleeding out occurs and the adhesion performance and appearance are markedly reduced. Also, since the effect of improving penetration resistance is small if the degree of butyralization is reduced, it is necessary to reduce the plasticizer content in the inner layer or increase the thickness ratio of the inner layer in order to increase the mechanical strength of the inner layer. was there. However, when the plasticizer content in the inner layer is reduced or the thickness ratio of the inner layer is increased, the inner layer becomes harder and the penetration resistance at low temperatures is significantly reduced.

  Therefore, in the laminated glass described in Patent Documents 1 and 2, the penetration impact resistance cannot actually be so high, and it is not possible to ensure the penetration impact resistance in a wide temperature range from low temperature to high temperature. could not.

  Further, in PVB, in order to improve the penetration resistance at low temperature, it is necessary to contain a plasticizer to some extent. However, when the plasticizer content is increased, the penetration resistance in the low temperature range is improved, but conversely, the penetration resistance in the high temperature range is lowered.

  In addition, when the amount of acetyl groups in PVB increases, the flexibility tends to increase when the plasticizer content is the same. Therefore, when PVB containing a large number of acetyl groups is used, the inner layer is difficult to harden even in a low temperature range and the penetration resistance is good, but the inner layer is too soft in the high temperature range, and the penetration resistance at high temperature tends to decrease. It was.

  An object of the present invention is a thermoplastic resin sheet obtained by laminating a plurality of resin layers mainly composed of polyvinyl acetal in view of the above-described state of the prior art, and has excellent penetration resistance from a low temperature range to a high temperature range. It is intended to provide a thermoplastic resin sheet that can be used as an intermediate film of laminated glass for automobiles, railway vehicles, aircrafts, and buildings having a laminate, and a laminate using the thermoplastic resin sheet.

The first invention comprises a plasticizer and a first polyvinyl acetal resin obtained by acetalization of polyvinyl alcohol with at least one aldehyde (a) selected from the group consisting of aldehydes having 4 to 6 carbon atoms. At least one selected from the group consisting of a first polyvinyl acetal resin layer (A) containing, a plasticizer , an aldehyde (a) which is n-butyraldehyde having 4 carbon atoms , and an aldehyde having 1 to 3 carbon atoms. A thermoplastic resin sheet laminated with a second polyvinyl acetal resin layer (B) containing a second polyvinyl acetal resin which is a co-acetalized product obtained by co-acetalization of polyvinyl alcohol with aldehyde (b). The first polyvinyl acetal resin layer (on both sides of at least one second polyvinyl acetal resin layer (B)) ) In the second polyvinyl acetal resin layer (B), the acetalization unit derived from the first aldehyde (a) is converted into a polymer unit (X), a second aldehyde ( When the acetalization unit derived from b) is the polymer unit (Y), the total of the polymer unit (X) and the polymer unit (Y) occupies 55 mol% or more of the entire coacetalization product, and The ratio of the first polymer unit (X) is 0.5 to 80 mol%, and the content of the plasticizer in the second polyvinyl acetal resin layer (B) is 100 parts by weight of the second polyvinyl acetal resin. On the other hand, it is 10 to 35 parts by weight, and the plasticizer content ratio of the first polyvinyl acetal resin layer (A) is defined as the plasticizer content (A), and the second polyvinyl acetal resin layer (B The plasticizer content when the plasticizer content (B), plasticizer content (A) / plasticizer content (B) is characterized to be in the range of 1.0 to 3.

In addition, in this specification, the said coacetalization is polyvinyl alcohol from the group which consists of aldehyde (a) which is multiple types of aldehyde, especially n-butyraldehyde of 4 carbon atoms, and C1-C3 aldehyde. A reaction in which at least one selected aldehyde (b) is used to simultaneously acetalize or sequentially acetalize. The coacetal compound is a polyvinyl acetal obtained by coacetalizing polyvinyl alcohol with the aldehyde, wherein the polyvinyl acetal is derived from the aldehyde (a) -derived acetalization unit and the aldehyde (b) -derived There is an acetalization unit. Here, as described above, the acetalization unit in the first aldehyde (a) is defined as the polymer unit (X), and the acetalization unit derived from the second aldehyde (b) is defined as the polymer unit (Y). ing. The polymer unit (X) and the polymer (Y) do not refer to the polymer portion constituting the copolymer, but refer to a part of the polyvinyl acetal as the polymer. That is, the polymer unit (X) refers to a polymer portion that is acetalized with aldehyde (a) in polyvinyl acetal.

The second invention includes a first polyvinyl acetal resin obtained by acetalization of polyvinyl alcohol with at least one aldehyde (a) selected from the group consisting of a plasticizer and an aldehyde having 4 to 6 carbon atoms. At least one aldehyde selected from the group consisting of a first polyvinyl acetal resin layer (A), a plasticizer , an aldehyde (a) which is n-butyraldehyde having 4 carbon atoms , and an aldehyde having 1 to 3 carbon atoms. A thermoplastic resin sheet laminated with a second polyvinyl acetal resin layer (B) containing a second polyvinyl acetal resin that is a co-acetalized product obtained by co-acetalization of polyvinyl alcohol according to (b). The first polyvinyl acetal resin layer (A) is formed on both surfaces of at least one second polyvinyl acetal resin layer (B). In the second polyvinyl acetal resin layer (B), the acetalization unit derived from the first aldehyde (a) is a polymer unit (X) and a second aldehyde (b ) Derived acetalization unit is the polymer unit (Y), the total of the polymer unit (X) and the polymer unit (Y) occupies 55 mol% or more of the entire coacetalization product, and The proportion of one polymer unit (X) is 20 to 80 mol%, and the content of the plasticizer in the second polyvinyl acetal resin layer (B) is 10 parts by weight with respect to 100 parts by weight of the second polyvinyl acetal resin. To 35 parts by weight, and the plasticizer content of the first polyvinyl acetal resin layer (A) is the plasticizer content (A), and the second polyvinyl acetal resin layer (B) The plasticizer content when the plasticizer content (B), plasticizer content (A) / plasticizer content (B) is characterized in that in the range of 1.0 to 3.

The third invention includes a first polyvinyl acetal resin obtained by acetalization of polyvinyl alcohol with at least one aldehyde (a) selected from the group consisting of a plasticizer and an aldehyde having 4 to 6 carbon atoms. At least one aldehyde selected from the group consisting of a first polyvinyl acetal resin layer (A), a plasticizer , an aldehyde (a) which is n-butyraldehyde having 4 carbon atoms , and an aldehyde having 1 to 3 carbon atoms. A thermoplastic resin sheet in which a second polyvinyl acetal resin layer (B) containing a second polyvinyl acetal resin that is a co-acetalized product obtained by co-acetalization of polyvinyl alcohol according to (b) is laminated, A first polyvinyl acetal resin layer (A) is formed on both sides of one second polyvinyl acetal resin layer (B). In the second polyvinyl acetal resin layer (B), the acetalization unit derived from the first aldehyde (a) is converted into a polymer unit (X) and a second aldehyde (b). When the derived acetalization unit is the polymer unit (Y), the total of the polymer unit (X) and the polymer unit (Y) occupies 55 mol% or more of the entire coacetalization product, and the first The ratio of the polymer unit (X) is 0.5 to 20 mol%, and the content of the plasticizer in the second polyvinyl acetal resin layer (B) is 100 parts by weight of the second polyvinyl acetal resin. 10 to 35 parts by weight, and the plasticizer content of the first polyvinyl acetal resin layer (A) is defined as the plasticizer content (A), and the second polyvinyl acetal resin layer (B) is acceptable. The agent content when the plasticizer content (B), plasticizer content (A) / plasticizer content (B) is characterized to be in the range of 1.0 to 3.

  In a specific aspect of the thermoplastic resin sheet according to the first and second inventions, in the coacetalized product constituting the second polyvinyl acetal resin layer (B), the polymer unit (Y) and the polymer unit The polymer unit (Y) / polymer unit (X) which is a molar ratio with (X) is 3.5 or less.

  In a specific aspect of the thermoplastic resin sheet in the first and third inventions, in the coacetalized product constituting the third polyvinyl acetal resin layer (B), the polymer unit (Y) and the polymer unit The polymer unit (Y) / polymer unit (X) which is a molar ratio with (X) is 200 or less.

In still another specific aspect of the thermoplastic resin sheet according to the first to third inventions (hereinafter collectively referred to as the present invention), a sheet consisting only of the polyvinyl acetal resin layer (A) measured at a measurement frequency of 10 Hz. The temperature t (A) indicating the maximum value of the loss tangent tan δ of the sheet is in the range of 20 to 50 ° C., and the temperature t (B indicating the maximum value of the loss tangent tan δ of the sheet made of the second polyvinyl acetal resin layer (B). ) Is in the range of 35-70 ° C, and t (B) -t (A) is in the range of 5 ° C or higher and 40 ° C or lower.

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, a temperature range in which the loss tangent tan δ is 0.3 or more in the sheet made of the first polyvinyl acetal resin layer (A), and the second polyvinyl acetal In the sheet made of the resin layer (B), there is a temperature range where the temperature range where the loss tangent tan δ is 0.3 or more overlaps.

  In still another specific aspect of the thermoplastic resin sheet according to the first and second inventions, more preferably, the maximum loss tangent tan δ of the sheet consisting only of the polyvinyl acetal resin layer (A) measured at a measurement frequency of 10 Hz. The temperature t (A) indicating the value is in the range of 20 to 50 ° C., and the temperature t (B) indicating the maximum value of the loss tangent tan δ of the sheet made of the second polyvinyl acetal resin layer (B) is 40 to 65 ° C. And t (B) -t (A) is preferably in the range of 5 ° C. or more and 25 ° C. or less.

  In still another specific aspect of the thermoplastic resin sheet according to the first and second inventions, more preferably, the loss tangent tan δ is 0.5 or more in the sheet made of the first polyvinyl acetal resin layer (A). It is preferable that there is an overlapping temperature range in the temperature range and the temperature range in which the loss tangent tan δ is 0.5 or more in the sheet made of the second polyvinyl acetal resin layer (B).

  In another specific aspect of the thermoplastic resin sheet according to the present invention, the first polyvinyl acetal resin layer (A) has a shear storage elastic modulus at 23 ° C. and 10 Hz of G ′ (A), and the second polyvinyl acetal resin layer. G '(B) / G' (A) is in the range of 1.0 to 10 when the shear storage modulus at 23 ° C and 10 Hz of (B) is G '(B).

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, the tear strength (B) of the second polyvinyl acetal resin layer (B) measured according to JIS K 7128, and the first polyvinyl acetal resin The tear strength (B) / tear strength (A), which is a ratio to the tear strength (A) of the layer (A), is 1.1 or more.

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, the tensile modulus of elasticity of the second polyvinyl acetal resin layer (B) measured at 23 ° C. and a tensile strain rate of 1250% / min. B) When the tensile elastic modulus of the first polyvinyl acetal resin layer (A) is taken as the tensile elastic modulus (A), the tensile elastic modulus (B) / tensile elastic modulus (A) is 1.1 or more.

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, the breaking energy (B) of the second polyvinyl acetal resin layer (B) measured at 23 ° C. and a tensile strain rate of 1250% / min is used. When the breaking energy of the first polyvinyl acetal resin layer (A) is the breaking energy (A), the breaking energy (B) / breaking energy (A) is 1.1 or more.

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, the maximum point stress of the second polyvinyl acetal resin layer (B) measured at 23 ° C. and a tensile strain rate of 1250% / min is determined as the maximum point stress ( B), and when the maximum point stress of the first polyvinyl acetal resin layer (A) is the maximum point stress (A), the maximum point stress (B) / maximum point stress (A) is 1.0 or more. .

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, the degree of polymerization of the polyvinyl alcohol for constituting the second polyvinyl acetal resin layer (B) is defined as PVA polymerization degree (B), first polyvinyl When the polymerization degree of the polyvinyl alcohol for constituting the acetal resin layer (A) is PVA polymerization degree (A), the PVA polymerization degree (B) / PVA polymerization degree (A) is 0.5 to 3.0. It is in the range.

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, the PVA polymerization degree (B) / PVA polymerization degree (A) is in the range of 1.0 to 3.0.

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, the ester group content in the second polyvinyl acetal resin layer (B) is 40 mol% or less.

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, the ester group content in the second polyvinyl acetal resin layer (B) is 20 mol% or less.

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, functional fine particles are contained in the first polyvinyl acetal resin layer (A) and / or the second polyvinyl acetal resin layer (B).

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, the first polyvinyl acetal resin layer (A) and / or the second polyvinyl acetal resin layer (B) contains a crosslinked polyvinyl acetal resin. Alternatively, the first polyvinyl acetal resin (A) and / or the second polyvinyl acetal resin (B) is a polyvinyl acetal resin obtained by intermolecular crosslinking.

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, the thickness of the second polyvinyl acetal resin layer (B) is the thickness (B), and the thickness of the first polyvinyl acetal resin layer (A) is the thickness ( When A), the thickness (B) / thickness (A) is in the range of 0.5-10.

  In still another specific aspect of the thermoplastic resin sheet according to the present invention, polyvinyl acetal resin layers (A) having different thicknesses are laminated on both surfaces of at least one polyvinyl acetal resin layer (B).

  The laminate according to the present invention includes a thermoplastic resin sheet configured according to the present invention as at least one layer.

  On the specific situation with the laminated body which concerns on this invention, the said thermoplastic resin sheet is narrowly attached between the glass plate and the transparent resin plate.

  On the other specific situation of the laminated body which concerns on this invention, the said transparent resin board is comprised by 1 type selected from the group which consists of a polycarbonate, an acrylic resin, an acrylic copolymer resin, and polyester.

  In still another specific aspect of the laminate according to the present invention, the transparent resin plate is covered with a transparent elastomer.

  In still another specific aspect of the laminate according to the present invention, the thermoplastic resin sheet is tightly attached to a pair of glass plates.

  In still another specific aspect of the laminate according to the present invention, at least one of the glass plates is colored transparent glass.

In still another specific aspect of the laminate according to the present invention, the surface density is 12 kg / m ² or less.

  When the thermoplastic resin sheet according to the first invention is used as an interlayer film of laminated glass, penetration resistance can be enhanced over a wide temperature range. This is because the inner layer of the thermoplastic resin sheet is composed of the second polyvinyl acetal resin layer (B), and in the second polyvinyl acetal resin layer (B), the acetalization unit derived from the first aldehyde (a) Is the polymer unit (X) and the acetalization unit derived from the second aldehyde (b) is the polymer unit (Y), the total of the polymer unit (X) and the polymer unit (Y) is This is because it accounts for 55 mol% or more of the entire acetalized product and the ratio of the first polymer unit (X) is in the range of 0.5 to 80 mol%.

  When the thermoplastic resin sheet according to the second invention is used as an interlayer film of laminated glass, penetration resistance can be enhanced in a wide temperature range, particularly in a low temperature range to a normal temperature range. This is because the inner layer of the thermoplastic resin sheet is composed of the second polyvinyl acetal resin layer (B), and in the second polyvinyl acetal resin layer (B), the acetalization unit derived from the first aldehyde (a) Is the polymer unit (X) and the acetalization unit derived from the second aldehyde (b) is the polymer unit (Y), the total of the polymer unit (X) and the polymer unit (Y) is This is because it accounts for 55 mol% or more of the entire acetalized product and the ratio of the first polymer unit (X) is in the range of 20 to 80 mol%.

  When the thermoplastic resin sheet according to the third invention is used as an interlayer film of laminated glass, penetration resistance can be enhanced in a wide temperature range, particularly in a normal temperature range to a high temperature range. This is because the inner layer of the thermoplastic resin sheet is composed of the second polyvinyl acetal resin layer (B), and in the second polyvinyl acetal resin layer (B), the acetalization unit derived from the first aldehyde (a) Is the polymer unit (X) and the acetalization unit derived from the second aldehyde (b) is the polymer unit (Y), the total of the polymer unit (X) and the polymer unit (Y) is This is because it accounts for 55 mol% or more of the entire acetalized product, and the ratio of the first polymer unit (X) is in the range of 0.5 to 20 mol%.

  That is, as described above, by adjusting the ratio of the polymer units (X) and (Y), the temperature range that maximizes the penetration resistance can be adjusted. By increasing the ratio of polymer unit (Y) / polymer unit (X), which is the molar ratio between polymer unit (Y) and polymer unit (X), penetration resistance performance is exhibited at higher temperatures. Will be able to.

  When the ratio of polymer unit (Y) / polymer unit (X) is increased, the amount of plasticizer that can be contained decreases, and the ratio of polymer unit (Y) / polymer unit (X) is small. Even when compared in the case where the same amount of plasticizer as that of the acetal resin is contained, the obtained polyvinyl acetal resin sheet itself becomes more rigid.

  Thus, the performance of the obtained polyvinyl acetal resin sheet can be adjusted by adjusting the ratio of the polymer unit (X) and the polymer unit (Y).

  Also, when creating a laminate, the thermoplastic resin sheet used has a certain degree of flexibility in order to be able to follow the shapes of various shapes of glass plates and transparent resin plates constituting the laminate. It is preferable. Therefore, the ratio of polymer unit (Y) / polymer unit (X) of the polyvinyl acetal resin sheet is preferably 200 or less, more preferably 3.5 or less.

  Moreover, in the thermoplastic resin sheet and laminated body which concern on this invention, since the intensity | strength of the 2nd polyvinyl acetal resin layer (B) used for an inner layer is strong, even if it produces laminated glass using glass with thin thickness , MBH 4 m or more in the falling ball test in JIS R 3212 can be achieved in a very wide temperature range. This means that even if the surface density of the laminated glass is reduced and the weight of the laminate is reduced, the impact resistance performance is sufficient. That is, it is shown that it is possible to achieve both reduction in weight of the vehicle and securing of impact resistance.

  Details of the present invention will be described below.

(First polyvinyl acetal resin layer (A))
In the thermoplastic resin sheet of the present invention, the first polyvinyl acetal resin layer (A) is a polyvinyl by at least one aldehyde (a) selected from the group consisting of a plasticizer and an aldehyde having 4 to 6 carbon atoms. It is a layer containing the 1st polyvinyl acetal resin obtained by acetalization of alcohol.

  Examples of the aldehyde having 4 to 6 carbon atoms include butyraldehyde, isobutyraldehyde, hexylaldehyde, and n-butyraldehyde is particularly preferable.

  The first polyvinyl acetal resin is obtained by acetalizing polyvinyl alcohol with at least one aldehyde (a) selected from these aldehydes.

  Regarding the polyvinyl alcohol, polyvinyl alcohol having an average degree of polymerization of 500 to 4500 is preferably used, and more preferably 1000 to 2500 PVA is used. When the average degree of polymerization of PVA is less than 500, the penetration resistance may be lowered when a laminated glass is formed. When it exceeds 3000, extrusion molding becomes worse, the strength of the interlayer film becomes too large, and it is used as safety glass. It may not be possible.

  The degree of acetalization in the first polyvinyl acetal resin is preferably 40 to 70 mol%. If the degree of acetalization is less than 40 mol%, the compatibility with the plasticizer is deteriorated, and the plasticizer bleeds out. Therefore, there is a possibility that adverse effects such as a decrease in the adhesive force between the interlayer film made of the thermoplastic resin sheet of the present invention and the glass may occur. If the degree of acetalization exceeds 70 mol%, the interlayer film may become too soft and may not exhibit sufficient penetration resistance.

  As the plasticizer, any conventionally used plasticizer can be used. For example, triethylene glycol di-2-ethylbutyrate (3GH), triethylene glycol di-2-ethylhexanoate (3GO) And triethylene glycol di-2-capryate. These may be used alone or in combination of two or more. Moreover, as a plasticizer of at least two first polyvinyl acetal resin layers (A) laminated on at least both surfaces of the second polyvinyl acetal resin layer (B), different types of plasticizers may be used. The same type of plasticizer may be used. The plasticizer content in the first polyvinyl acetal resin (A) may be usually in the range of 10 to 50 parts by weight with respect to 100 parts by weight of the first polyvinyl acetal resin (A). Preferably, it is 30-45 weight part with respect to 100 weight part of 1st polyvinyl acetal resin (A), More preferably, it is 35-45 weight part with respect to 100 weight part of 1st polyvinyl acetal resin (A). If it is less than 10 parts by weight, the amount of the plasticizer is too small, so that it is difficult to mold the intermediate film, and the flexibility is low, so the intermediate film is hard, the handling property becomes very bad, and the resistance at low temperature is low. Penetration performance may be significantly reduced. When the amount exceeds 50 parts by weight, the penetration resistance when the intermediate film is formed may deteriorate, or the plasticizer may bleed out and the appearance may be significantly impaired.

(Second polyvinyl acetal resin layer (B))
In the first to third inventions, the second polyvinyl acetal resin layer (B) is selected from the group consisting of aldehyde (a) which is n-butyraldehyde having 4 carbon atoms and aldehyde having 1 to 3 carbon atoms. A second polyvinyl acetal resin which is a coacetalized product obtained by coacetalization of polyvinyl alcohol with at least one aldehyde (b) and a plasticizer.

As the aldehyde (a), the same aldehyde as the aldehyde (a) used to obtain the first polyvinyl acetal resin described above can be used. In the first to third inventions, n having 4 carbon atoms is used. -Butyraldehyde is used .

  As the aldehyde (b), aldehydes having 1 to 3 carbon atoms, such as formaldehyde, acetaldehyde, and propionaldehyde can be used. Two or more aldehydes (b) may be used in combination.

  In the second polyvinyl acetal resin layer (B) obtained by coacetalizing polyvinyl alcohol with aldehydes (a) and (b), the acetalization unit derived from the first aldehyde (a) is a polymer unit ( X), when the acetalization unit derived from the second aldehyde (b) is the polymer unit (Y), the total of the polymer unit (X) and the polymer unit (Y) decreases with the plasticizer. Since compatibility is deteriorated and problems such as bleed out occur, the amount is 55 mol% or more of the entire coacetalized product.

In the second polyvinyl acetal resin layer (B) obtained by acetalizing polyvinyl alcohol only with aldehyde (b), the compatibility between the plasticizer and the polyvinyl acetal resin layer (B) is reduced when the degree of acetalization is lowered. bad will, you problem occurs, such as bleed out.

  Moreover, the ratio of the polymer unit (X) and the polymer unit (Y) is adjusted so that the penetration resistance performance of the finally obtained structure exhibits the maximum performance in the required temperature range. When sufficient penetration resistance is required in the normal temperature range to the high temperature range, the polymer is a molar ratio of the polymer unit (X) and the polymer unit (Y) in the second polyvinyl acetal resin layer (B). It is preferable that the unit (Y) / polymer unit (X) is enlarged, or the second polyvinyl acetal resin layer (B) is constituted only by the polymer unit (Y). More preferably, when the second polyvinyl acetal resin layer (B) is composed of the polymer unit (X) and the polymer unit (Y), the polymer unit (Y in the polyvinyl acetal resin layer (B) ) / Polymer unit (X) ratio is 200 or less.

  Furthermore, when sufficient penetration resistance is required in the low temperature range to the normal temperature range, the molar ratio of the polymer unit (X) and the polymer unit (Y) in the second polyvinyl acetal resin layer (B). It is preferable to reduce the polymer unit (Y) / polymer unit (X). More preferably, it is 3.5 or less.

  Moreover, also about the polyvinyl alcohol for obtaining the 2nd polyvinyl acetal resin, the thing of the average polymerization degree similar to the polyvinyl alcohol used for obtaining the 1st polyvinyl acetal resin can be used. However, when the second polyvinyl acetal resin layer (B) comprises an inner layer when a thermoplastic resin sheet is used as an intermediate film, an average polymerization degree of polyvinyl alcohol having a range of 1700 to 2500 is used as a raw material. desirable. If the average degree of polymerization is less than 1700, sufficient penetration resistance may not be exhibited, and if it exceeds 3000, the viscosity of the resin increases, and the extrusion moldability may deteriorate.

  As the plasticizer contained in the second polyvinyl acetal resin layer (B), the plasticizer contained in the first polyvinyl acetal resin layer (A) described above can be used. The same plasticizer may be used for the polyvinyl acetal resin layer (A) and the second polyvinyl acetal resin layer (B), or different types of plasticizers may be used.

  The content of the plasticizer in the second polyvinyl acetal resin layer (B) may be usually in the range of 10 to 40 parts by weight with respect to 100 parts by weight of the second polyvinyl acetal resin. Preferably, it is 20-35 weight part with respect to 100 weight part of 2nd polyvinyl acetal resin (B), More preferably, it is 25-35 weight part with respect to 100 weight part of 2nd polyvinyl acetal resin (B). If it is less than 10 parts by weight, the amount of the plasticizer is too small, so that it is difficult to mold the intermediate film, and the flexibility is low, so the intermediate film is hard, the handling property becomes very bad, and the resistance at low temperature is low. Penetration performance may be significantly reduced. When the amount exceeds 40 parts by weight, the penetration resistance when the intermediate film is formed may deteriorate, or the plasticizer may bleed out and the appearance may be significantly impaired.

(Laminated structure)
The lamination structure in the thermoplastic resin sheet according to the present invention is not particularly limited as long as the first polyvinyl acetal resin layer (A) is laminated on both surfaces of at least one second polyvinyl acetal resin layer (B). For example, when the thermoplastic resin sheet of the present invention is used as an interlayer film for laminated glass, a preferred laminated structure is a) a three-layer laminated film of layer (A) / layer (B) / layer (A), b) layer Examples thereof include a five-layer laminated film of (A) / layer (B) / layer (A) / layer (B) / layer (A). In the case of a laminated film of three or more layers, the laminated structure may be asymmetric as long as at least one of the surface layers is a layer (A).

  The reason why the three-layer laminated film of the above layer (A) / layer (B) / layer (A) is preferable is not only the relative relationship between the dynamic viscoelasticity of the layer (A) and the layer (B), but also the obtained intermediate layer In the method of combining films, good workability can be obtained as in the case of a normal PVB-based intermediate film.

  In the laminated body which concerns on this invention, the thermoplastic resin sheet mentioned above is arrange | positioned between the 1st, 2nd transparent plates as an intermediate film. The first and second transparent plates are made of a glass plate or a transparent resin.

(Reason why penetration resistance is enhanced by the thermoplastic resin sheet of the present invention)
FIG. 1 is a schematic diagram for explaining the operation of the thermoplastic resin sheet of the present invention, in which the horizontal axis represents temperature, and the vertical axis represents penetration resistance when a laminated glass is formed using a thermoplastic resin sheet. Show.

  In FIG. 1, a solid line A shows an example of a result when a PVB single layer thermoplastic resin sheet obtained by acetalizing polyvinyl alcohol using only butyraldehyde is used as an interlayer film of laminated glass. Moreover, the broken line B replaced only the inner-layer part of the structure which consists only of the said single layer PVB sheet | seat with the relatively hard PVB layer with few plasticizer content as described in patent document 1 and patent document 2. An example of the penetration resistance in the case is shown. As is clear from the comparison of the solid line A and the broken line B, when the inner layer is composed of a PVB layer with a small plasticizer content, the maximum value of the penetration resistance is increased, but the temperature dependence of the penetration resistance is on the high temperature side. Because of the shift, the penetration resistance at high temperatures is improved, but the penetration resistance at low temperatures is extremely reduced.

  On the other hand, when the thermoplastic resin sheet of the present invention is used, as shown by the solid line C, not only the maximum penetration resistance is increased, but also excellent penetration resistance is exhibited over a wide temperature range. The The reason for this is that the inner layer is composed of a polyvinyl acetal resin made of a coacetalized product containing the polymer units (X) and (Y) at a specific ratio or an acetalized product of only the polymer unit (Y). by. That is, since the aldehyde (a) has a large molecular structure and a large steric hindrance when it is acetalized, the produced acetal resin becomes flexible. In the present invention, by using the aldehyde (b) having a smaller steric hindrance than the aldehyde (a), the distance between the molecules is shortened, the intermolecular force is further strengthened, and the aldehyde (a) is produced using only the aldehyde (a). It is thought that the rigidity of the resin is improved over the acetal resin. Furthermore, since the polyvinyl acetal resin (B) of the present invention has the characteristics as described above, the weight which is the molar ratio of the polymer unit (X) to the polymer unit (Y) in the polyvinyl acetal resin (B). When the combined unit (Y) / polymer unit (X) is small, the polyvinyl butyral resin layer (B) contains more plasticizer than the polyvinyl acetal resin layer (A). Can also be rigid. Furthermore, since it can contain a large amount of plasticizer while ensuring rigidity, it is possible to ensure impact resistance in all temperature ranges that could not be achieved with conventional PVB resins, and it is particularly excellent from low to normal temperatures. It has become possible to develop high impact resistance.

  Further, when the polymer unit (Y) / polymer unit (X), which is the molar ratio of the polymer unit (X) and the polymer unit (Y), is large in the polyvinyl acetal resin (B), or the polymer unit When (X) is not contained, the polyvinyl acetal resin (B) is further rigid and can improve the penetration resistance. Even in this case, the penetration resistance performance of the thermoplastic resin sheet formed by laminating the polyvinyl acetal resin layer (A) and the polyvinyl acetal resin layer (B) is the entire temperature range that could not be achieved by the conventional PVB resin. Although it is possible to ensure the impact resistance, the impact resistance performance from the normal temperature range to the high temperature range is relatively excellent.

That is, the inventor of the present application uses the first polyvinyl acetal resin layer (A) as an outer layer and the polymer layer (X) and the polymer unit (Y) as a central inner layer, and the above-mentioned coacetalized product. By using the second polyvinyl acetal resin layer (B 1 ) and further by setting the ratio of the polymer unit (X) and the polymer unit (Y) to the above-mentioned specific ratio, excellent penetration resistance over a wide temperature range It has been found experimentally that the performance can be improved.

Further, the present inventor uses a conventional thermoplastic resin sheet as an intermediate film to reduce the weight of an automobile, and a glass plate used for laminated glass so that the surface density of the laminated glass is 12 kg / m ² or less. When the thickness of the laminated glass was reduced, the impact resistance performance of the laminated glass was lowered, and it was experimentally confirmed that the temperature range in which MBH 4 m or more in the falling ball test in JIS R 3212 can be achieved was narrowed.

On the other hand, when a laminated glass having a surface density of 12 kg / m ² or less is produced using the above-described thermoplastic resin sheet according to the present invention, the impact resistance performance is achieved even though the surface density of the laminated glass is lowered. Are all 4 m or more in the range of 0 ° C. to 40 ° C., and MBH of 4 m or more in the falling ball test in JIS R 3212 is achieved in a very wide temperature range. This is because the thermoplastic resin sheet according to the present invention has sufficient rigidity. This means that the thermoplastic resin sheet has sufficient impact resistance even when the surface density of the laminated glass is reduced and the weight of the laminate is reduced. That is, it is shown that it is possible to achieve both weight reduction of the vehicle and securing of impact resistance.

(Preferred embodiment)
In the thermoplastic resin sheet of the present invention, it is possible to ensure impact resistance in all temperature ranges that could not be achieved with conventional PVB resins, but when importance is attached to penetration resistance in normal temperature range to high temperature range. When the second polyvinyl acetal resin layer (B) is composed of a coacetalized product, the polymer unit ratio that is the molar ratio of the polymer unit (Y) and the polymer unit (X), It is preferable that the polymer unit (Y) / polymer unit (X) is 200 or less, or that the second polyvinyl acetal resin layer (B) is composed only of the polymer unit (Y).

  In the present invention, when importance is attached to penetration resistance in a low temperature range to a normal temperature range, when the second polyvinyl acetal resin layer (B) is composed of a coacetalized product, a polymer is used. It is preferable that the polymer unit ratio, which is the molar ratio of the unit (Y) and the polymer unit (X), and the polymer unit (Y) / polymer unit (X) is 3.5 or less. By setting it to 3.5 or less, excellent penetration resistance can be expressed over a wider temperature range. Preferably, it is 1.0-2.0.

  Furthermore, the temperature t (A) indicating the maximum value of the loss tangent tan δ of the sheet consisting only of the polyvinyl acetal resin layer (A) measured at a measurement frequency of 10 Hz is in the range of 20 to 50 ° C., and the second polyvinyl acetal resin The temperature t (B) indicating the maximum value of the loss tangent tan δ of the sheet made of the layer (B) is in the range of 35 to 70 ° C, and t (B) -t (A) is 5 ° C or higher and 40 ° C or lower. Even in the range, it is possible to obtain even more excellent penetration resistance over a wide temperature range. More preferably, the temperature t (B) indicating the maximum value of the loss tangent tan δ of the sheet made of the second polyvinyl acetal resin layer (B) is in the range of 40 to 65 ° C., and t (B) −t (A ) Is in the range of 5 ° C. or more and 25 ° C. or less.

  That is, as described in Patent Document 2, when the Tg of the surface resin layer is 32 to 35 ° C. and the Tg of the inner resin layer is 35 to 60 ° C., the difference between the two Tg is small Therefore, the characteristic curve in the DSC chart of the entire thermoplastic resin sheet has a mountain shape. Therefore, when the penetration resistance is measured in the falling ball test, it may not be possible to obtain excellent penetration resistance over a wide temperature range. In addition, when the difference in Tg is too large, the characteristic curve of the DSC chart of the entire thermoplastic resin sheet has two peaks, but it may deviate from the practical temperature range of the laminated glass and may not be practical.

  On the other hand, as described above, the difference between the maximum point temperature of the loss tangent of the second polyvinyl acetal resin layer (B) and the maximum point temperature of the loss tangent of the first polyvinyl acetal resin layer (A) is By setting it as the said specific range, the outstanding penetration-proof performance can be acquired in all the temperature ranges at the time of actual use of 0-40 degreeC.

  In the thermoplastic resin sheet of the present invention, preferably, in the sheet comprising the first polyvinyl acetal resin layer (A), the temperature range where the loss tangent tan δ is 0.3 or more, and the second polyvinyl acetal resin layer ( The sheet of B) is configured to have a temperature range that overlaps the temperature range in which the loss tangent tan δ is 0.3 or more. In other words, the temperature range where the loss tangent is 0.3 or more is arranged so as to overlap in the two types of polyvinyl acetal resin layers. The range where the loss tangent that contributes to the dissipation of 0.3 or more overlaps. Therefore, it is possible to relax the temperature dependency of the penetration resistance and obtain excellent penetration resistance over a wide temperature range. Since the loss tangent contributes to energy dissipation, the temperature range in which the loss tangent tan δ is 0.5 or more in the sheet made of the first polyvinyl acetal resin layer (A) and the second polyvinyl acetal resin layer (B) It is more preferable that the sheet has a temperature range in which a temperature range where the loss tangent tan δ is 0.5 or more overlaps.

  Further, the shear storage elastic modulus at 23 ° C. and 10 Hz of the first polyvinyl acetal resin layer (A) is G ′ (A), and the shear storage elastic modulus at 23 ° C. and 10 Hz of the second polyvinyl acetal resin layer (B) is When G ′ (B) is set, G ′ (B) / G ′ (A) is preferably in the range of 1.0 to 10, and even in that case, the resistance is further improved over a wide temperature range. Penetration performance can be obtained.

  In the thermoplastic resin sheet of the present invention, preferably, the tear strength (B) of the second polyvinyl acetal resin layer (B) measured according to JIS K 7128 and the first polyvinyl acetal resin layer (A The tear strength (B) / tear strength (A), which is a ratio to the tear strength (A), is 1.1 or more. Accordingly, the tear strength (B) of the second polyvinyl acetal resin layer constituting the inner layer is increased as described above, whereby the penetration resistance itself is effectively enhanced.

  Preferably, the tensile modulus of elasticity of the second polyvinyl acetal resin layer (B) measured at 23 ° C. and a tensile strain rate of 1250% / min is defined as the tensile elastic modulus (B), and the first polyvinyl acetal resin layer (A ) Is the tensile elastic modulus (A), the tensile elastic modulus (B) / the tensile elastic modulus (A) is 1.1 or more. When the tensile elastic modulus at 23 ° C. of the second polyvinyl acetal resin layer is increased at the specific ratio, the penetration resistance at room temperature can be further enhanced. The tensile elastic modulus (B) / tensile elastic modulus (A) is preferably 10 or more.

  In the thermoplastic resin sheet according to the present invention, preferably, the breaking energy (B) of the second polyvinyl acetal resin layer (B) measured at 23 ° C. and a tensile strain rate of 1250% / min is defined as the first breaking energy (B). When the breaking energy of the polyvinyl acetal resin layer (A) is defined as breaking energy (A), the breaking energy (B) / breaking energy (A) is 1.1 or more.

  Preferably, the maximum point stress (B) is the maximum point stress of the second polyvinyl acetal resin layer (B) measured at 23 ° C. and a tensile strain rate of 1250% / min, and the first polyvinyl acetal resin layer ( When the maximum point stress of A) is the maximum point stress (A), the maximum point stress (B) / maximum point stress (A) is 1.0 or more.

  As described above, the breaking energy in the second polyvinyl acetal resin layer (B) is 1.1 times or more the breaking energy of the first polyvinyl acetal resin layer (A), and the second polyvinyl acetal resin layer (B). By making the maximum point stress in the 1.0 point or more of the maximum point stress in the first polyvinyl acetal resin layer (A), the penetration resistance improvement effect by the second polyvinyl acetal resin layer (B) is further enhanced. Can be increased.

  Moreover, in the thermoplastic resin sheet which concerns on this invention, the polymerization degree of the said polyvinyl alcohol for comprising a 2nd polyvinyl acetal resin layer (B) is set to PVA polymerization degree (B), 1st polyvinyl acetal resin layer (A ), When the polymerization degree of the polyvinyl alcohol is PVA polymerization degree (A), the PVA polymerization degree (B) / PVA polymerization degree (A) is preferably in the range of 0.5 to 3.0. Of these, more preferably within the range of 1.0 to 3.0. By increasing the average degree of polymerization of the polyvinyl alcohol used in the second polyvinyl acetal resin layer (B) used as the inner layer, the tensile properties at room temperature are improved, thereby effectively improving the penetration resistance. Therefore, it is desirable that the PVA polymerization degree (B) / PVA polymerization degree (A) is 0.5 or more. However, if it exceeds 3.0, the polymerization degree of the polyvinyl acetal resin (B) is too large, and the extrusion moldability may be deteriorated.

  The content ratio of the ester group in the coacetalized product constituting the second polyvinyl acetal resin layer (B) is preferably 40 mol% or less, more preferably 20 mol% or less. By setting it to 20 mol% or less, the lipophilicity is enhanced, whereby more plasticizer can be contained, and therefore the penetration resistance can be further improved. If the ester group content exceeds 40 mol%, the interlayer film becomes too soft, and the penetration resistance cannot be ensured. The content ratio of the ester group is preferably 15 mol% or less.

  In the thermoplastic resin sheet according to the present invention, preferably, the plasticizer content rate in the first polyvinyl acetal resin layer (A) is the plasticizer content rate (A), and the second polyvinyl acetal resin (B) When the plasticizer content rate is defined as the plasticizer content rate (B), the plasticizer content rate (A) / plasticizer content rate (B) is in the range of 1.0 to 3. By setting the plasticizer content (A) / plasticizer content (B) in the range of 1.0 to 3, the second polyvinyl acetal resin layer (B) is relatively hardened, and the penetration resistance is further improved. It can be further enhanced. Preferably it is 1.0-2.0. If the plasticizer content ratio is less than 1.0, the second polyvinyl acetal resin layer (B) may be relatively soft, and the penetration resistance may not be improved. There is a possibility that the resin layer (A) becomes too soft and molding becomes difficult, or the second polyvinyl acetal resin layer (B) becomes too hard and the flexibility is impaired.

Preferably, in the present invention, functional fine particles are contained in the polyvinyl acetal resin layer (A) and / or (B). Such functional fine particles are not particularly limited, but fine particles having a mid-infrared absorbing function or a near-infrared absorbing function such as ITO and LaB ₆ are preferably used. By including such fine particles, the thermoplastic resin sheet can be provided with a heat shielding function. In addition, even when the ambient temperature is low, such as in winter, the wavelength of the near-infrared and mid-infrared regions can be absorbed, so the temperature of the laminated glass in which the thermoplastic resin sheet is used is maintained at 0 ° C. or higher. Easy to do. Accordingly, it is possible to suppress a decrease in penetration resistance at low temperatures.

  In the thermoplastic resin sheet according to the present invention, preferably, the first polyvinyl acetal resin layer (A) and / or the second polyvinyl acetal resin layer (B) contains a crosslinked polyvinyl butyral resin. Further, the first polyvinyl acetal resin (A) and / or the second polyvinyl acetal resin (B) is a polyvinyl acetal resin in which intermolecular crosslinking is performed, and these may be laminated. By including the cross-linked polyvinyl butyral resin and laminating the cross-linked polyvinyl acetal resin, the penetration resistance can be further enhanced. When cross-linking polyvinyl acetal resin, as a method of cross-linking polyvinyl acetal resin, for example, when polyvinyl alcohol is acetalized with an aldehyde such as butyraldehyde, a dialdehyde such as glutaraldehyde is used to form a diacetal between molecules. A method of lightly crosslinking by bonding; after reaching at least 90% of the desired degree of acetalization in the acetalization reaction of polyvinyl alcohol, an acid catalyst is added thereto and reacted at 60 to 95 ° C. Examples include a method of crosslinking between molecules by monobutyral bonding; a method of adding a crosslinking agent that reacts with a hydroxyl group remaining in the obtained polyvinyl acetal resin and crosslinking the hydroxyl group. Examples of the crosslinking agent that reacts with a hydroxyl group include an epoxy compound, an isocyanate compound, and a boric acid compound.

(Other components that can be contained in the polyvinyl acetal resin layer (A) or (B))
For the purpose of adjusting the adhesion of the interlayer film to the glass, other components such as carboxylic acid metal salt and modified silicone oil can be added to the polyvinyl acetal resin layer (A) and / or (B). .

  In still another specific aspect of the laminate according to the present invention, the adhesive force P between the polyvinyl acetal resin layer (A) and the first transparent plate, and the polyvinyl acetal resin layer (A) and the second transparent plate. The adhesive strength Q is different.

  Examples of the method for adjusting the adhesive strength include a method of reducing the amount of hydroxyl groups in the polyvinyl acetal resin (A), a method of changing the kind of additives such as a carboxylic acid metal salt and a modified silicone oil, a carboxylic acid metal salt, and a modified silicone. Examples thereof include a method of changing the amount of additives such as oil, and a method of improving the adhesion by treating the glass surface with a silane coupling agent. Of these, the method of changing the addition amount of additives such as carboxylic acid metal salts and modified silicone oil is the most easily implemented method.

  The carboxylic acid metal salt is preferably an alkali metal salt or alkaline earth metal salt of an aliphatic monocarboxylic acid or aliphatic dicarboxylic acid having 12 or less carbon atoms, and the metal component includes Mg, Na, K, etc. Are acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid and the like. Examples of the preferred carboxylic acid metal salt include potassium acetate, magnesium acetate, potassium propionate, magnesium propionate and the like, and potassium acetate and magnesium acetate are particularly preferable.

  Examples of the modified silicone oil include ether-modified silicone oil, epoxy-modified silicone oil, ester-modified silicone oil, amine-modified silicone oil, and alkali-modified silicone oil. These are generally viscous liquids obtained by reacting a compound to be modified with polysiloxane.

  Moreover, as a component constituting the thermoplastic resin sheet, conventionally known ultraviolet absorbers, antioxidants, pigments, dyes, and the like may be added as necessary.

  The thickness of the thermoplastic resin sheet according to the present invention is not particularly limited, but when the thermoplastic resin sheet is used as an interlayer film for laminated glass, the thickness of the thermoplastic resin sheet is preferably 0.3 to 1.6 mm. The thicker the thickness, the better the penetration resistance, but the above range is preferable in consideration of the minimum penetration resistance required for laminated glass.

  The layer (A) may be a single layer and may be a plurality of layers. When the thickness is reduced, the penetration resistance may be remarkably lowered. The thickness of the layer (B) is preferably 10% or more of the total thickness of the intermediate film. When the thickness is less than 10% of the entire thermoplastic resin sheet, it is difficult to obtain sufficient penetration resistance.

(Preferred embodiment)
A preferred embodiment of the laminate provided by the first invention is a laminate in which a thermoplastic resin sheet is disposed between the first and second transparent plates as an intermediate film, and the thermoplastic resin sheet Is a first polyvinyl acetal resin obtained by acetalization of polyvinyl alcohol with at least one aldehyde (a) selected from the group consisting of a plasticizer and an aldehyde having 4 to 6 carbon atoms By an acetal resin layer (A), a plasticizer, and at least one aldehyde (b) selected from the group consisting of aldehyde (a) which is n-butyraldehyde having 4 carbon atoms and aldehyde having 1 to 3 carbon atoms A second polyvinyl acetal containing a second polyvinyl acetal resin which is a co-acetalized product obtained by co-acetalization of polyvinyl alcohol A thermoplastic resin sheet laminated with a fat layer (B), and the first polyvinyl acetal resin layer (A) is laminated on both surfaces of at least one second polyvinyl acetal resin layer (B). In the second polyvinyl acetal resin layer (B) having the structure, the acetalization unit derived from the first aldehyde (a) is the polymer unit (X), and the acetalization unit derived from the second aldehyde (b) is When the polymer unit (Y) is used, the total of the polymer unit (X) and the polymer unit (Y) accounts for 55 mol% or more of the entire coacetalized product, and the first polymer unit (X ) Is 0.5 to 80 mol%, and when adhered to the same transparent plate, the adhesive force P between the polyvinyl acetal resin layer (A) and the first transparent plate, and polyvinyl aceter Characterized in that the adhesive force Q of the resin layer (A) and a second transparent plate are different.

Another preferred embodiment of the laminate according to the second invention is a laminate in which a thermoplastic resin sheet is disposed as an intermediate film between the first and second transparent plates, and the thermoplastic resin sheet is A first polyvinyl acetal comprising a first polyvinyl acetal resin obtained by acetalization of polyvinyl alcohol with at least one aldehyde (a) selected from the group consisting of a plasticizer and an aldehyde having 4 to 6 carbon atoms Polyvinyl by at least one aldehyde (b) selected from the group consisting of a resin layer (A), a plasticizer , an aldehyde (a) which is n-butyraldehyde having 4 carbon atoms , and an aldehyde having 1 to 3 carbon atoms A second polyvinyl acetal resin layer (B) containing a second polyvinyl acetal resin which is a co-acetalized product obtained by co-acetalization of alcohol Is a thermoplastic resin sheet having a structure in which the first polyvinyl acetal resin layer (A) is laminated on both surfaces of at least one second polyvinyl acetal resin layer (B), In the second polyvinyl acetal resin layer (B), the acetalization unit derived from the first aldehyde (a) is the polymer unit (X), and the acetalization unit derived from the second aldehyde (b) is the polymer unit (Y ), The total of the polymer unit (X) and the polymer unit (Y) accounts for 55 mol% or more of the entire coacetalized product, and the ratio of the first polymer unit (X) is 20%. -80 mol%, and when adhered to the same transparent plate, the adhesive force P between the polyvinyl acetal resin layer (A) and the first transparent plate, and the polyvinyl acetal resin layer (A Characterized in that it is different from the the adhesive strength Q of the second transparent plate.

Still another preferred embodiment of the laminate according to the third invention is a laminate in which a thermoplastic resin sheet is disposed between the first and second transparent plates as an intermediate film, and the thermoplastic resin sheet Is a first polyvinyl acetal resin obtained by acetalization of polyvinyl alcohol with at least one aldehyde (a) selected from the group consisting of a plasticizer and an aldehyde having 4 to 6 carbon atoms By an acetal resin layer (A), a plasticizer, and at least one aldehyde (b) selected from the group consisting of aldehyde (a) which is n-butyraldehyde having 4 carbon atoms and aldehyde having 1 to 3 carbon atoms A second polyvinyl acetal resin comprising a second polyvinyl acetal resin which is a co-acetalized product obtained by co-acetalization of polyvinyl alcohol (B) is a thermoplastic resin sheet laminated with a structure in which the first polyvinyl acetal resin layer (A) is laminated on both surfaces of at least one second polyvinyl acetal resin layer (B). In the second polyvinyl acetal resin layer (B), the acetalization unit derived from the first aldehyde (a) is the polymer unit (X), and the acetalization unit derived from the second aldehyde (b) is the polymer. When the unit (Y) is used, the total of the polymer unit (X) and the polymer unit (Y) accounts for 55 mol% or more of the entire coacetalized product, and the first polymer unit (X) When the ratio is 0.5 to 20 mol% and bonded to the same transparent plate, the adhesive force P between the polyvinyl acetal resin layer (A) and the first transparent plate, and the polyvinyl acetal tree Wherein the layer (A) and the adhesive force Q between the second transparent plate are different.

  In the laminated body, at least one of the first transparent plate and the second transparent plate can be composed of a glass plate.

  In another specific aspect of the laminate, at least one of the first transparent plate and the second transparent plate is made of a transparent resin plate.

  In still another specific aspect of the laminate, the transparent resin plate is composed of one selected from the group consisting of polycarbonate, acrylic resin, acrylic copolymer resin, and polyester.

  In still another specific aspect of the laminate, the transparent resin plate is coated with a transparent elastomer.

  In still another specific aspect of the laminate, the first and second transparent plates are made of glass plates.

  In still another specific aspect of the laminate, at least one of the glass plates is colored transparent glass.

In still another specific aspect of the laminate, the surface density is 12 kg / m ² or less.

  When the laminated body is used to close an opening of a building or a vehicle, preferably, the surface on the side where the adhesive force P and the adhesive force Q are higher is the inner side of the building or It arrange | positions so that it may be located in a vehicle inner side surface.

In each of the laminates described in the above-mentioned preferred embodiments, the second polyvinyl acetal resin layer (B) is constituted by the thermoplastic resin sheet in the first to third inventions, so that the wide temperature range. Cross-through resistance is improved. Furthermore, when bonded to the same transparent plate, the adhesive force P between the polyvinyl acetal resin layer (A) and the first transparent plate, and the adhesive force between the polyvinyl acetal resin layer (A) and the second transparent plate. Since Q is different, it is possible to sufficiently absorb impact energy between the transparent plate on the side having low adhesive force and the thermoplastic resin sheet, and the transparent plate laminate against impact from the side having low adhesive strength Excellent penetration resistance. In addition, when the transparent plate laminate is broken, the broken pieces of the first transparent plate or the second transparent plate on the side having a high adhesive force are difficult to peel from the thermoplastic resin sheet.

  For example, in a transparent plate laminate in which a thermoplastic resin sheet is sandwiched with glass or the like, in order to reduce scattering of glass pieces when the glass is broken, increase the adhesion between the glass and the thermoplastic resin sheet. Good. However, simply increasing the adhesion between the thermoplastic resin sheet used as the interlayer and the glass does not provide sufficient penetration resistance required for laminated glass and cannot satisfy the required performance. Therefore, in the laminate of the second invention, the second polyvinyl acetal resin layer (B) is constituted so as to include the polymer units (X) and (Y) at the above-mentioned specific ratio, and sufficient penetration resistance is provided. As described above, the adhesive force P and the adhesive force Q are differentiated to maintain sufficient absorbency for impact energy on the side where the adhesive force is low, and on the side where the adhesive force is high, The scattering of glass fragments is reduced.

  When the transparent plate laminate is used to close the opening of a building or a vehicle, the surface on the side where the adhesive force P and the adhesive force Q are higher is the inner side of the building or the inner side of the vehicle. If it arrange | positions so that it may be located, the safety | security of the person in a building or the passenger | crew in a vehicle can be ensured. Furthermore, since the transparent plate laminate can absorb more impact energy in the outer side of the building or the outer side of the vehicle, the penetration resistance of the transparent plate laminate against the impact from the outside of the building or the outside of the vehicle can be improved. it can. Further, when the surface on the side where the adhesive force P and the adhesive force Q are higher is positioned on the inner side of the building or the inner side of the vehicle, the inner side of the building or the inner side of the vehicle may be damaged. The scattering of broken pieces of the first and second transparent plates can be effectively prevented. Therefore, it is difficult for humans in the building or passengers in the vehicle to be seriously injured by the glass pieces scattered.

  Moreover, as a manufacturing method of the thermoplastic resin sheet of this invention, the method of forming into a film each forming a polyvinyl acetal resin layer (A) and a polyvinyl acetal resin layer (B) separately, for example; polyvinyl acetal resin layer ( Various conventionally known methods such as a method of integrally forming A) and the polyvinyl acetal resin layer (B) using a multilayer molding machine are employed. In the method of laminating the polyvinyl acetal resin layers (A) and (B) at the time of producing the laminated glass, the workability is reduced by laminating a plurality of laminated glasses, and the polyvinyl acetal resin layers (A) and (B ) There is a problem that the image seen through the laminated glass is distorted due to the optical distortion caused by the poor smoothness of the interface between them. Therefore, the method of integrally molding using a multilayer molding machine is preferable.

  Further, in order to produce laminated glass using the thermoplastic resin sheet of the present invention, a method used for producing ordinary laminated glass is adopted, for example, an intermediate film is sandwiched between glass plates from both sides, and hot press The method of manufacturing a laminated glass is mentioned.

  Moreover, when the laminated body of this invention is a laminated glass, it is preferable that at least 1 glass plate is a colored transparent glass among the glass plates which comprise the laminated glass. As the colored transparent glass, green soda lime silica glass or the like is generally used. By using colored transparent glass, it is possible to absorb light having a specific wavelength in visible light, so that an occupant inside the vehicle can be reduced from feeling uncomfortable when the skin is stimulated by sunlight.

  Moreover, the use for which the thermoplastic resin sheet according to the present invention is used as an intermediate film is not necessarily limited to laminated glass. That is, according to this invention, the laminated body provided with the said thermoplastic resin sheet as at least 1 layer can be provided according to a suitable use. Even in this case, the thermoplastic resin sheet imparts sufficient penetration resistance to the laminate.

  As the laminate according to the present invention, the thermoplastic resin sheet is sandwiched between the glass plate and the transparent resin plate, or the thermoplastic resin sheet is sandwiched between the pair of transparent resin plates. An example is a structure in which a thermoplastic resin sheet is tightly attached to a pair of glass plates.

The surface density of the laminate according to the present invention is not particularly limited, but it is preferable that the surface density is reduced in consideration of reduction in vehicle weight due to reduction in laminated glass weight and improvement in fuel consumption. Preferably it is 12 kg / m ² or less.

  Although it does not specifically limit as said transparent resin board, 1 type selected from the group which consists of a polycarbonate, an acrylic resin, an acrylic copolymer resin, and polyester can be used suitably. The transparent resin plate may be covered with a transparent elastomer.

  In the present invention, when the laminate is used to close an opening of a building or a vehicle, the adhesive force P between the polyvinyl acetal resin layer (A) and the first transparent plate, and the polyvinyl acetal resin layer ( The surface on the side where the adhesive strength Q between A) and the second transparent plate is high is preferably arranged so as to be located on the inner side of the building or the inner side of the vehicle. By installing in this way, the penetration resistance of the transparent board laminated body with respect to the impact from the building outer side or the vehicle outer side can be improved. In addition, more impact energy can be absorbed in the outer side of the building or the outer side of the vehicle, and the safety of a person in the building or a passenger in the vehicle can be ensured. Furthermore, when the laminate is broken, the broken pieces of the first and second transparent plates peeled off from the thermoplastic resin sheet can be prevented from being scattered inside the building or inside the vehicle.

  Hereinafter, the present invention will be described in more detail by giving specific examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.

Example 1
Triethylene glycol as a plasticizer is added to 100 parts by weight of PVB (average polymerization degree 1700, butyralization degree 68.5 mol%, residual acetyl group 0.7 mol%) obtained by acetalizing polyvinyl alcohol having a polymerization degree of 1700 with butyraldehyde. -Add and mix 40 parts by weight of di-2-ethylhexanoate (3GO), and a magnesium acetate / 2-ethylbutyrate magnesium mixture as an adhesion modifier so that the amount of magnesium is 50 ppm with respect to the total amount of the resin composition. A first resin for forming the first polyvinyl acetal resin layer (A) was prepared.

  Separately, a coacetalized polyvinyl acetal resin obtained by coacetalizing polyvinyl alcohol with a polymerization degree of 2000 using acetaldehyde and butyraldehyde (average polymerization degree 2000, total acetalization degree 69.5 mol%, residual acetyl group (1.3 mol%, acetalization degree with acetaldehyde 37.8 mol%, acetalization degree with butyraldehyde 31.8 mol%) 100 parts by weight of triethylene glycol-di-2-ethylhexanoate as a plasticizer (3GO) 25 parts by weight was mixed to prepare a resin for the second polyvinyl acetal resin layer (B).

  A first outer layer (first polyvinyl acetal resin layer (A)) / inner layer (second polyvinyl acetal resin layer) by supplying the first and second resins to a multilayer extrusion molding machine and integrally molding them. (B)) / second outer layer: A thermoplastic resin sheet having a three-layer structure of the first polyvinyl acetal resin layer (A) and a thickness of 0.75 mm was obtained.

The obtained thermoplastic resin sheet having a three-layer structure was sandwiched between 2.5 mm float glass and pre-pressed with a nipper roll, and then the laminated glass structure was put into an autoclave, and the conditions were 140 ° C. and 13 atm. Processed to complete the laminated glass construction. The surface density of the finished laminated glass was 13.3 kg / m ² .

  Further, a sheet having a thickness of 0.93 mm for the first polyvinyl acetal resin layer (A) is molded, and the shear storage modulus G ′ of the sheet at 23 ° C., the loss tangent at 23 ° C., and the maximum value of the loss tangent The peak temperature of the loss tangent, the temperature range where the loss tangent is 0.5 or more, and the temperature range where the loss tangent is 0.3 or more were evaluated. Similarly, tear strength (A), breaking energy (A), maximum point stress (A) and tensile modulus (A) of the sheet were evaluated in the following manner.

  Similarly, a 1.02 mm sheet of the second polyvinyl acetal resin layer (B) is separately prepared. Similarly, the shear storage elastic modulus G ′ at 23 ° C., loss tangent at 23 ° C., loss tangent maximum value, loss tangent Measure peak temperature, loss tangent temperature range 0.5 or higher, loss tangent temperature range 0.3 or higher, and tear strength (B), breaking energy (B), maximum point stress (B) and tensile elasticity The rate (B) was determined.

(A) Measurement of shear storage modulus G ′ at 23 ° C. (b) Measurement of loss tangent at 23 ° C., loss tangent peak temperature, temperature range of loss tangent 0.5 or more, temperature range of loss tangent 0.3 or more A shear strain was applied with a dynamic viscoelasticity tester at a set strain of 0.08% and a measurement frequency of 10 Hz, and the shear storage modulus at each temperature was measured while the temperature was raised from −50 ° C. to 150 ° C. at 3 ° C./min. The value at 23 ° C. was defined as the shear storage modulus G ′ at 23 ° C. Further, from the measured loss tangent value at each temperature obtained at the same time, the peak temperature of loss tangent, the temperature range of loss tangent 0.5 or higher, and the temperature range of loss tangent 0.3 or higher were determined.
(C) Tear strength Based on the method specified in JIS K 7128, the tensile strength was measured at a pulling speed of 500 mm / min.
(D) Breaking energy (e) Maximum point stress (f) Tensile modulus

  A thermoplastic resin sheet is cut into a test piece having a width of 10 mm and a length of 8 cm, and the test piece is attached to a tensile tester at a distance between chucks of 40 mm, and a tensile test is performed at a tensile speed of 500 mm / min (tensile strain rate of 1250% / min). went. From the obtained stress-strain curve, the breaking energy, the maximum point stress, and the tensile elastic modulus were determined.

  Further, the structure of this example having a thickness of 0.75 mm obtained as described above, and the shear storage elastic modulus G ′, the loss tangent peak temperature difference at 23 ° C., the tear strength ratio, measured in the same manner as described above, The break energy ratio, maximum point stress ratio, and tensile modulus ratio are shown in Table 2 and Table 5 below. The loss tangent peak temperature difference is the loss tangent peak temperature (B) −loss tangent peak temperature (A), and the tear strength ratio, rupture energy ratio, maximum point stress ratio, and tensile modulus ratio are all 2 is the ratio of the value in the sheet comprising the polyvinyl acetal resin layer (B) to the value in the first polyvinyl acetal resin layer (A), that is, B / A.

  The thermoplastic resin sheet obtained as described above was subjected to a falling ball test in order to evaluate the penetration resistance in the following manner, and a Pummel test in order to evaluate the adhesive force between the thermoplastic resin sheet and the glass.

(G) Falling ball test It measured based on JISR3212. That is, a steel ball having a mass of 2260 ± 20 g and a diameter of about 82 mm is dropped from various heights onto a central portion of the sample on a laminated glass sample having an area of about 300 × 300 mm stored at a predetermined temperature for 4 hours or more. Is done. When this steel ball was dropped, the height at which the iron ball did not penetrate 50% was regarded as acceptable, and the height was designated as penetration resistance (MBH).

(H) Pummel test The laminated glass laminate is cooled to -18 ° C, placed on a metal substrate and ground with a hammer weighing 500 g. At this time, the laminate is evaluated with a Pummel value between 0 (no adhesive force) and 10 (complete adhesive force) according to the amount of glass peeled from the thermoplastic resin sheet. Table 1 below shows the relationship between the Pummel value and the film exposure (%). Details of the test are described in British Patent No. 1,093,864. In addition, the larger the Pummel value, the greater the adhesive force between the thermoplastic resin sheet and the glass, and the smaller the Pummel value, the smaller the adhesive force between the thermoplastic resin sheet and the glass. That is, the lower the degree of exposure of the film, the less dangerous glass pieces are peeled off and scattered when an impact is applied to the laminated glass, which indicates that it is safer for passengers such as vehicles.

  In the present specification, it is assumed that the adhesive force is different when the Pummel value is different, and the adhesive force is the same when the Pummel value is the same.

(I) Impact resistance test In order to evaluate the amount of peeling of the glass, an impact resistance test was conducted in accordance with JIS R 3211, 3212. That is, on a laminated glass sample having an area of about 300 × 300 mm stored at a predetermined temperature for 4 hours or more, the center of the sample is at a height of 11 m at 40 ± 2 ° C. and 9.5 m at −20 ± 2 ° C. A steel ball having a mass of 227 ± 2 g and a diameter of about 38 mm was dropped on the part, and the total mass of the peeled pieces was measured from the opposite side of the impact surface. That is, the smaller the amount of peeling, the less the amount of dangerous glass pieces that are peeled and scattered when an impact is applied to the laminated glass, indicating that it is safer for passengers such as vehicles. In JIS R 3211 and 3212, the peelable amount for passing the test is specified for the thickness of the laminated glass, but in the present invention, the relative peel amount is evaluated for safety. It was set as a substitute evaluation.

  The results are shown in Tables 2 to 10 below.

(Examples 2 to 7)
As shown in Tables 2 to 10 below, the configuration of the first polyvinyl acetal resin layer (A) and the second polyvinyl acetal resin layer (B) was changed, and the second polyvinyl acetal resin was changed as necessary. A thermoplastic resin sheet was obtained in the same manner as in Example 1 except that the layer thickness ratio was changed (Example 3), and a laminate was constructed and evaluated. The results are shown in Tables 2-10.

(Examples 8 to 9)
A thermoplastic resin sheet was obtained in the same manner as in Example 1 except that the glass thickness was changed and the surface density of the laminate was 9.8 kg / m ^2, and the laminate was constructed and evaluated. The results are shown in Tables 2-10.

(Example 10)
A first polyvinyl acetal resin layer (A) and a second polyvinyl acetal resin layer (B) having a thickness of 0.125 mm, each containing a different amount of magnesium, were produced separately. The three types of layers thus obtained were laminated to obtain a (A) / (B) / (A) configuration, and thermocompression bonding was performed with a press to obtain a 0.75 mm three-layer thermoplastic resin sheet. Further, a laminate was formed in the same manner as in Example 1.

  In the falling ball test, evaluation was performed in the same manner as in Example 1 except that the test was performed by applying steel balls from both the high and low adhesive surfaces of the thermoplastic resin sheet and glass. The results are shown in Tables 2-10.

(Examples 11 and 13 to 15 and Reference Examples 1 to 4 ) Example 12 is a missing number, as shown in Tables 2 to 10 below, the first polyvinyl acetal resin layer (A) and the second polyvinyl acetal Except having changed the structure of the resin layer (B), the thermoplastic resin sheet was obtained like Example 1, and the laminated body was comprised and evaluated. The results are shown in Tables 2-10.

(Comparative Examples 1-3)
As shown in Tables 2 to 10 below, a thermoplastic resin sheet having a thickness of 0.75 mm consisting only of the first polyvinyl acetal resin layer (A) was obtained, and a laminate was formed in the same manner as in Example 1, and a falling ball test was performed. Evaluation was performed.

(Comparative Examples 4-7)
As shown in the following Tables 2 to 10, the first polyvinyl acetal resin layer (A) and the second polyvinyl acetal resin layer (B) were constituted to obtain a thermoplastic resin sheet. And the laminated body was comprised similarly to Example 1 using each thermoplastic resin sheet, and it evaluated similarly to Example 1. FIG. The results are shown in Tables 2 to 10 below.

(Comparative Example 8)
Except for changing the thickness of the glass and setting the surface density of the laminate to 9.8 kg / m ² , the same thermoplastic resin sheet as in Comparative Example 1 was used to constitute the laminate, and the same as in Example 1. Evaluation was performed. The results are shown in Tables 2-10.

The schematic diagram for demonstrating the effect | action of the thermoplastic resin sheet of this invention.

Claims (30)

A first polyvinyl acetal resin containing a first polyvinyl acetal resin obtained by acetalization of polyvinyl alcohol with at least one aldehyde (a) selected from the group consisting of a plasticizer and an aldehyde having 4 to 6 carbon atoms Polyvinyl alcohol by a layer (A), a plasticizer, and at least one aldehyde (b) selected from the group consisting of an aldehyde (a) which is n-butyraldehyde having 4 carbon atoms and an aldehyde having 1 to 3 carbon atoms A thermoplastic resin sheet laminated with a second polyvinyl acetal resin layer (B) containing a second polyvinyl acetal resin which is a co-acetalized product obtained by co-acetalization of
When the acetalization unit derived from the first aldehyde (a) is the polymer unit (X) and the acetalization unit derived from the second aldehyde (b) is the polymer unit (Y), the polymer unit (X ) And the polymer unit (Y) account for 55 mol% or more of the entire coacetalized product, and the ratio of the first polymer unit (X) is 0.5 to 80 mol%,
The content of the plasticizer in the second polyvinyl acetal resin layer (B) is 10 to 35 parts by weight with respect to 100 parts by weight of the second polyvinyl acetal resin, and
The plasticizer content rate of the 1st polyvinyl acetal resin layer (A) was made into the plasticizer content rate (A), and the plasticizer content rate of the 2nd polyvinyl acetal resin layer (B) was made into the plasticizer content rate (B). Sometimes, the thermoplastic resin sheet, wherein the plasticizer content (A) / plasticizer content (B) is in the range of 1.0 to 3. A first polyvinyl acetal resin containing a first polyvinyl acetal resin obtained by acetalization of polyvinyl alcohol with at least one aldehyde (a) selected from the group consisting of a plasticizer and an aldehyde having 4 to 6 carbon atoms Polyvinyl alcohol by a layer (A), a plasticizer, and at least one aldehyde (b) selected from the group consisting of an aldehyde (a) which is n-butyraldehyde having 4 carbon atoms and an aldehyde having 1 to 3 carbon atoms A thermoplastic resin sheet laminated with a second polyvinyl acetal resin layer (B) containing a second polyvinyl acetal resin that is a co-acetalized product obtained by co-acetalization of The first polyvinyl acetal resin layer (A) is laminated on both sides of the polyvinyl acetal resin layer (B) of No. 2 Have that structure,
In the second polyvinyl acetal resin layer (B), the acetalization unit derived from the first aldehyde (a) is the polymer unit (X), and the acetalization unit derived from the second aldehyde (b) is the polymer unit. When (Y), the total of the polymer unit (X) and the polymer unit (Y) accounts for 55 mol% or more of the entire coacetalized product, and the ratio of the first polymer unit (X) Is 20 to 80 mol%,
The content of the plasticizer in the second polyvinyl acetal resin layer (B) is 10 to 35 parts by weight with respect to 100 parts by weight of the second polyvinyl acetal resin, and
The plasticizer content rate of the 1st polyvinyl acetal resin layer (A) was made into the plasticizer content rate (A), and the plasticizer content rate of the 2nd polyvinyl acetal resin layer (B) was made into the plasticizer content rate (B). Sometimes, the thermoplastic resin sheet, wherein the plasticizer content (A) / plasticizer content (B) is in the range of 1.0 to 3. A first polyvinyl acetal resin containing a first polyvinyl acetal resin obtained by acetalization of polyvinyl alcohol with at least one aldehyde (a) selected from the group consisting of a plasticizer and an aldehyde having 4 to 6 carbon atoms Polyvinyl alcohol by a layer (A), a plasticizer, and at least one aldehyde (b) selected from the group consisting of an aldehyde (a) which is n-butyraldehyde having 4 carbon atoms and an aldehyde having 1 to 3 carbon atoms A thermoplastic resin sheet in which a second polyvinyl acetal resin layer (B) containing a second polyvinyl acetal resin, which is a co-acetalized product obtained by co-acetalization, is laminated, comprising at least one second layer The first polyvinyl acetal resin layer (A) is laminated on both surfaces of the polyvinyl acetal resin layer (B). It has an elephant,
In the second polyvinyl acetal resin layer (B), the acetalization unit derived from the first aldehyde (a) is the polymer unit (X), and the acetalization unit derived from the second aldehyde (b) is the polymer unit. When (Y), the total of the polymer unit (X) and the polymer unit (Y) accounts for 55 mol% or more of the entire coacetalized product, and the ratio of the first polymer unit (X) Is 0.5 to 20 mol%,
The content of the plasticizer in the second polyvinyl acetal resin layer (B) is 10 to 35 parts by weight with respect to 100 parts by weight of the second polyvinyl acetal resin, and
The plasticizer content rate of the 1st polyvinyl acetal resin layer (A) was made into the plasticizer content rate (A), and the plasticizer content rate of the 2nd polyvinyl acetal resin layer (B) was made into the plasticizer content rate (B). Sometimes, the thermoplastic resin sheet, wherein the plasticizer content (A) / plasticizer content (B) is in the range of 1.0 to 3.   In the coacetalized product constituting the second polyvinyl acetal resin layer (B), the polymer unit (Y) / polymer which is the molar ratio of the polymer unit (Y) to the polymer unit (X) The thermoplastic resin sheet according to claim 1 or 2, wherein the unit (X) is 3.5 or less.   In the coacetalized product constituting the second polyvinyl acetal resin layer (B), the polymer unit (Y) / polymer which is the molar ratio of the polymer unit (Y) to the polymer unit (X) Unit (X) is 200 or less, The thermoplastic resin sheet of Claim 1 or 3 characterized by the above-mentioned. The temperature t (A) indicating the maximum value of the loss tangent tan δ of the sheet consisting only of the polyvinyl acetal resin layer (A) measured at a measurement frequency of 10 Hz is in the range of 20 to 50 ° C., and the second polyvinyl acetal resin layer ( The temperature t (B) showing the maximum value of the loss tangent tan δ of the sheet consisting of B) is in the range of 35 to 70 ° C, and t (B) -t (A) is in the range of 5 ° C or more and 40 ° C or less. It is, The thermoplastic resin sheet of any one of Claims 1-5 characterized by the above-mentioned. The temperature t (A) indicating the maximum value of the loss tangent tan δ of the sheet consisting only of the polyvinyl acetal resin layer (A) measured at a measurement frequency of 10 Hz is in the range of 20 to 50 ° C., and the second polyvinyl acetal resin layer ( The temperature t (B) showing the maximum value of the loss tangent tan δ of the sheet consisting of B) is in the range of 40 to 65 ° C, and t (B) -t (A) is in the range of 5 ° C or more and 25 ° C or less. the thermoplastic resin sheet according to any one of claims 1, 2 and 4, characterized in that. The temperature range in which the loss tangent tan δ is 0.3 or more in the sheet made of the first polyvinyl acetal resin layer (A), and the loss tangent tan δ in the sheet made of the second polyvinyl acetal resin layer (B) is 0.3 or more. The thermoplastic resin sheet according to any one of claims 1 to 6 , wherein there is a temperature range in which the temperature range is overlapping. The temperature range in which the loss tangent tan δ is 0.5 or more in the sheet made of the first polyvinyl acetal resin layer (A), and the loss tangent tan δ in the sheet made of the second polyvinyl acetal resin layer (B) is 0.5 or more. the thermoplastic resin sheet according to any one of claims 1, 2 and 4, the temperature range is characterized in that the temperature range overlaps exists. The shear storage elastic modulus at 23 ° C. and 10 Hz of the first polyvinyl acetal resin layer (A) is G ′ (A), and the shear storage elastic modulus at 23 ° C. and 10 Hz of the second polyvinyl acetal resin layer (B) is G ′. The thermoplastic resin according to any one of claims 1 to 9 , wherein G '(B) / G' (A) is in the range of 1.0 to 10 when (B) is defined. Sheet. Tear, which is the ratio between the tear strength (B) of the second polyvinyl acetal resin layer (B) measured according to JIS K 7128 and the tear strength (A) of the first polyvinyl acetal resin layer (A) The thermoplastic resin sheet according to any one of claims 1 to 10 , wherein the strength (B) / tear strength (A) is 1.1 or more. The tensile modulus of elasticity of the second polyvinyl acetal resin layer (B) measured at 23 ° C. and a tensile strain rate of 1250% / min is the tensile modulus of elasticity (B), and the tensile modulus of elasticity of the first polyvinyl acetal resin layer (A). The thermoplastic resin sheet according to any one of claims 1 to 11 , wherein the tensile elastic modulus (B) / the tensile elastic modulus (A) is 1.1 or more, where is a tensile elastic modulus (A). The breaking energy of the second polyvinyl acetal resin layer (B) measured at 23 ° C. and the tensile strain rate of 1250% / min was taken as the breaking energy (B), and the breaking energy of the first polyvinyl acetal resin layer (A) was broken. The thermoplastic resin sheet according to any one of claims 1 to 12 , wherein, when the energy is (A), the breaking energy (B) / breaking energy (A) is 1.1 or more. The maximum point stress of the second polyvinyl acetal resin layer (B) measured at 23 ° C. and the tensile strain rate of 1250% / min is defined as the maximum point stress (B), and the maximum point of the first polyvinyl acetal resin layer (A) stresses the case of the maximum point stress (a) and, according to any one of claims 1 to 13, the maximum point stress (B) / maximum point stress (a) is equal to or less than 1.0 Thermoplastic resin sheet. The degree of polymerization of the polyvinyl alcohol for constituting the second polyvinyl acetal resin layer (B) is the degree of polymerization of PVA (B), and the degree of polymerization of the polyvinyl alcohol for constituting the first polyvinyl acetal resin layer (A). the when the PVA polymerization degree (a), claim 1-14 in which PVA polymerization degree (B) / PVA polymerization degree (a) is characterized in that in the range of 0.5 to 3.0 The thermoplastic resin sheet according to Item 1. The thermoplastic resin sheet according to claim 15 , wherein the degree of PVA polymerization (B) / the degree of PVA polymerization (A) is in the range of 1.0 to 3.0. The thermoplastic resin sheet according to any one of claims 1 to 16 , wherein the content ratio of the ester group in the second polyvinyl acetal resin layer (B) is 40 mol% or less. 18. The thermoplastic resin sheet according to claim 17 , wherein an ester group content in the second polyvinyl acetal resin layer (B) is 20 mol% or less. The content of the plasticizer in the first polyvinyl acetal resin layer (A), relative to the first polyvinyl acetal resin 100 parts by weight, 10 to 50 parts by weight, according to any one of claims 1 to 18 Thermoplastic resin sheet. The first polyvinyl acetal resin layer (A) and / or according to any one of claims 1 to 19, the functional fine particles in the second polyvinyl acetal resin layer (B) is characterized in that it is contained Thermoplastic resin sheet. The first polyvinyl acetal resin layer (A) and / or the second polyvinyl acetal resin layer (B) contains a crosslinked polyvinyl acetal resin, or the first polyvinyl acetal resin (A) and / or the first polyvinyl acetal resin layer (B). 21. The thermoplastic resin sheet according to any one of claims 1 to 20 , wherein the polyvinyl acetal resin (B) of No. 2 is a polyvinyl acetal resin in which intermolecular crosslinking has occurred. When the thickness of the second polyvinyl acetal resin layer (B) is thickness (B) and the thickness of the first polyvinyl acetal resin layer (A) is thickness (A), the thickness (B) / thickness (A) is the thermoplastic resin sheet according to any one of claims 1 to 21, characterized in that in the range of 0.5 to 10. The thermoplastic resin according to any one of claims 1 to 22 , wherein polyvinyl acetal resin layers (A) having different thicknesses are laminated on both surfaces of at least one polyvinyl acetal resin layer (B). Sheet. A laminate comprising the thermoplastic resin sheet according to any one of claims 1 to 23 as at least one layer. 25. The laminate according to claim 24 , wherein the thermoplastic resin sheet is closely attached between a glass plate and a transparent resin plate. The laminate according to claim 25 , wherein the transparent resin plate is composed of one selected from the group consisting of polycarbonate, acrylic resin, acrylic copolymer resin, and polyester. The laminate according to claim 25 , wherein the transparent resin plate is coated with a transparent elastomer. The laminate according to claim 24 , wherein the thermoplastic resin sheet is tightly attached to a pair of glass plates. The laminated body according to any one of claims 25 to 28 , wherein at least one of the glass plates is a colored transparent glass. The laminate according to any one of claims 24 to 29 , wherein the surface density is 12 kg / m ² or less.

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