JP2018154519A - Intermediate film for laminated glass, and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate film for laminated glass which can keep high sound insulation properties in a high frequency region while emphasizing high sound insulation properties in a middle frequency region.SOLUTION: An intermediate film for laminated glass contains at least one layer A composed of a composition containing a thermoplastic elastomer, and is a hydrogenated product of a block copolymer having a polymer block (a) and a polymer block (b), where a content of the polymer block (a) in the hydrogenated product of the block copolymer is 15 mass% or less, the composition containing the thermoplastic elastomer is a composition such that a peak of which tanδ measured by performing a complex shear viscosity test on the condition of a frequency of 1 Hz becomes the largest is in a range of -20°C or higher and -6°C or lower, a shear storage elastic modulus at -5°C is 0.7 MPa or more and less than 10 MPa, and a value of tanδ at -5°C is 1.0 or more, and a thickness of the layer A is 100 μm or more and 400 μm or less.SELECTED DRAWING: None

Description

  The present invention relates to an interlayer film for laminated glass and laminated glass excellent in sound insulation in a frequency range from 2000 Hz to 10,000 Hz.

A glass plate used for window glass or the like is excellent in durability and daylighting property, but is known to have a very low damping performance (tan δ against bending vibration). For this reason, the resonance state caused by the vibration of the glass and the incident sound wave, that is, the decrease in sound insulation due to the coincidence effect is remarkable.
In recent years, efforts have been made to reduce automobile weight and improve fuel efficiency by reducing the weight of laminated glass. Generally, it is possible to reduce the weight by reducing the thickness of the laminated glass. However, since the sound insulation performance is reduced according to the weight reduction, a means to compensate for the decrease in the sound insulation performance is required for the weight reduction of the laminated glass. ing.

  As a method of improving sound insulation, there is a method of using an interlayer film for laminated glass (hereinafter, also simply referred to as “intermediate film”) having excellent damping performance. The intermediate film has the ability to absorb vibration energy by converting vibration energy into heat energy. As an example of such an intermediate film, an interlayer film for laminated glass made of polyvinyl butyral and having a certain impact resistance and sound insulation (for example, see Patent Document 1), a copolymer of polystyrene and a rubber-based resin, An intermediate film laminated with a plasticized polyvinyl acetal resin has been proposed (see, for example, Patent Document 2).

International Publication No. 2005/018969 Pamphlet JP 2007-91491 A

  However, even when using an interlayer film for laminated glass as described in the above patent document, the sound insulation performance in the laminated glass is not sufficiently satisfactory, and further comfort of the in-vehicle environment, or There is a demand for further improvement in sound insulation due to demands for improving fuel efficiency of automobiles by reducing the weight of laminated glass. In particular, there is a need for improvement in sound insulation in a frequency range from 2000 Hz to 6000 Hz, which is easily perceived by human ears as wind noise, wiper driving sound, and the like. Among these ranges, the range from 2000 Hz to 4000 Hz is often dominated by the sound insulation according to the mass. Therefore, the sound insulation of the interlayer film is in the range from 4000 Hz to 6000 Hz (hereinafter, the frequency from 4000 Hz to 6000 Hz). Improvement of the frequency band is also described as “medium frequency range”. On the other hand, although not as sensitive as the above range, human ears can also recognize sounds in the frequency range from 6000 Hz to 10000 Hz (hereinafter, the frequency range from 6000 Hz to 10000 Hz is also simply referred to as “high frequency range”). Since sound in the high frequency range may be generated during operation, it is required that the sound insulation in the high frequency range is sufficiently high in addition to the high sound insulation in the middle frequency range.

  Therefore, the present invention has a high sound insulation in a frequency range from 6000 Hz to 10000 Hz in addition to a high sound insulation property in a frequency range from 2000 Hz to 6000 Hz at 20 ° C., which is considered to be a temperature at which the intermediate film is usually used. An object is to provide an interlayer film.

As a result of intensive studies to solve the above problems, the present inventors have improved the sound insulation in the frequency range from 2000 Hz to 6000 Hz and also in the frequency range from 6000 Hz to 10000 Hz under the operating temperature of the intermediate film at 20 ° C. In order to sufficiently improve sound insulation, it is important to control the frequency range where the coincidence effect occurs to an appropriate frequency range, and for that purpose, it is effective to use an interlayer film for laminated glass having a specific configuration. As a result, the present invention has been completed. That is, the present invention provides the following aspects.
[1] An interlayer film for laminated glass comprising at least one layer A composed of a composition containing a thermoplastic elastomer,
A block copolymer in which the thermoplastic elastomer has a polymer block (a) containing 60 mol% or more of aromatic vinyl monomer units and a polymer block (b) containing 60 mol% or more of conjugated diene monomer units. A hydrogenated polymer,
The content of the polymer block (a) in the hydrogenated product of the block copolymer is 15% by mass or less based on the total mass of the hydrogenated product of the block copolymer,
The composition containing the thermoplastic elastomer has a peak at which tan δ measured by conducting a complex shear viscosity test under a frequency of 1 Hz in accordance with JIS K 7244-10 is -20 ° C or higher and -6 ° C or lower. The shear storage modulus at −5 ° C. is 0.7 MPa or more and less than 10 MPa, and the value of tan δ at −5 ° C. is 1.0 or more,
An interlayer film for laminated glass, wherein the thickness of the A layer is 100 μm or more and 400 μm or less.
[2] The peak value of tan δ measured by conducting a complex shear viscosity test under the condition of a frequency of 1 Hz in accordance with JIS K 7244-10 of the thermoplastic elastomer-containing composition constituting the A layer is 2.0 or more. The interlayer film for laminated glass according to [1].
[3] The content of the polymer block (a) in the hydrogenated product of the block copolymer is 3% by mass or more and 15% by mass or less based on the total mass of the hydrogenated product of the block copolymer. The interlayer film for laminated glass according to [1] or [2].
[4] An interlayer film for laminated glass having an A layer and a B layer laminated on both sides of the A layer, the two float glasses having a length of 300 mm, a width of 25 mm, and a thickness of 1.9 mm. In the laminated glass sandwiching the interlayer film for laminated glass, the loss factor at the third-order resonance frequency measured by the central vibration method at 20 ° C. is 0.25 or more and calculated according to ISO 16940 (2008). The interlayer film for laminated glass according to any one of [1] to [3], wherein the bending rigidity at the third resonance frequency is 90 N · m or more and 180 N · m or less.
[5] The interlayer film for laminated glass according to [4], wherein the B layer is composed of a resin composition containing a polyvinyl acetal resin or an ionomer resin.
[6] The layer B is composed of a resin composition containing a polyvinyl acetal resin and a plasticizer, and the content of the plasticizer is 50 parts by mass or less with respect to 100 parts by mass of the polyvinyl acetal resin. [4] An interlayer film for laminated glass as described in 1.
[7] The interlayer film for laminated glass according to [6], wherein the plasticizer is an ester plasticizer or an ether plasticizer having a melting point of 30 ° C. or lower and a hydroxyl value of 15 to 450 mgKOH / g.
[8] The shear storage elastic modulus at −5 ° C. measured by performing a complex shear viscosity test of the resin composition constituting the B layer according to JIS K 7244-10 at a frequency of 1 Hz is 100 MPa or more. The interlayer film for laminated glass according to any one of [4] to [7].
[9] The peak in which the tan δ measured by performing the complex shear viscosity test under the condition of a frequency of 1 Hz in accordance with JIS K 7244-10 is 20 ° C. or more is the resin composition constituting the B layer. The interlayer film for laminated glass according to any one of [4] to [8].
[10] The interlayer film for laminated glass according to any one of [4] to [9], wherein the thickness of the B layer is 100 μm or more and 600 μm or less.
[11] The interlayer film for laminated glass according to any one of [1] to [10], wherein the total thickness of the interlayer film for laminated glass is 1.5 mm or less.
[12] In a laminated glass in which an interlayer film for laminated glass is sandwiched between two float glasses having a length of 300 mm, a width of 25 mm, and a thickness of 1.9 mm, at a third resonance frequency measured by a central vibration method at 20 ° C. The sound transmission loss calculated from the loss coefficient and the bending rigidity at the third resonance frequency calculated according to ISO 16940 (2008) is 37 dB or more in the range of 4000 to 6299 Hz, and 6300 to 10000 Hz. The interlayer film for laminated glass according to any one of the above [1] to [11], which is 40 dB or more in the range of.
[13] In a laminated glass in which an interlayer film for laminated glass is sandwiched between two float glasses having a length of 300 mm, a width of 25 mm, and a thickness of 1.9 mm, at a third resonance frequency measured by a central vibration method at 20 ° C. The value of (acoustic transmission loss at 6300 Hz) / (acoustic transmission loss at 4000 Hz) calculated from the loss coefficient of the above and the bending stiffness at the third-order resonance frequency calculated according to ISO 16940 (2008) is 0. The interlayer film for laminated glass according to any one of [1] to [12], which is 9 or more and 1.2 or less.
[14] In a laminated glass in which an interlayer film for laminated glass is sandwiched between two float glasses having a length of 300 mm, a width of 25 mm, and a thickness of 1.9 mm, at a third resonance frequency measured by a central vibration method at 20 ° C. The value of (acoustic transmission loss at 8000 Hz) / (acoustic transmission loss at 4000 Hz) calculated from the loss coefficient of the above and the bending stiffness at the third-order resonance frequency calculated according to ISO 16940 (2008) is 1. The interlayer film for laminated glass according to any one of [1] to [13], which is 1 or more and 1.4 or less.
[15] The interlayer film for laminated glass according to any one of [1] to [14], wherein at least one layer contains a heat shielding material.
[16] The heat shielding material is tin-doped indium oxide, antimony-doped tin oxide, zinc antimonate, metal-doped tungsten oxide, phthalocyanine compound, diimonium dye, aminium dye, phthalocyanine dye, anthraquinone dye, polymethine dye, Benzenedithiol-type ammonium compound, thiourea derivative, thiol metal complex, aluminum-doped zinc oxide, tin-doped zinc oxide, silicon-doped zinc oxide, lanthanum hexaboride and vanadium oxide are at least one selected from the above, The interlayer film for laminated glass according to [15].
[17] The interlayer film for laminated glass according to any one of [1] to [16], wherein at least one layer contains an ultraviolet absorber.
[18] The ultraviolet absorber is selected from the group consisting of benzotriazole compounds, benzophenone compounds, triazine compounds, hindered amine compounds, benzoate compounds, malonic acid ester compounds, indole compounds, and oxalic acid anilide compounds. The interlayer film for laminated glass according to [17], which is at least one kind.
[19] A laminated glass in which the interlayer film for laminated glass according to any one of [1] to [18] is disposed between at least two glasses.
[20] The laminated glass according to [19], which is an automotive windshield, automotive side glass, automotive sunroof, automotive rear glass, or head-up display glass.

  According to the present invention, it is possible to provide an intermediate film having high sound insulation in a frequency range from 6000 Hz to 10000 Hz in addition to high sound insulation in a frequency range from 2000 Hz to 6000 Hz at a use temperature of 20 ° C.

It is sectional drawing which shows the structure which is one aspect | mode of the intermediate film for laminated glasses of this invention. It is a figure which shows the calculation result of the sound transmission loss by Example 1. FIG. It is a figure which shows the calculation result of the sound transmission loss by Example 2. FIG. It is a figure which shows the calculation result of the sound transmission loss by Example 3. It is a figure which shows the calculation result of the sound transmission loss by Example 4. FIG. It is a figure which shows the calculation result of the sound transmission loss by Example 5. FIG. It is a figure which shows the calculation result of the sound transmission loss by Example 6. It is a figure which shows the calculation result of the sound transmission loss by Example 7. It is a figure which shows the calculation result of the sound transmission loss by the comparative example 1. It is a figure which shows the calculation result of the sound transmission loss by the comparative example 2. It is a figure which shows the calculation result of the sound transmission loss by the comparative example 3. It is a figure which shows the calculation result of the sound transmission loss by the comparative example 4. It is a figure which shows the calculation result of the sound transmission loss by the comparative example 5. It is a figure which shows the calculation result of the sound transmission loss by the comparative example 6. It is a figure which shows the calculation result of the sound transmission loss by the comparative example 7.

  Hereinafter, embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiment described here, and various modifications can be made without departing from the spirit of the present invention.

(A layer)
The interlayer film for laminated glass of the present invention includes at least one layer A composed of a composition containing a thermoplastic elastomer. In the present invention, the thermoplastic elastomer contained in the thermoplastic elastomer-containing composition constituting the A layer is a polymer block (a) (60 mol% or more of aromatic vinyl monomer units derived from an aromatic vinyl compound). Hereinafter, also referred to as “polymer block (a)”) and polymer block (b) containing 60 mol% or more of conjugated diene monomer units derived from the conjugated diene compound (hereinafter referred to as “polymer block (b)”). And a hydrogenated product of a block copolymer (hereinafter also referred to as “block copolymer (A)”).

  Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p -Methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl- 2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichloro Rostyrene, α-chloro-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro -P-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β- Chloro-2,4-dichlorostyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene , M-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethyl Examples thereof include styrene, a styrene derivative substituted with a silyl group, indene, and vinylnaphthalene. These aromatic vinyl compounds may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, styrene, α-methylstyrene, p-methylstyrene, and a mixture thereof are preferable, and styrene is more preferable from the viewpoint of production cost and physical property balance.

  Content of the aromatic vinyl monomer unit in a polymer block (a) is 60 mol% or more with respect to all the monomer units which comprise a polymer block (a). If the aromatic vinyl monomer unit in the polymer block (a) is less than 60 mol%, moldability and strength are likely to be lowered. The content of the aromatic vinyl monomer unit in the polymer block (a) is preferably 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, particularly from the viewpoint of mechanical properties. Preferably it is 95 mol% or more, and may be 100 mol% substantially. That is, the upper limit of the content of the aromatic vinyl monomer unit in the polymer block (a) is 100 mol%.

  The polymer block (a) may contain a monomer unit derived from an unsaturated monomer other than the aromatic vinyl monomer unit within the range not hindering the object and effect of the present invention. Good. Examples of other unsaturated monomers include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, N-vinyl carbazole, β- Examples include pinene, 8,9-p-mentene, dipentene, methylene norbornene, and 2-methylenetetrahydrofuran.

  Content of the monomer unit derived from the other unsaturated monomer in the polymer block (a) is less than 40 mol% with respect to all the monomer units constituting the polymer block (a). , Preferably less than 20 mol%, more preferably less than 15 mol%, even more preferably less than 10 mol%, particularly preferably less than 5 mol%, and in a preferred embodiment of the invention the polymer block (a) Contains substantially no monomer unit derived from the other unsaturated monomer. When the polymer block (a) contains a monomer unit derived from another unsaturated monomer, the bonding form is not particularly limited, and may be random or tapered.

  The block copolymer (A) may have at least one polymer block (a). When the block copolymer (A) has two or more polymer blocks (a), these polymer blocks (a) may be the same as or different from each other. In this specification, “the polymer block is different” means that the monomer unit constituting the polymer block, the weight average molecular weight, the stereoregularity, and the ratio and the common ratio of each monomer unit when it has a plurality of monomer units. It means that at least one of the polymerization forms (random, gradient, block) is different. The same applies to the polymer block (b) described later.

  The weight average molecular weight (Mw) of the polymer block (a) contained in the block copolymer (A) is not particularly limited, and the polymer block (a) of the block copolymer (A) has. Among them, the weight average molecular weight of at least one polymer block (a) is preferably 3,000 to 60,000, and more preferably 4,000 to 50,000. When the block copolymer (A) has at least one polymer block (a) having a weight average molecular weight within the above range, the mechanical strength is further improved and the film moldability is also excellent. Here, the weight average molecular weight is a polystyrene equivalent weight average molecular weight determined by gel permeation chromatography (GPC) measurement.

  The glass transition temperature of the polymer block (a) is preferably −14 ° C. or lower, more preferably −15 ° C. or lower, preferably −30 ° C. or higher, and −20 ° C. or higher. Is more preferable. When the glass transition temperature of the polymer block (a) is within the above range, the value of tan δ of the thermoplastic elastomer-containing composition comprising the block copolymer (A) can be easily controlled within a specific range. This leads to an improvement in the sound insulation of the resulting interlayer film.

The content of the polymer block (a) in the hydrogenated product of the block copolymer (A) (when it has a plurality of polymer blocks (a), it is the total content thereof) is the block copolymer weight. It is 15 mass% or less with respect to the total mass of the hydrogenated material of a union (A). The value of tan δ also changes depending on the morphology of the block copolymer (A), and tan δ tends to increase particularly when a microphase separation structure composed of a sphere structure is taken. Since the content of the polymer block (a) in the hydrogenated product of the block copolymer (A) greatly affects the ease of forming the sphere structure, the content of the block polymer (a) is adjusted. This is very important for further improving the sound insulation of the obtained interlayer film. Therefore, from the viewpoint of enhancing sound insulation, in the present invention, the content of the polymer block (a) is 15% by mass or less based on the total mass of the hydrogenated product of the block copolymer (A). is important. From the above viewpoint, the content of the polymer block (a) in the hydrogenated product of the block copolymer (A) is 14% by mass or less based on the total mass of the hydrogenated product of the block copolymer (A). Preferably, it is 13 mass% or less, more preferably 12.5 mass% or less, even more preferably 11 mass% or less, and particularly preferably 7 mass% or less. Preferably, it is very preferably 4.5% by mass or less. From the viewpoint of sound insulation, the lower limit of the content of the polymer block (a) is preferably 3% by mass or more, for example, with respect to the total mass of the hydrogenated product of the block copolymer (A). More preferably, it is 5% by mass or more. On the other hand, from the viewpoint of improving the handleability and mechanical properties of the film, 6 to 15% by mass is preferable, 8 to 15% by mass is more preferable, and 10 to 15% by mass is particularly preferable. In one embodiment of the present invention, the content of the polymer block (a) is preferably 3 to 15% by mass with respect to the total mass of the hydrogenated product of the block copolymer (A). More preferably, it is 5-15 mass%, and it is further more preferable that it is 4-15 mass%. When the content of the polymer block (a) is within the above range, the handleability and mechanical properties of the resulting film can be enhanced while ensuring high sound insulation.
In addition, content of the polymer block (a) in a block copolymer (A) is calculated | required by a < ¹ > H-NMR spectrum.

  Examples of the conjugated diene compound constituting the polymer block (b) include isoprene, butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and myrcene. These conjugated diene compounds may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, isoprene, butadiene, a mixture of isoprene and butadiene are preferable, and isoprene is more preferable from the viewpoints of availability, versatility, and controllability of the bonding form described later.

  In the case of a mixture of butadiene and isoprene, the mixing ratio [isoprene / butadiene] (mass ratio) is not particularly limited, but is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and further The ratio is preferably 40/60 to 70/30, particularly preferably 45/55 to 65/35. The mixing ratio [isoprene / butadiene] is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, still more preferably 40/60 to 70/30, particularly in molar ratio. Preferably it is 45 / 55-55 / 45.

  Content of the conjugated diene monomer unit in a polymer block (b) is 60 mol% or more with respect to all the structural units which comprise a polymer block (b). If the conjugated diene monomer unit in the polymer block (b) is less than 60 mol%, the amount of segments exhibiting sound insulation is reduced, which is not desirable as an intermediate film. The content of the conjugated diene monomer unit in the polymer block (b) is preferably 65 mol% or more, more preferably 80 mol% or more. The upper limit is not particularly limited, and may be 100 mol%.

The polymer block (b) may have only monomer units derived from one kind of conjugated diene compound, or may have monomer units derived from two or more kinds of conjugated diene compounds. Good. In the present invention, the polymer block (b) contains 60 mol% or more of a conjugated diene monomer unit. As the conjugated diene monomer unit, a monomer unit derived from isoprene (hereinafter referred to as “a conjugated diene monomer unit”). , A monomer unit derived from butadiene (hereinafter sometimes abbreviated as “butadiene unit”), or a single monomer derived from a mixture of isoprene and butadiene. It is preferable to contain 60 mol% or more of body units in each case. When the polymer block (b) contains 60 mol% or more of at least one monomer unit selected from the group consisting of the monomer units as a conjugated diene monomer unit, good sound insulation is obtained. It can be set as the intermediate film which has the segment shown.
When the polymer block (b) has two or more kinds of conjugated diene monomer units, their bonding form is random, tapered, completely alternating, partially block-like, block, or two or more kinds thereof Any of these combinations may be used.

  The polymer block (b) may contain a monomer unit derived from an unsaturated monomer other than the conjugated diene monomer unit as long as the object and effects of the present invention are not hindered. . In this case, the content of monomer units derived from other unsaturated monomers in the polymer block (b) is 40 moles relative to all monomer units constituting the polymer block (b). %, Preferably less than 35 mol%, more preferably less than 20 mol%.

Examples of other unsaturated monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, vinylnaphthalene and Aromatic vinyl compounds such as vinyl anthracene, and methyl methacrylate, methyl vinyl ether, N-vinyl carbazole, β-pinene, 8,9-p-mentene, dipentene, methylene norbornene, 2-methylenetetrahydrofuran, 1,3-cyclopentadiene , 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene and the like. Of these, styrene, α-methylstyrene, and p-methylstyrene are preferable, and styrene is more preferable. When the polymer block (b) contains a monomer unit derived from another unsaturated monomer other than the conjugated diene monomer unit, the specific combination thereof is preferably isoprene, styrene, butadiene. And isolene, more preferably isoprene and styrene. When the polymer block (b) includes such a combination, tan δ may be increased.
When the polymer block (b) contains a monomer unit derived from another unsaturated monomer, the bonding form is not particularly limited, and may be random or tapered.

When the monomer unit constituting the polymer block (b) is any of an isoprene unit, a butadiene unit, a mixed unit of isoprene and butadiene, the bonding form of isoprene and butadiene is 1 in the case of butadiene. , 2-bond and 1,4-bond, and in the case of isoprene, 1,2-bond, 3,4-bond and 1,4-bond can be formed.
In the block copolymer, the total content of 3,4-bond units and 1,2-bond units in the polymer block (b) (hereinafter sometimes referred to as “vinyl bond amount”) is preferable. Is 20 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more. Moreover, although it does not restrict | limit in particular, The amount of vinyl bonds in a polymer block (b) becomes like this. Preferably it is 90 mol% or less, More preferably, it is 85 mol% or less. Here, the amount of vinyl bonds is calculated by dissolving the block copolymer before hydrogenation in CDCl ₃ and measuring the ¹ H-NMR spectrum. Total peak area of monomer units derived from isoprene and / or butadiene, and 3,4-bond units and 1,2-bond units in isoprene units, 1,2-bond units in butadiene units, or of isoprene and butadiene In the case of monomer units derived from a mixture, the vinyl bond content (the total content of 3,4-bond units and 1,2-bond units) is calculated from the ratio of peak areas corresponding to the respective bond units. can do.
In the case where the polymer block (b) is composed only of butadiene, the “content of 3,4-bond units and 1,2-bond units” is “content of 1,2-bond units”. And apply.

  The weight average molecular weight of the polymer block (b) contained in the block copolymer (A) is preferably 15,000 to 800,000 in the state before hydrogenation from the viewpoint of sound insulation and the like. Preferably it is 50,000-700,000, More preferably, it is 70,000-600,000, Especially preferably, it is 90,000-500,000, Most preferably, it is 130,000-450,000. Here, the weight average molecular weight is a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) measurement, and the weight average molecular weight of the polymer block (b) is the polymer block (b). It means a value calculated from the difference in weight average molecular weight before and after copolymerization.

  The glass transition temperature of the polymer block (b) is preferably −14 ° C. or lower, more preferably −15 ° C. or lower, preferably −30 ° C. or higher, and −20 ° C. or higher. Is more preferable. When the glass transition temperature of the polymer block (b) is within the above range, the value of tan δ of the thermoplastic elastomer-containing composition comprising the block copolymer (A) can be easily controlled within a specific range. This leads to an improvement in the sound insulation of the resulting interlayer film.

  The block copolymer (A) only needs to have at least one polymer block (b). When the block copolymer (A) has two or more polymer blocks (b), these polymer blocks (b) may be the same as or different from each other.

  The content of the polymer block (b) in the block copolymer (A) (when having a plurality of polymer blocks (b), the total content thereof) is the total mass of the block copolymer (A). The amount is preferably 85 to 97% by mass. When the content of the polymer block (b) is within the above range, the block copolymer (b) has appropriate flexibility and good moldability. Further, the value of tan δ also changes depending on the morphology of the block copolymer (A), and particularly when a microphase separation structure composed of a sphere structure is taken, tan δ tends to increase. Since the content of the polymer block (b) in the block copolymer (A) greatly affects the ease of forming the sphere structure, adjusting the content of the block polymer (b) is advantageous. This is very important for further improving the sound insulation of the interlayer film. Therefore, from the viewpoint of enhancing sound insulation, in the present invention, the content of the polymer block (b) is more preferably 85 to 97% by mass with respect to the total mass of the block copolymer (A). 85 to 96.5 mass% is more preferable, and 95.5 to 96.5 mass% is particularly preferable. On the other hand, from the viewpoint of improving the handleability and mechanical properties of the film, 85 to 94 mass% is preferable, 85 to 92 mass% is more preferable, and 85 to 90 mass% is still more preferable. In a preferred embodiment of the present invention, the content of the polymer block (b) is 85 to 97% by mass based on the total mass of the hydrogenated product of the block copolymer (A), and the polymer block ( When the content of b) is within the above range, the handleability and mechanical properties of the resulting film can be enhanced while ensuring high sound insulation.

  As long as the polymer block (a) and the polymer block (b) are bonded to each other, the block copolymer (A) is not limited in the form of bonding, and is linear, branched, radial, or these Any combination of two or more of these may be used. Among them, the bond form of the polymer block (a) and the polymer block (b) is preferably linear, and examples thereof include the polymer block (a) with A and the polymer block (b). When represented by B, a diblock copolymer represented by AB, a triblock copolymer represented by ABA, a tetrablock copolymer represented by ABAB, A Examples thereof include a pentablock copolymer represented by -B-A-B-A. Among these, a linear triblock copolymer or a diblock copolymer is preferable, and an ABA type triblock copolymer is preferably used from the viewpoints of flexibility, ease of manufacture, and the like.

In the present invention, the thermoplastic elastomer contained in the composition constituting the A layer is a hydrogenated product of the block copolymer (A) (hereinafter also referred to as “hydrogenated block copolymer (A)”). .
From the viewpoints of heat resistance, weather resistance, and sound insulation, 80 mol% or more of the carbon-carbon double bond of the polymer block (b) is hydrogenated (hereinafter sometimes abbreviated as “hydrogenated”). More preferably, 85 mol% or more is hydrogenated, more preferably 90 mol% or more is hydrogenated, and particularly preferably 93 mol% or more is hydrogenated. (Hereinafter, this value is also referred to as a hydrogenation rate (hydrogenation rate)). Although there is no restriction | limiting in particular in the upper limit of a hydrogenation rate, 99 mol% may be sufficient as an upper limit, and 98 mol% may be sufficient as it. In addition, a hydrogenation rate is the value which calculated | required content of the carbon-carbon double bond in the conjugated diene monomer unit in a polymer block (b) by ¹ H-NMR measurement after hydrogenation.

  The weight average molecular weight of the hydrogenated block copolymer (A) determined by gel permeation chromatography in terms of standard polystyrene is preferably 15,000 to 800,000, more preferably 50,000 to 700,000, and even more preferably. Is 70,000 to 600,000, particularly preferably 90,000 to 500,000, most preferably 130,000 to 450,000. If the weight average molecular weight of the hydrogenated block copolymer (A) is not less than the above lower limit value, the heat resistance will be high, and if it is not more than the above upper limit value, the moldability will be good.

Although the manufacturing method of a block copolymer (A) is not specifically limited, For example, it can manufacture by anionic polymerization method, cationic polymerization method, radical polymerization method etc. For example, in the case of anionic polymerization, specifically,
(I) a method of sequentially polymerizing an aromatic vinyl compound, a conjugated diene compound, and then an aromatic vinyl compound using an alkyl lithium compound as an initiator;
(Ii) a method in which an alkyl lithium compound is used as an initiator, an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized, and then a coupling agent is added to perform coupling;
(Iii) A method of sequentially polymerizing a conjugated diene compound and then an aromatic vinyl compound using a dilithium compound as an initiator.

  When a conjugated diene compound is used, the amount of vinyl bonds in the thermoplastic elastomer can be increased by adding an organic Lewis base during anionic polymerization, and by adjusting the amount of the organic Lewis base added, The amount of vinyl bonds can be easily controlled. By controlling these, the peak temperature and height of tan δ of the thermoplastic elastomer can be adjusted. For example, when an organic Lewis base is added and the vinyl bond amount of the thermoplastic elastomer increases, the value of tan δ tends to increase. By controlling this value within a specific range, the sound insulation of the resulting interlayer film can be reduced. Can be improved.

  Examples of the organic Lewis base include esters such as ethyl acetate; amines such as triethylamine, N, N, N ′, N′-tetramethylethylenediamine (TMEDA) and N-methylmorpholine; nitrogen-containing heterocyclic groups such as pyridine. Aromatic compounds; Amides such as dimethylacetamide; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF) and dioxane; Glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; Sulphoxides such as dimethyl sulfoxide; Ketones such as acetone and methyl ethyl ketone; Is mentioned.

  A hydrogenated block copolymer (A) can be obtained by subjecting the block copolymer (A) to a hydrogenation reaction. As a method for subjecting the unhydrogenated block copolymer (A) to a hydrogenation reaction, the obtained unhydrogenated block copolymer (A) is dissolved in a solvent inert to the hydrogenation catalyst. Alternatively, a method may be used in which the unhydrogenated block copolymer (A) is used as it is without being isolated from the reaction solution and reacted with hydrogen in the presence of a hydrogenation catalyst. The hydrogenation rate is preferably 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, and particularly preferably 93 mol% or more.

  Examples of hydrogenation catalysts include Raney nickel; heterogeneous catalysts in which metals such as Pt, Pd, Ru, Rh, Ni are supported on carbon, alumina, diatomaceous earth, etc .; transition metal compounds, alkylaluminum compounds, alkyllithium compounds Ziegler catalysts composed of a combination with the above; metallocene catalysts and the like. The hydrogenation reaction can usually be performed under conditions of a hydrogen pressure of 0.1 MPa or more and 20 MPa or less, a reaction temperature of 20 ° C. or more and 250 ° C. or less, and a reaction time of 0.1 hours or more and 100 hours or less.

A layer which comprises the intermediate film for laminated glasses of this invention is comprised from the composition containing the thermoplastic elastomer which consists of the said hydrogenated block copolymer (A). In the present invention, the thermoplastic elastomer-containing composition has a peak at which tan δ measured by performing a complex shear viscosity test in accordance with JIS K 7244-10 at a frequency of 1 Hz (hereinafter referred to as “tan δ peak”). Temperature)) in the range of −20 ° C. or more and −6 ° C. or less. Here, tan δ is obtained by complex shear viscosity measurement, which is also called loss tangent, and is obtained by dividing the shear loss elastic modulus by the shear storage elastic modulus. The higher this value, the higher the sound insulation is expected. Is done. When the maximum peak of tan δ is in a range lower than −20 ° C., the sound insulation performance in the frequency range from 6000 Hz to 10000 Hz is significantly reduced. Moreover, when it exists in the range higher than -6 degreeC, the fall of the sound-insulating property of the middle frequency range of 4000 Hz to 6000 Hz becomes remarkable. In the present invention, the thermoplastic elastomer-containing composition constituting the A layer preferably has the maximum peak of tan δ in the range of −15 ° C. or higher, more preferably −12 ° C. or higher. The maximum peak of tan δ is preferably in the range of −7 ° C. or lower, more preferably −8 ° C. or lower.
The tan δ is specifically measured by the method described in Examples described later.

  As a method of adjusting the peak temperature of tan δ, the content of the polymer block (a) as a hard segment is adjusted with respect to the total amount of the block copolymer, the polymer block (a) as a hard segment, Examples thereof include a method of adjusting the kind of monomer constituting the polymer block (b) which is a soft segment, the bonding form, the glass transition temperature of each segment itself, and the like. Specifically, for example, reducing the content of the polymer block (a) relative to the total amount of the block copolymer, changing the type and combination of monomers constituting the polymer block (b), and the amount of vinyl bonds By increasing the value, the peak temperature of tan δ can be controlled (increased).

  In the present invention, the thermoplastic elastomer-containing composition constituting the A layer has a shear storage elastic modulus at −5 ° C. of 0.7 MPa or more and less than 10 MPa as measured by performing a complex shear viscosity test at a frequency of 1 Hz. is there. If the shear storage modulus at −5 ° C. is less than 0.7 MPa, the sound insulation at 20 ° C. in the frequency range from 6000 Hz to 10000 Hz is lowered. Moreover, if it is 10 MPa or more, the sound insulation property at 20 ° C. in the middle frequency range is lowered.

Conventionally, in laminated glass applications that are affected by a relatively large external load, the shear storage modulus at 25 ° C. measured by performing a complex shear viscosity test under the condition of a frequency of 1 Hz is when an interlayer film is used for laminated glass. It is known as a factor related to the rigidity, moldability, etc. Therefore, in the preparation of the interlayer film for laminated glass, the shear storage modulus at 25 ° C. is controlled for the purpose of improving the rigidity and formability of the laminated glass. However, even if the shear storage modulus at 25 ° C. is adjusted to a specific range, the sound insulation property of the laminated glass in the middle frequency range of 2000 to 6000 Hz at an actual use temperature of 20 ° C. is necessarily controlled to be high according to the time-temperature conversion rule. I couldn't. On the other hand, in the present invention, in order to improve the sound insulation in the middle frequency range of 2000 to 6000 Hz, it is important to adjust the frequency range in which the coincidence effect occurs to an appropriate frequency range. It is found that it is important to control the rheology, and by setting the shear storage modulus at −5 ° C. to a range of 0.7 MPa or more and less than 10 MPa, the frequency range where the coincidence effect occurs is controlled to an appropriate position, This significantly improves the sound insulation in the frequency range of 2000 to 6000 Hz. From the viewpoint of controlling the frequency range where the coincidence effect occurs to a more appropriate frequency range, in the present invention, the shear storage modulus at −5 ° C. is preferably 1.0 MPa or more, and is 1.3 MPa or more. It is more preferable. Further, it is preferably less than 5 MPa, more preferably less than 3 MPa.
The shear storage modulus at −5 ° C. is specifically measured by the method described in the examples described later.

  As a method for adjusting the shear storage modulus at −5 ° C. of the thermoplastic elastomer-containing composition, for example, the content of the polymer block (a) that is a hard segment is adjusted, or the polymer block that is a hard segment ( Examples thereof include a) and a method of adjusting the kind of monomer constituting the polymer block (b) which is a soft segment, the bonding form, the glass transition temperature of each segment itself, and the like. Specifically, for example, the shear storage modulus at −5 ° C. can be controlled by adjusting the amount of vinyl bonds and adjusting the glass transition temperature.

  In the present invention, the value of tan δ at −5 ° C. measured by conducting a complex shear viscosity test at a frequency of 1 Hz in the thermoplastic elastomer-containing composition constituting the A layer is 1.0 or more. If the value of tan δ at −5 ° C. is less than 1.0, the sound insulation in the middle frequency range cannot be sufficiently increased even if other factors are appropriately controlled. As described above, the higher the value of tan δ, the higher the sound insulation property can be expected. However, when the sound insulation property of the intermediate film at a use temperature of 20 ° C. is taken into consideration, in the measurement at a frequency of 1 Hz, By selecting a thermoplastic elastomer by paying attention to the value, it is possible to obtain an intermediate film having a high sound insulating property particularly in the middle frequency range. This is because the condition of “frequency range near 20 ° C. and 5000 Hz” corresponds to around −5 ° C. when the measurement frequency is 1 Hz according to the temperature-time conversion rule. In the present invention, the value of tan δ at −5 ° C. is preferably 1.3 or more, and more preferably 1.5 or more, since sound insulation in the middle frequency range can be further improved. The upper limit value of tan δ at −5 ° C. is not particularly limited, but is usually 5.0 or less.

  Examples of a method for increasing the value of tan δ at −5 ° C. include increasing the peak value of tan δ and adjusting the peak temperature of tan δ by the above-described method. Examples of methods for increasing the peak value of tan δ include making the microphase separation structure a sphere structure, and increasing the content of 3,4-bond units and 1,2-bond units in the polymer block (b). Can be mentioned. The peak value of tan δ is preferably 2.0 or more, more preferably 2.2 or more, and more preferably 2.4 or more. When the height of the peak value of tan δ is equal to or higher than the lower limit, higher sound insulation can be realized. The upper limit value of the peak value of tan δ is not particularly limited, and is usually 5.0 or less.

  The thermoplastic elastomer-containing composition constituting the interlayer film for laminated glass of the present invention is preferably 60 masses of the thermoplastic elastomer comprising the hydrogenated block copolymer (A) described above relative to the total mass of the composition. %, More preferably 70% by mass or more, and still more preferably 80% by mass or more. In addition to the above thermoplastic elastomers, other thermoplastic resins (for example, additives such as crystal nucleating agents; hydrogenated coumarone / indene resins, water, etc.) as long as the effects of the present invention are not impaired as required. Hydrogenated resins such as hydrogenated rosin resins, hydrogenated terpene resins, and alicyclic hydrogenated petroleum resins; tackifying resins such as aliphatic resins composed of olefin and diolefin polymers; hydrogenated polyisoprene, hydrogenated Polybutadiene, butyl rubber, polyisobutylene, polybutene, polyolefin elastomer, specifically ethylene-propylene copolymer, ethylene-butylene copolymer, propylene-butylene copolymer, polyolefin resin, olefin polymer, polyethylene resin Etc.).

  In the interlayer film for laminated glass of the present invention, the thickness of the layer A composed of the thermoplastic elastomer-containing composition is 100 μm or more and 400 μm or less. The optimum thickness of the A layer varies depending on the thickness of other layers constituting the intermediate film (for example, B layer described later) and the elastic modulus of each layer, but the A layer composed of the thermoplastic elastomer-containing composition is thick. As the sound insulation becomes higher, the elastic modulus of the entire interlayer film tends to decrease. As a result, when the thickness of the A layer is greater than 400 μm, the frequency range in which the coincidence effect of the laminated glass is likely to occur on the high frequency side higher than 6000 Hz, and the sound insulation performance at 6000 Hz or higher may be significantly reduced. From the viewpoint of further improving the sound insulation in the high frequency range, the thickness of the A layer is preferably 380 μm or less, and more preferably 360 μm or less. Further, when the thickness of the A layer is less than 100 μm, the elastic modulus is high, and the frequency range in which the coincidence effect is generated may occur between the middle frequency range, and the sound insulation performance is lowered in the middle frequency range of 4000 to 6000 Hz. May become noticeable. In particular, the sound insulation in this frequency range is important for practical use, and the effect of improving the sound insulation is also reduced as the thickness of the A layer decreases. Therefore, the thickness of the A layer is preferably 120 μm or more, and 150 μm. More preferably.

  The A layer may contain, as necessary, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiblocking agent, a pigment, a dye, a heat shielding material, and the like, which will be described later, as other components.

Examples of the antioxidant include a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant.
Examples of the phenolic antioxidant include 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl Acrylate compounds such as -6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate; 2,6-di-t-butyl-4-methylphenol, 2,6 -Di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-) di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6- t-butyl Phenol), 4,4′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (6-tert-butyl-m-cresol), 4,4′-thiobis ( 3-methyl-6-tert-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-) 5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,1,3-tris (2-methyl-4-hydroxy -5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3- ( 3 ' , 5′-di-t-butyl-4′-hydroxyphenyl) propionate) methane or alkyl substitution such as triethylene glycol bis (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate) Phenolic compounds; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-octylthio-1,3,5-triazine, 6- (4-hydroxy-3,5-dimethyl) Anilino) -2,4-bis-octylthio-1,3,5-triazine, 6- (4-hydroxy-3-methyl-5-t-butylanilino) -2,4-bis-octylthio-1,3 Triazine groups such as 5-triazine or 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino) -1,3,5-triazine Yes phenolic compounds; and the like.

  Examples of phosphorus antioxidants include tris (2,4-di-t-butylphenyl) phosphate, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, and tris. (Dinonylphenyl) phosphite, Tris (2-t-butyl-4-methylphenyl) phosphite, Tris (cyclohexylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl Phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, or 1 Monophosphite compounds such as decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl Phosphite), 4,4′-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite) 4,4′-isopropylidene-bis (diphenylmonoalkyl (C12-C15) phosphite), 1 , 1,3-tris (2-methyl-4-di-tridecyl phosphite-5-t-butylphenyl) butane or tetrakis (2,4-di-tbutylphenyl) -4,4′-biphenylenephos Diphosphite compounds such as phyto; and the like. Of these, monophosphite compounds are preferred.

  Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3′-thiodipropionate, pentaerythritol-tetrakis- ( β-lauryl-thiopropionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane and the like.

  When it contains antioxidant, it is preferable that the content is 0.001 mass part or more with respect to 100 mass parts of thermoplastic elastomer contained in A layer, and it is more preferable that it is 0.01 mass part or more. preferable. Moreover, it is preferable that it is 5 mass parts or less with respect to 100 mass parts of thermoplastic elastomers, and, as for content of antioxidant, it is more preferable that it is 1 mass part or less. When the amount of the antioxidant is within the above range, a sufficient antioxidant effect can be imparted.

  Examples of the ultraviolet absorber include benzotriazole compounds, hindered amine compounds, benzoate compounds, triazine compounds, benzophenone compounds, malonic acid ester compounds, indole compounds, oxalic acid anilide compounds, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  When the ultraviolet absorber is contained, the content thereof is preferably 10 ppm or more, more preferably 100 ppm or more, based on the mass of the thermoplastic elastomer contained in the A layer. Moreover, it is preferable that it is 50,000 ppm or less by mass reference | standard with respect to the thermoplastic elastomer contained in A layer, and, as for content of a ultraviolet absorber, it is more preferable that it is 10,000 ppm or less. If the addition amount of the ultraviolet absorber is within the above range, a sufficient ultraviolet absorption effect can be expected.

  Examples of the light stabilizer include hindered amine light stabilizers.

By including a heat-shielding material, a heat-shielding function is imparted to the interlayer film for laminated glass, and the transmittance of near-infrared light having a wavelength of 1500 nm can be reduced when a laminated glass is used.
Examples of the heat shielding material include a heat ray shielding particle having a heat ray shielding function and a material containing an organic dye compound having a heat ray shielding function in a resin or glass. Examples of the heat ray shielding particles include tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, tin-doped zinc oxide, silicon-doped zinc oxide, and other oxide particles, LaB ₆ (lanthanum hexaboride) particles, and the like. Examples thereof include particles of an inorganic material having a heat ray shielding function. Examples of organic dye compounds having a heat ray shielding function include diimonium dyes, aminium dyes, phthalocyanine dyes, anthraquinone dyes, polymethine dyes, benzenedithiol ammonium compounds, thiourea derivatives, and thiol metal complexes. Is mentioned. These heat shielding materials may be used individually by 1 type, and may be used in combination of 2 or more type. When the heat shielding material is included, the heat shielding material includes tin-doped indium oxide, antimony-doped tin oxide, zinc antimonate, metal-doped tungsten oxide (for example, cesium-doped tungsten oxide), phthalocyanine compound, diimonium dye, aminium dye, From phthalocyanine dyes, anthraquinone dyes, polymethine dyes, benzenedithiol-type ammonium compounds, thiourea derivatives, thiol metal complexes, aluminum-doped zinc oxide, tin-doped zinc oxide, silicon-doped zinc oxide, lanthanum hexaboride, and vanadium oxide It is preferably at least one selected from the group consisting of

When heat ray shielding particles are used as the heat shielding material, the content thereof is preferably 0.01% by mass or more, more preferably 0.05% by mass or more with respect to all elastomers and resin components constituting the intermediate film. Is more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. Moreover, it is preferable that it is 5 mass% or less, and it is more preferable that it is 3 mass% or less.
The heat-shielding material may be contained in any of the A layer and the B layer described later, and the content is determined by both the A layer constituting the intermediate film and the B layer when the B layer is present. Means the total amount of the elastomer and resin contained in 100% by mass. The same applies to the content in the organic dye compound described later. When the content of the heat ray shielding particles is within the above range, the transmittance of near-infrared light having a wavelength of 1500 nm is effectively suppressed without affecting the visible light transmittance of the laminated glass using the obtained interlayer film. Can be lowered. From the viewpoint of the transparency of the interlayer film, the average particle size of the heat ray shielding particles is preferably 100 nm or less, and more preferably 50 nm or less. In addition, the average particle diameter of a heat ray shielding particle here says what is measured with a laser diffraction apparatus.

  When an organic dye compound is used as the heat shielding material, the content thereof is preferably 0.001% by mass or more, and 0.005% by mass or more with respect to all elastomers and resin components constituting the intermediate film. Is more preferable, and it is more preferable that it is 0.01 mass% or more. Moreover, it is preferable that it is 1 mass% or less, and it is more preferable that it is 0.5 mass% or less. When the content of the heat-shielding compound is within the above range, the transmittance of near-infrared light having a wavelength of 1500 nm is effectively achieved without affecting the visible light transmittance of the laminated glass using the obtained interlayer film. Can be lowered.

  Examples of the anti-blocking agent include inorganic particles and organic particles. Inorganic particles include Group IA, Group IIA, Group IVA, Group VIA, Group VIIA, Group VIIIA, Group IB, Group IIB, Group IIIB, Group IVB oxides, hydroxides, sulfides, nitrides, halogens , Carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates and their water-containing compounds, and composite compounds and natural mineral particles centered on them Is mentioned. Examples of the organic particles include fluororesins, melamine resins, styrene-divinylbenzene copolymers, acrylic resin silicones, and cross-linked products thereof.

(B layer)
The interlayer film for laminated glass of the present invention preferably includes a B layer laminated on both surfaces of the A layer, and the B layer is preferably a layer having adhesion to glass.
The B layer is an intermediate film having an A layer and a B layer laminated on both sides thereof. When sandwiched between two float glasses having a length of 300 mm, a width of 25 mm, and a thickness of 1.9 mm, the B layer is heated at 20 ° C. The loss coefficient at the third resonance frequency measured by the vibration method is 0.3 or more, and the bending rigidity at the third resonance frequency calculated according to ISO 16940 (2008) is 90 N · m or more and 180 N · m. It is preferable to select so that:

  Here, the sound insulating property of the laminated glass can be evaluated by a loss coefficient obtained by a damping test by the central vibration method. The dumping test is a test for evaluating what value the loss factor depends on the frequency and temperature. When the frequency is constant, the loss coefficient that is maximum in a certain temperature range is called the maximum loss coefficient. The maximum loss coefficient is an index indicating the goodness of damping. Specifically, it is an index indicating how fast the bending vibration generated in the plate-like object is attenuated. That is, the maximum loss coefficient is an index of sound insulation, and it can be said that the higher the maximum loss coefficient, the higher the sound insulation of the laminated glass.

The interlayer film for laminated glass of the present invention has a loss factor at the third resonance frequency measured by the central vibration method at 20 ° C. measured under the above conditions in order to achieve high sound insulation when used for laminated glass. Is preferably high. When the loss factor is 0.25 or more, an interlayer film for laminated glass that can realize sufficiently high sound insulation when used in laminated glass is preferable. The loss factor is more preferably 0.28 or more, and still more preferably 0.3 or more. The upper limit value of the loss coefficient is not particularly limited, but is usually 0.8 or less, for example, from the upper limit of the tan δ value of the thermoplastic elastomer-containing composition used for the A layer.
In addition, the said loss factor is specifically measured by the method described in the Example mentioned later.

  The loss factor in the interlayer film for laminated glass can be controlled by the tan δ value and shear modulus of the material used for the interlayer film. For example, at a specific frequency, the tan δ of the A layer constituting the intermediate layer is increased, the shear storage elastic modulus of each layer is adjusted, and the bending rigidity of the entire intermediate film is controlled within the range described later. Thus, the loss factor can be increased.

In addition, if the bending stiffness at the third resonance frequency calculated according to ISO 16940 (2008) calculated in the above-described damping test is 90 N · m or more and 180 N · m or less, the frequency range in which the coincidence effect occurs is appropriately set. Therefore, the laminated glass can be further improved in sound insulation in the frequency range of 2000 to 6000 Hz when used for laminated glass. In particular, when the bending rigidity is 90 N · m or more, it is possible to suppress the occurrence of a frequency at which the coincidence effect appears on the high frequency side, and thus it is possible to prevent a decrease in sound insulation at 6300 Hz or more, particularly 8000 Hz or more, The interlayer film for laminated glass has excellent sound insulation in the high frequency range. In addition, when the bending rigidity is 180 N · m or less, a decrease in sound insulation due to the coincidence effect that occurs on the medium frequency side can be suppressed to a small extent, and therefore, sound insulation in the medium frequency region that is particularly important in practice is excellent. It becomes an interlayer film for laminated glass. In the present invention, when used for laminated glass, the flexural rigidity is 100 N · m or more so as to provide an interlayer film for laminated glass that can impart high sound insulation in the high frequency range in addition to the intermediate frequency range. Is more preferably 120 N · m or more, and particularly preferably 140 N · m or more.
In addition, the said bending rigidity is specifically measured by the method described in the Example mentioned later.

  The bending rigidity of the interlayer film for laminated glass can be controlled by adjusting the shear storage elastic modulus of each layer constituting the interlayer film. For example, when a material having a relatively high shear storage modulus is used for the intermediate film, the bending rigidity can be relatively increased.

  For example, the B layer can be composed of a resin composition. Examples of the resin that can constitute the B layer include thermoplastic resins such as polyvinyl acetal resin, ionomer resins, and the like. Among these, from the viewpoint of producing a safety glass having a low glass scattering property when broken when used as an interlayer film for laminated glass, the B layer constituting the interlayer film for laminated glass of the present invention is composed of polyvinyl acetal resin or ionomer. It is preferable to be comprised from the resin composition containing resin.

  When using a polyvinyl acetal resin for B layer, it is preferable that the average acetalization degree of polyvinyl acetal resin is 40 mol% or more, and it is preferable that it is 90 mol% or less. When the average degree of acetalization is within the above range, the compatibility with the plasticizer is good, and a polyvinyl acetal resin can be easily obtained, which is preferable from the viewpoint of the process. The average degree of acetalization is more preferably 60 mol% or more, and further preferably 65 mol% or more from the viewpoint of water resistance. The average degree of acetalization is preferably 85 mol% or less, and more preferably 80 mol% or less.

  The content of vinyl acetate units in the polyvinyl acetal resin is preferably 30 mol% or less, and more preferably 20 mol% or less. When the content of the vinyl acetate unit is not more than the above upper limit value, it is difficult to cause blocking during the production of the polyvinyl acetal resin, and the production becomes easy. The lower limit of the average content of vinyl acetate units is not particularly limited.

  The content of the vinyl alcohol unit in the polyvinyl acetal resin is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more. The content of the vinyl alcohol unit in the polyvinyl acetal resin is preferably 35 mol% or less, more preferably 30 mol% or less, further preferably 25 mol% or less, and more preferably 20 mol% or less. It is particularly preferred. When the content of the vinyl alcohol unit is not less than the above lower limit, when a compound having a hydroxyl group, which will be described later, is used as a plasticizer, the hydroxyl group and polyvinyl acetal of the plasticizer have sufficient interaction (hydrogen bonding). As a result, the compatibility between the polyvinyl acetal and the plasticizer is improved, and the plasticizer tends to be difficult to migrate to another layer. Further, when the content of the vinyl alcohol unit is not more than the above upper limit value, the penetration resistance and impact resistance functions required for the intermediate film as safety glass can be suitably controlled.

  The polyvinyl acetal resin is usually composed of a vinyl acetal unit, a vinyl alcohol unit, and a vinyl acetate unit. The amount of each unit is determined by, for example, JIS K6728 “Testing method for polyvinyl butyral” or nuclear magnetic resonance (NMR). It can be measured.

  When the polyvinyl acetal resin contains a unit other than the vinyl acetal unit, the unit amount of vinyl alcohol and the unit amount of vinyl acetate are measured, and the vinyl acetal when these unit amounts do not contain a unit other than the vinyl acetal unit. By subtracting from the unit amount, the remaining vinyl acetal unit amount can be calculated.

  The polyvinyl acetal resin can be produced by a conventionally known method, and typically can be produced by acetalizing polyvinyl alcohol with an aldehyde. Specifically, for example, polyvinyl alcohol is dissolved in warm water, and the obtained aqueous solution is held at a predetermined temperature (for example, 0 ° C. or higher, preferably 10 ° C. or higher, 90 ° C. or lower, preferably 20 ° C. or lower). Then, the required acid catalyst and aldehydes are added and the acetalization reaction proceeds with stirring. Next, the reaction temperature is increased to about 70 ° C. to complete the reaction, and then neutralization, washing with water and drying are performed, whereby a polyvinyl acetal resin powder can be obtained.

  The viscosity average polymerization degree of polyvinyl alcohol as a raw material for the polyvinyl acetal resin is preferably 100 or more, more preferably 300 or more, more preferably 400 or more, and further preferably 600 or more. 700 or more, particularly preferably 750 or more. When the viscosity average polymerization degree of polyvinyl alcohol is too low, penetration resistance and creep resistance, particularly creep resistance under high temperature and high humidity conditions such as 85 ° C. and 85% RH may be deteriorated. Further, the viscosity average polymerization degree of polyvinyl alcohol is preferably 5000 or less, more preferably 3000 or less, further preferably 2500 or less, particularly preferably 2300 or less, and 2000 or less. Most preferred. When the viscosity average polymerization degree of polyvinyl alcohol is too high, it may be difficult to form the B layer.

  Furthermore, in order to improve the laminate suitability of the obtained interlayer film for laminated glass and obtain a laminated glass having a more excellent appearance, the viscosity average polymerization degree of polyvinyl alcohol is preferably 1500 or less, and preferably 1100 or less. Is more preferable, and it is further more preferable that it is 1000 or less.

  In addition, since the viscosity average polymerization degree of polyvinyl acetal resin corresponds with the viscosity average polymerization degree of polyvinyl alcohol used as a raw material, the above-described preferable viscosity average polymerization degree of polyvinyl alcohol matches the preferable viscosity average polymerization degree of polyvinyl acetal resin. .

  In order to set the vinyl acetate unit of the obtained polyvinyl acetal resin to 30 mol% or less, it is preferable to use polyvinyl alcohol having a saponification degree of 70 mol% or more. When the saponification degree of polyvinyl alcohol is not less than the above lower limit value, the transparency and heat resistance of the resin tend to be excellent, and the reactivity with aldehydes also becomes good. The saponification degree is more preferably 95 mol% or more.

  The viscosity average polymerization degree and saponification degree of polyvinyl alcohol can be measured based on, for example, JIS K 6726 “Testing method for polyvinyl alcohol”.

  Aldehydes used for acetalization of polyvinyl alcohol are not particularly limited, but aldehydes having 1 to 12 carbon atoms are preferred. When the number of carbon atoms in the aldehyde is within the above range, the acetalization reactivity is good, and the resin block is hardly generated during the reaction, so that the polyvinyl acetal resin can be easily synthesized.

  Examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, n-heptylaldehyde, n-octylaldehyde, n-nonyl. Aliphatic, aromatic, and alicyclic aldehydes such as aldehyde, n-decylaldehyde, benzaldehyde, cinnamaldehyde and the like can be mentioned. Of these, aliphatic aldehydes having 2 or more and 6 or less carbon atoms are preferable, and n-butyraldehyde is particularly preferable. Moreover, the said aldehydes may be used independently and may use 2 or more types together. Further, a small amount of polyfunctional aldehydes or aldehydes having other functional groups may be used in a range of 20% by mass or less of the total aldehydes.

  As the polyvinyl acetal resin, polyvinyl butyral resin is most preferable. As the polyvinyl butyral resin, a modified polyvinyl butyral resin obtained by saponifying a polyvinyl alcohol polymer obtained by saponifying a copolymer of a vinyl ester and another monomer using butyraldehyde can also be used. . Here, examples of the other monomer include ethylene, propylene, and styrene. In addition, as the other monomer, a monomer having a hydroxyl group, a carboxyl group, or a carboxylate group can be used.

  When the B layer is composed of a polyvinyl butyral resin, a plasticizer can be further added. There is no restriction | limiting in particular as a plasticizer which can be added to B layer, Monovalent carboxylic ester plasticizer; Polyvalent carboxylic ester plasticizer; Phosphate ester plasticizer; Organic phosphite plasticizer; Carboxylic acid Polymer plasticizers such as polyesters, carbonated polyesters and polyalkylene glycols; ester compounds of hydroxycarboxylic acids and polyhydric alcohols such as castor oil; hydroxycarboxylic ester plastics such as ester compounds of hydroxycarboxylic acids and monohydric alcohols Agent. These plasticizers may be used alone or in combination of two or more.

  Monovalent carboxylic acid ester plasticizers include butanoic acid, isobutanoic acid, hexanoic acid, 2-ethylbutanoic acid, heptanoic acid, octylic acid, 2-ethylhexanoic acid, lauric acid and the like, and ethylene Examples thereof include compounds obtained by a condensation reaction with a polyhydric alcohol such as glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol and glycerin. Specifically, triethylene glycol di-2-diethylbutanoate, triethylene glycol diheptanoate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dioctanoate, tetraethylene glycol di-2-ethyl Butanoate, tetraethylene glycol diheptanoate, tetraethylene glycol di-2-ethylhexanoate, tetraethylene glycol dioctanoate, diethylene glycol di-2-ethylhexanoate, PEG # 400 di-2-ethylhexanoate , Triethylene glycol mono 2-ethylhexanoate, glycerin or diglycerin completely or partially esterified with 2-ethylhexanoic acid. Here, PEG # 400 represents polyethylene glycol having an average molecular weight of 350 to 450.

  Examples of the polyvalent carboxylic acid ester plasticizer include polyvalent carboxylic acids such as adipic acid, succinic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and trimet acid, and methanol, ethanol, butanol, hexanol, Examples thereof include compounds obtained by a condensation reaction with an alcohol having 1 to 12 carbon atoms such as 2-ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol, butoxyethanol, butoxyethoxyethanol, and benzyl alcohol. Specifically, dihexyl adipate, di-2-ethylbutyl adipate, diheptyl adipate, dioctyl adipate, di-2-ethylhexyl adipate, di (butoxyethyl) adipate, di (butoxyethoxyethyl) adipate, adipic acid Mono (2-ethylhexyl), dibutyl sebacate, dihexyl sebacate, di-2-ethylbutyl sebacate, dibutyl phthalate, dihexyl phthalate, di (2-ethylbutyl) phthalate, dioctyl phthalate, di (2-ethylhexyl phthalate) ), Benzylbutyl phthalate, didodecyl phthalate, and the like.

  Phosphate ester plasticizers and phosphite ester plasticizers include phosphoric acid or phosphorous acid and methanol, ethanol, butanol, hexanol, 2-ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol, Examples thereof include compounds obtained by a condensation reaction with an alcohol having 1 to 12 carbon atoms such as butoxyethanol, butoxyethoxyethanol, and benzyl alcohol. Specifically, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (butoxyethyl) phosphate, tri (2-ethylhexyl) phosphite, etc. Can be mentioned.

  Examples of the carboxylic acid polyester plasticizer include oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 A polyvalent carboxylic acid such as cyclohexanedicarboxylic acid, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3- Butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1 , 5-pentanediol, 3-methyl- , 4-pentanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9-nonanediol, 2- Methyl-1,8-octanediol, 1,2-decanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol 1,4-cyclohexanediol, 1,2-bis (hydroxymethyl) cyclohexane, 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, and other polyhydric alcohols are copolymerized alternately. Carboxylic acid polyester obtained by glycolic acid, lactic acid, 2-hydroxybutyric acid, Aliphatic hydroxycarboxylic acids such as 4-hydroxybutyric acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 8-hydroxyhexanoic acid, 10-hydroxydecanoic acid, 12-hydroxydodecanoic acid, 4-hydroxybenzoic acid, 4 Polymer of hydroxycarboxylic acid having an aromatic ring such as-(2-hydroxyethyl) benzoic acid (hydroxycarboxylic acid polyester); γ-butyrolactone, γ-valerolactone, δ-valerolactone, β-methyl-δ-valerolactone Carboxylic acid polyesters obtained by ring-opening polymerization of aliphatic lactone compounds such as δ-hexanolactone, ε-caprolactone, and lactide, and lactone compounds having an aromatic ring such as phthalide. The terminal structure of these carboxylic acid polyesters is not particularly limited, and may be a hydroxyl group or a carboxyl group, or may be an ester bond obtained by reacting a terminal hydroxyl group or a terminal carboxyl group with a monovalent carboxylic acid or a monohydric alcohol. .

  Examples of the carbonated plasticizer include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1 , 4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentane Diol, 3-methyl-2,4-pentanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1, 9-nonanediol, 2-methyl-1,8-octanediol, , 2-decanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1, Transesterification of polyhydric alcohols such as 2-bis (hydroxymethyl) cyclohexane, 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane and carbonates such as dimethyl carbonate and diethyl carbonate And carbonic acid polyester obtained by alternating copolymerization. Although the terminal structure of these carbonic acid polyester compounds is not particularly limited, a carbonic acid ester group or a hydroxyl group is preferable.

  As polyalkylene glycol plasticizers, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and oxetane are subjected to ring-opening polymerization using a monohydric alcohol, a polyhydric alcohol, a monovalent carboxylic acid and a polyvalent carboxylic acid as an initiator. The obtained polymer is mentioned.

  Examples of hydroxycarboxylic acid ester plasticizers include monovalent hydroxycarboxylic acids such as methyl ricinoleate, ethyl ricinoleate, butyl ricinoleate, methyl 6-hydroxyhexanoate, ethyl 6-hydroxyhexanoate, and butyl 6-hydroxyhexanoate. Alcohol ester; ethylene glycol di (6-hydroxyhexanoic acid) ester, diethylene glycol di (6-hydroxyhexanoic acid) ester, triethylene glycol di (6-hydroxyhexanoic acid) ester, 3-methyl-1,5-pentanediol di (6-hydroxyhexanoic acid) ester, 3-methyl-1,5-pentanediol di (2-hydroxybutyric acid) ester, 3-methyl-1,5-pentanediol di (3-hydroxybutyric acid) ester, 3-methyl -1,5 Hydroxycarbons such as pentanediol di (4-hydroxybutyric acid) ester, triethylene glycol di (2-hydroxybutyric acid) ester, glycerin tri (ricinoleic acid) ester, L-tartaric acid di (1- (2-ethylhexyl)), castor oil In addition to the acid polyhydric alcohol ester; a compound obtained by replacing the hydroxycarboxylic acid-derived group of the hydroxycarboxylic acid polyhydric alcohol ester with a carboxylic acid-derived group or a hydrogen atom not containing a hydroxyl group can also be used. In addition, what is obtained by a conventionally well-known method can be used for these hydroxycarboxylic acid ester.

  The plasticizer contained in the B layer has a melting point of 30 ° C. or less and a hydroxyl value of 15 mgKOH / g from the viewpoint of improving compatibility with polyvinyl butyral resin, low migration to other layers, and non-migration. An ester plasticizer or ether plasticizer that is 450 mgKOH / g or less, or an ester plasticizer or ether plasticizer that is amorphous and has a hydroxyl value of 15 mgKOH / g or more and 450 mgKOH / g or less is used. It is preferable. Here, non-crystalline means that the melting point is not observed at a temperature of −20 ° C. or higher. The hydroxyl value is preferably 15 mgKOH / g or more, more preferably 30 mgKOH / g or more, and most preferably 45 mgKOH / g or more. The hydroxyl value is preferably 450 mgKOH / g or less, more preferably 360 mgKOH / g or less, and most preferably 280 mgKOH / g or less. Examples of the ester plasticizer include polyesters satisfying the above-mentioned regulations (such as the above-mentioned carboxylic acid polyester plasticizer and carbonated polyester plasticizer) and hydroxycarboxylic acid ester compounds (such as the above-mentioned hydroxycarboxylic acid ester plasticizer). Examples of the ether plasticizer include polyether compounds (such as the above-mentioned polyalkylene glycol plasticizer) that satisfy the above-mentioned regulations.

  The plasticizer content in the B layer is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and further preferably 40 parts by mass or less with respect to 100 parts by mass of the polyvinyl acetal resin. preferable. When the content of the plasticizer is not more than the above upper limit value, the laminated glass using the resulting interlayer film is excellent in impact resistance. The lower limit of the content of the plasticizer is not particularly limited, and may be, for example, 10 parts by mass or more, or 0 part by mass with respect to 100 parts by mass of the thermoplastic resin constituting the B layer.

  Since the compound having a hydroxyl group is highly compatible with the polyvinyl acetal resin and has a low migration property to the A layer, and the sound insulation is stably exhibited, the plasticizer added to the B layer includes a compound having a hydroxyl group. It can be used suitably. Examples of the compound having a hydroxyl group include polyester polyols “Kuraray polyol” P-510 and P-1010 manufactured by Kuraray Co., Ltd.

  The ratio of the content of the compound having a hydroxyl group to the total amount of the plasticizer contained in the B layer is preferably 10% by mass or more, more preferably 15% by mass or more, and 20% by mass or more. Is more preferable. Further, the ratio of the content of the compound having a hydroxyl group to the total amount of the plasticizer contained in the B layer is preferably 100% by mass or less, more preferably 90% by mass or less, and 80% by mass or less. More preferably it is.

  The ionomer resin is not particularly limited, and includes, for example, a monomer unit derived from ethylene and a monomer unit derived from an α, β-unsaturated carboxylic acid, and at least a part of the α, β-unsaturated carboxylic acid. Is a resin neutralized with metal ions. Examples of metal ions include sodium ions. In the present invention, in the ethylene-α, β-unsaturated carboxylic acid copolymer serving as the base polymer, the content of the monomer unit of α, β-unsaturated carboxylic acid is preferably 2% by mass or more. More preferably, it is 5 mass% or more. Further, the content ratio of the monomer unit of α, β-unsaturated carboxylic acid is preferably 30% by mass or less, and more preferably 20% by mass or less. In the present invention, an ionomer of an ethylene-acrylic acid copolymer and an ionomer of an ethylene-methacrylic acid copolymer are preferable from the viewpoint of availability. As the ethylene ionomer, sodium ionomer of ethylene-acrylic acid copolymer and sodium ionomer of ethylene-methacrylic acid copolymer can be mentioned as particularly preferred examples. Only one type of ionomer resin may be used alone, or two or more types may be used in combination.

  Examples of the α, β-unsaturated carboxylic acid constituting the ionomer include acrylic acid, methacrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, maleic anhydride and the like, and acrylic acid or methacrylic acid is particularly preferable.

  The layer B can contain a resin other than the polyvinyl acetal resin or ionomer resin, but preferably contains 40% by mass or more of the polyvinyl acetal resin or ionomer resin from the viewpoint of maintaining high adhesiveness with glass. It is more preferable to contain 50% by mass or more, still more preferably 60% by mass or more, particularly preferably 80% by mass or more, and still more preferably 90% by mass or more.

  In a preferred embodiment of the interlayer film for laminated glass of the present invention, the resin constituting the B layer is an ionomer resin. Even when an ionomer resin is used as the resin constituting the B layer, the loss factor and the bending rigidity of the laminated glass are appropriately controlled by using the A layer having excellent sound insulation properties according to the present invention. An intermediate film having excellent sound insulation and high sound insulation in a high frequency range can be obtained.

  In the present invention, the resin composition constituting the B layer has a shear storage modulus at a temperature of −5 ° C. measured by performing a complex shear viscosity test at a frequency of 1 Hz according to JIS K 7244-10, and is 100 MPa or more. It is preferable that it is 200 MPa or more. When the shear storage elastic modulus under the above conditions is 100 MPa or more, an appropriate elastic modulus can be imparted to the interlayer film for laminated glass composed of the A layer and the B layer laminated on both sides thereof, and the frequency at which the coincidence effect appears is high. Occurrence on the frequency side can be suppressed, and sound insulation at 6000 Hz or higher can be further improved. The B layer having a shear storage modulus of 100 MPa or more can be obtained, for example, by setting the amount of the plasticizer to 50 parts by mass or less with respect to 100 parts by mass of the polyvinyl acetal resin. The upper limit of the shear storage modulus at −5 ° C. is not particularly limited, but is preferably 500 MPa or less from the viewpoint of moldability and handleability of the laminate.

  The value of the shear storage modulus at −5 ° C. can be controlled by the amount of plasticizer added in the case of a polyvinyl acetal resin, and by the kind of constituent monomer or the amount of metal ions in the case of an ionomer resin.

  In the present invention, the resin composition constituting the B layer has a peak at which tan δ measured by conducting a complex shear viscosity test under a frequency of 1 Hz in accordance with JIS K 7244-10 is in the range of 20 ° C. or more. Preferably, it has in the range of 25 degreeC or more, More preferably, it has in the range of 30 degreeC or more. When the peak at which tan δ is maximum is in the range of the lower limit value or more, an appropriate bending strength can be imparted to the B layer, and the frequency range in which the coincidence effect controlled by the A layer appears can be maintained in an appropriate frequency range. When used in laminated glass, high sound insulation can be realized over a wide range from the middle frequency range to the high frequency range. The upper limit value of the peak temperature at which the tan δ is maximized is not particularly limited, but is usually 150 ° C. or lower.

  The B layer may further contain, as necessary, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiblocking agent, a pigment, a dye, a functional inorganic compound, a heat shielding material, and the like as other components. Good.

  Antioxidants, ultraviolet absorbers, light stabilizers, anti-blocking agents, heat shield materials, etc. that may be contained in the B layer include the same materials as those described in the description of the previous A layer, It may be the same as or different from the material and content that the A layer may contain. In the interlayer film for laminated glass of the present invention, these other components may be contained only in either the A layer or the B layer, or may be contained in both the A layer and the B layer. Moreover, when contained in both A layer and B layer, the same component may be contained and a different component may be contained.

  In B layer, the adhesiveness to the glass etc. of the intermediate film obtained can be controlled as needed. Examples of the method for controlling the adhesiveness include a method of adding an additive usually used as an adhesiveness adjusting agent for laminated glass or various additives for adjusting the adhesiveness.

  As the adhesiveness adjusting agent, for example, those disclosed in International Publication No. 03/033583 can be used. Examples include organic acids such as carboxylic acids such as octanoic acid, hexanoic acid, butyric acid, acetic acid and formic acid; and salts of inorganic acids such as hydrochloric acid and nitric acid. Of these, alkali metal salts and alkaline earth metal salts such as potassium salt, sodium salt and magnesium salt are preferable.

  The optimum addition amount of the adhesion modifier varies depending on the additive used, but the adhesion force of the obtained interlayer film to the glass is generally determined in the Pummel test (Pummeltest; described in International Publication No. 03/033583). Is preferably adjusted to 3 or more and 10 or less, and more preferably adjusted to 3 or more and 6 or less when particularly high penetration resistance is required. Moreover, when high glass scattering prevention property is required, it is more preferable to adjust so that it may become 7 or more and 10 or less. When high glass scattering prevention property is required, it is also a useful method not to add an adhesion modifier.

(Interlayer film for laminated glass)
The method for producing the interlayer film for laminated glass of the present invention is not particularly limited. For example, in the case of the configuration having the B layer laminated on both surfaces of the A layer, after uniformly kneading the resin composition constituting the B layer, B layer is prepared by a known film forming method such as extrusion method, calendering method, pressing method, casting method, inflation method, etc., and A layer is prepared by a thermoplastic elastomer in the same manner, and these are press molded, etc. The B layer, the A layer and other necessary layers may be formed by coextrusion.

  Among known film forming methods, a method of manufacturing a laminate using an extruder is particularly preferably employed. The resin temperature (composition temperature) at the time of extrusion is preferably 150 ° C. or higher, and more preferably 170 ° C. or higher. Moreover, the resin temperature (composition temperature) at the time of extrusion is preferably 250 ° C. or less, and more preferably 230 ° C. or less. When the temperature at the time of extrusion is within the above range, the decomposition of the resin or the like contained in the composition can be suppressed, so that the resin or the like is hardly deteriorated and the discharge from the extruder can be stabilized. In order to efficiently remove the volatile substance, it is preferable to remove the volatile substance from the vent port of the extruder by reducing the pressure.

  The film thickness of the A layer is 100 μm or more and 400 μm or less as described above. The thicknesses of the B layers are each preferably 100 μm or more, more preferably 150 μm or more, and further preferably 200 μm or more. The film thicknesses of the B layers are each preferably 600 μm or less, more preferably 500 μm or less, further preferably 350 μm or less, and further preferably 300 μm or less. When the film thickness of the B layer is not less than the above lower limit value, an appropriate bending rigidity can be imparted to the intermediate film, and a decrease in sound insulation in a high frequency region can be suppressed, and the film thickness of the B layer is not more than the above upper limit value. And the total thickness of the intermediate film does not become too thick, which is advantageous for reducing the weight of the laminated glass.

  In the present invention, the interlayer film for laminated glass may have a single-layer structure composed of only the A layer, or may have a laminated structure in which the A layer is sandwiched between the B layers as shown in FIG. The laminated structure in the intermediate film is appropriately determined depending on the purpose. In addition to the laminated structure of B layer / A layer / B layer, B layer / A layer / B layer / A layer, B layer / A layer / B layer / A layer A stacked structure of / B layer may be used.

  Further, the interlayer film for laminated glass of the present invention may contain one or more layers other than the A layer and the B layer (referred to as the C layer), for example, B layer / A layer / C layer / B layer, B layer / A layer / B layer / C layer, B layer / C layer / A layer / C layer / B layer, B layer / C layer / A layer / B layer / C layer, B layer / A layer / C layer / B layer / C layer, C layer / B layer / A layer / B layer / C layer, C layer / B layer / A layer / C layer / B layer / C layer, C layer / B layer / C layer / A A laminated structure such as layer / C layer / B layer / C layer may also be used. In the laminated configuration, when two or more A layers, B layers, and / or C layers are included, the components constituting each A layer, B layer, and C layer may be the same as or different from each other.

  The C layer that can be included in the interlayer film for laminated glass of the present invention may be a layer made of a known resin. Examples of the resin constituting the C layer include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, polytetrafluoroethylene, acrylic resin, polyamide, polyacetal, polycarbonate, polyester such as polyethylene terephthalate and polybutylene terephthalate. , Cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyethersulfone, polyarylate, liquid crystal polymer, polyimide and the like. Moreover, you may contain additives, such as a plasticizer, antioxidant, a ultraviolet absorber, a light stabilizer, an antiblocking agent, a pigment, dye, and a heat-shielding material, as needed.

  The interlayer film for laminated glass of the present invention preferably has a concavo-convex structure formed on the surface by a conventionally known method such as melt fracture or embossing. The shape of the melt fracture and the emboss is not particularly limited, and conventionally known shapes can be adopted.

  Further, the total thickness of the interlayer film for laminated glass of the present invention is preferably 400 μm or more, and more preferably 500 μm or more. Further, the total thickness of the intermediate film is preferably 1.5 mm or less, and more preferably 1 mm or less. If the total thickness is equal to or greater than the above lower limit value, it is excellent in handleability when producing laminated glass, and if the total thickness of the interlayer film is equal to or less than the above upper limit value, it leads to weight reduction of the entire laminated glass and reduces the cost of the interlayer film. This is preferable.

  The interlayer film for laminated glass of the present invention is a laminated glass in which the interlayer film for laminated glass is sandwiched between two float glasses having a length of 300 mm, a width of 25 mm, and a thickness of 1.9 mm. The sound transmission loss calculated according to ISO 16940 (2008) using the loss coefficient and bending stiffness at the third-order resonance frequency measured is 37 dB or more in the range of 4000 Hz to 6299 Hz in the middle frequency range, and in the range of 6300 Hz to 10000 Hz. It is preferably 40 dB or more. In addition, the phrase “more than 37 dB in the range of 4000 Hz to 6299 Hz in the middle frequency range” means that the sound transmission loss is 37 dB or more over the entire frequency range of 4000 Hz to 6299 Hz, and is described in this specification. Similar descriptions in the frequency range are the same. Moreover, the said measurement is performed in the layer structure which comprises the final intermediate film for laminated glasses. The sound transmission loss in the middle frequency range of 4000 Hz to 6299 Hz is more preferably 38 dB or more, and further preferably 39 dB or more. The sound transmission loss in the range of 6300 Hz to 10,000 Hz is more preferably 41 dB or more, and further preferably 42 dB or more. As a result, the interlayer film of the present invention can keep the sound insulation performance from 6000 Hz to 10000 Hz sufficiently high while enhancing the sound insulation performance in the middle frequency range between 4000 Hz and 6000 Hz, which is practically important.

  Conventionally, attempts have been made to increase the sound insulation from 4000 Hz to 6000 Hz, which is the middle frequency range, by lowering the elastic modulus of the intermediate film. However, by reducing the elastic modulus of the intermediate film, the frequency at which the coincidence effect appears is increased. It tends to occur in the frequency range, and for example, sound insulation in a high frequency range of 8000 Hz to 10000 Hz, that is, sound transmission loss is significantly reduced. In the present invention, as described above, each component constituting the A layer and the B layer, a combination thereof, a film thickness and the like are selected, and the peak temperature of tan δ and the value of the shear storage modulus at −5 ° C. are controlled. Thus, the frequency range in which the coincidence effect appears can be controlled to an appropriate frequency range, and the sound insulation can be improved over a wide range from 2000 Hz to 10000 Hz including not only the middle frequency range but also the high frequency range.

  In the present invention, as a parameter indicating a good balance between sound insulation properties in the middle frequency range and the high frequency range, a ratio of a sound transmission loss of 4000 Hz and a sound transmission loss of 6300 Hz, that is, (sound transmission loss at 6300 Hz) / (4000 Hz). The value of (sound transmission loss) is preferably 0.9 or more and 1.2 or less. It can be said that the sound insulation in the high frequency region is lower as this value is smaller than 0.9, and the sound insulation in the middle frequency region is lower as it is larger than 1.2.

  Similarly, the ratio of the sound transmission loss of 4000 Hz and the sound transmission loss of 8000 Hz was taken as a parameter indicating a good balance of sound insulation in the middle frequency range and the high frequency range, (acoustic transmission loss at 8000 Hz) / (4000 Hz). When the value of (acoustic transmission loss) is obtained, it is preferable that this value is 1.1 or more and 1.4 or less. It can be said that the sound insulation in the high frequency region is lower as the value is smaller than 1.1, and the sound insulation in the middle frequency region is lower as the value is larger than 1.4.

(Laminated glass)
By using the interlayer film for laminated glass of the present invention, a laminated glass excellent in sound insulation can be obtained. Therefore, the interlayer film for laminated glass of the present invention can be suitably used for an automobile windshield, an automobile side glass, an automobile sunroof, an automobile rear glass, or a head-up display glass. When the laminated glass having the structure of the interlayer film for laminated glass of the present invention is applied to the glass for head-up display, the sectional shape of the interlayer film used is such that one end face side is thick and the other end face side is thin. Preferably there is. In that case, the cross-sectional shape may be a wedge shape that gradually becomes thinner from one end face side to the other end face side, or between one end face and the other end face. A part of the cross-section may be wedge-shaped so that it has the same thickness up to an arbitrary position and gradually becomes thinner from the arbitrary position to the other end surface, as long as there is no problem in manufacturing. It may have any shape regardless of the position.

  In the laminated glass of the present invention, usually two glasses are used. Although the thickness of the glass which comprises the laminated glass of this invention is not specifically limited, Usually, it is preferable that it is 100 mm or less. Moreover, since the interlayer film of the present invention is excellent in sound insulation, high sound insulation is exhibited even when a thinner glass is used, so that the laminated glass can be reduced in weight. From the viewpoint of weight reduction, at least one glass is preferably 2.8 mm or less, more preferably 2.5 mm or less, and further preferably 2.0 mm or less. It is especially preferable that it is 8 mm or less. In particular, the thickness of one glass is 1.8 mm or more, the thickness of the other glass is 1.8 mm or less, and the difference in thickness of each glass is 0.2 mm or more, so that the bending strength is not impaired. A laminated glass that achieves both a reduction in thickness and weight can be produced. The difference in thickness between the glasses is preferably 0.5 mm or more.

The sound insulation of laminated glass can be evaluated by the loss factor obtained by the damping test by the central vibration method as described in the interlayer film for laminated glass. The higher the maximum loss coefficient of laminated glass, the higher the sound insulation of laminated glass. Can be said to be expensive.
The laminated glass obtained from the interlayer film of the present invention is laminated by pressing the interlayer film between two pieces of glass 300 mm long, 25 mm wide, and 1.9 mm thick, and bonded at a temperature of 140 ° C. and a pressure of 1 MPa for 60 minutes. It is preferable that the maximum loss coefficient at the third-order resonance frequency measured by a damping test by the central vibration method at 20 ° C. of the laminated glass after the production of the laminated glass is 20 ° C. or more is 0.28 or more. More preferably, it is more preferably 0.3 or more.

  Further, it is preferable that the bending rigidity at the third resonance frequency calculated in accordance with ISO 16940 (2008) by the damping test is 90 N · m to 180 N · m. When the bending stiffness is within the above range, high sound insulation can be realized over a wide range from the middle frequency range to the high frequency range. In the laminated glass of the present invention, the bending rigidity is more preferably 140 N · m or more and 180 N · m or less.

  The laminated glass of the present invention uses a loss coefficient and bending rigidity at the third resonance frequency, and the sound transmission loss calculated according to ISO 16940 (2008) is from 37 dB or more and from 6300 Hz in the middle frequency range of 4000 Hz to 6299 Hz. It is preferably 40 dB or more in the range of 10,000 Hz. The sound transmission loss in the middle frequency range of 4000 Hz to 6299 Hz is more preferably 38 dB or more, and further preferably 39 dB or more. The sound transmission loss in the range of 6300 Hz to 10,000 Hz is more preferably 41 dB or more, and further preferably 42 dB or more.

  Further, as a parameter indicating a good balance between sound insulation in the middle frequency range and the high frequency range, the ratio of the acoustic transmission loss of 4000 Hz and the acoustic transmission loss of 6300 Hz, that is, (acoustic transmission loss at 6300 Hz) / (acoustic transmission at 4000 Hz). The value of (loss) is preferably 0.9 or more and 1.2 or less. Similarly, the ratio of the sound transmission loss of 4000 Hz and the sound transmission loss of 8000 Hz was taken as a parameter indicating a good balance of sound insulation in the middle frequency range and the high frequency range, (acoustic transmission loss at 8000 Hz) / (4000 Hz). When the value of (acoustic transmission loss) is obtained, it is preferable that this value is 1.1 or more and 1.4 or less.

(Laminated glass manufacturing method)
The laminated glass of the present invention can be produced by a conventionally known method, and examples thereof include a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, and a method using a nip roll. Moreover, an autoclave process can also be additionally performed after temporary pressure bonding.

In the case of using a vacuum laminator device, for example, a known device used for manufacturing a solar cell is used, and at a reduced pressure of 1 × 10 ⁻⁶ MPa to 3 × 10 ⁻² MPa at 100 ° C. to 200 ° C., In particular, lamination is performed at a temperature of 130 ° C. or higher and 170 ° C. or lower. A method using a vacuum bag or a vacuum ring is described in, for example, European Patent No. 1235683, and is laminated at 130 ° C. or higher and 145 ° C. or lower, for example, under a pressure of about 2 × 10 ⁻² MPa.

  In the case of using a nip roll, for example, there is a method in which after the first temporary pressure bonding at a temperature equal to or lower than the flow start temperature of the polyvinyl acetal resin, the pressure bonding is further performed under conditions close to the flow start temperature. Specifically, for example, a method of heating to 30 ° C. or more and 100 ° C. or less with an infrared heater or the like, then degassing with a roll, further heating to 50 ° C. or more and 150 ° C. or less, and then pressure bonding with the roll for adhesion or temporary adhesion Is mentioned.

  The autoclave process that is additionally performed after the temporary pressure bonding depends on the thickness and configuration of the module. For example, under a pressure of 1 MPa to 15 MPa, a temperature of 120 ° C. to 160 ° C. is 0.5 hours to 2 hours. To be implemented.

  The glass used when producing the laminated glass is not particularly limited, and conventionally known inorganic glass such as float plate glass, polished plate glass, mold plate glass, mesh plate glass, and heat ray absorbing plate glass; organic such as polymethyl methacrylate and polycarbonate Glass; etc. can be used. These may be colorless, colored, transparent or non-transparent. These may be used alone or in combination of two or more.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these Examples. In the following examples, “%” means “% by mass” unless otherwise specified.

  In the following Examples and Comparative Examples, as polyvinyl butyral resin (PVB), polyvinyl alcohol having the same viscosity average polymerization degree as the target viscosity average polymerization degree is acetalized with n-butyraldehyde under a hydrochloric acid catalyst. Was used. The viscosity average degree of polymerization of the polyvinyl alcohol is a value measured based on JIS K 6726 “Testing method for polyvinyl alcohol”.

1. Evaluation of physical properties (the shear storage modulus and tan δ of the thermoplastic elastomer-containing composition constituting the layer A at −5 ° C., the peak height and the peak temperature, and the shear storage modulus of the resin composition constituting the layer B and tan δ peak temperature)
A thermoplastic elastomer (hydrogenated block copolymer) constituting layer A is pressed at a temperature of 230 ° C. and a pressure of 10 MPa for 3 minutes to produce a single-layer sheet having a thickness of 1.0 mm. A test sheet was cut out into a shape. Similarly, the resin composition constituting the B layer was pressurized at a temperature of 170 ° C. and a pressure of 10 MPa for 5 minutes to produce a single-layer sheet having a thickness of 1.0 mm, and the single-layer sheet was cut into a disk shape and tested. It was set as a sheet.

  For the measurement, based on JIS K7244-10 (2005), as a parallel plate vibration rheometer, a warp control type dynamic viscoelasticity device having a disc diameter of 8 mm (manufactured by TA Instruments Japan Co., Ltd. (ARES -G2)) was used.

  With the test sheet produced above, the gap between the two flat plates of the distortion control type dynamic viscoelastic device is completely filled, the strain is 0.1%, and the test sheet is vibrated at a frequency of 1 Hz, The temperature was increased from −70 ° C. to 200 ° C. at a constant rate of 3 ° C./min. The temperature of the test sheet and the disc is maintained until there is no change in the measured values of the shear loss modulus and shear storage modulus, and the value of tan δ of the hydrogenated block copolymer constituting the A layer at -5 ° C, peak The maximum value of the intensity (tan δ peak height) and the temperature at which the maximum value was obtained (tan δ peak temperature) were determined. Similarly, the shear storage elastic modulus and tan δ peak temperature of the resin composition constituting the B layer were determined.

2. Content of polymer block (a) The hydrogenated block copolymer constituting the A layer was dissolved in CDCl ₃ and ¹ H-NMR spectrum was measured [apparatus: JNM-Lambda 500 (manufactured by JEOL Ltd.), measurement Temperature: 50 ° C.], and the content of the polymer block (a) was calculated from the peak intensity derived from styrene.

3. Glass transition temperature of polymer block (b) The glass transition temperature of the polymer block (b) contained in the thermoplastic elastomer constituting the A layer is determined by using differential scanning calorimetry (DSC, manufactured by Seiko Denshi Kogyo Co., Ltd.) The temperature was increased from −120 ° C. to 100 ° C. at a rate of temperature increase of 10 ° C./min, and the temperature at the inflection point of the obtained measurement curve was read and used as the glass transition temperature.

4). Sound insulation property evaluation (loss coefficient and bending rigidity at the third resonance frequency and third resonance frequency of laminated glass, sound transmission loss at 4000 Hz, 5000 Hz, 6300 Hz, 8000 Hz, and 10000 Hz)
Each interlayer film obtained in each Example / Comparative Example is sandwiched between two commercially available float glass (length 300 mm x width 25 mm x thickness 1.9 mm), and crimped at a temperature of 140 ° C., a pressure of 1 MPa, for 60 minutes. To make a laminated glass. Thereafter, the excitation force built into the impedance head of the exciter (power amplifier / model 371-A) in the mechanical impedance device (manufactured by Ono Sokki Co., Ltd .; mass cancellation amplifier: massscanner MA-5500; channel data station: DS-2100) The central part of the laminated glass was fixed to the tip of the detector. At 20 ° C., a vibration was applied to the central portion of the laminated glass in the frequency range of 0 to 10000 Hz, and a damping test of the laminated glass by the central vibration method was performed by detecting the excitation force and acceleration waveform at this point. . Based on the obtained excitation force and the velocity signal obtained by integrating the acceleration signal, the mechanical impedance of the excitation point (the central part of the laminated glass with vibration) is obtained, the horizontal axis is the frequency, and the vertical axis In the impedance curve obtained as the mechanical impedance, the loss factor of the laminated glass was determined from the peak frequency and the half width. Further, using the third resonance frequency and the loss coefficient at the third resonance frequency, the bending stiffness at the third resonance frequency was calculated according to ISO 16940 (2008). In addition, the sound transmission loss from 1000 Hz to 10000 Hz was calculated according to ISO 16940 (2008) using the loss coefficient and bending rigidity at the third resonance frequency (FIGS. 2 to 15). Tables 1 and 2 show the measurement results of the third resonance frequency and the loss coefficient at the third resonance frequency, the bending rigidity at the third resonance frequency, and the calculation results of sound transmission loss at 4000 Hz, 5000 Hz, 6300 Hz, 8000 Hz, and 10,000 Hz.

<Example 1>
According to the composition shown in Table 1, the layer A contains 12% by mass of styrene units and 88% by mass of isoprene units, and the peak temperature at which the peak height of tan δ is maximized is −8.5 ° C. Linear hydrogenated styrene-isoprene-styrene triblock copolymer (hydrogenation rate 91%, weight average molecular weight 182,000) based on dynamic viscoelasticity measurement at a frequency, and an ionomer film (layer B) SENTRYGLAS (registered trademark) Interlayer manufactured by DuPont) was used. Each of these was formed into an A layer having a thickness of 250 μm and a B layer having a thickness of 250 μm by an extrusion method. The obtained A layer was sandwiched between two B layers and press-molded at 150 ° C. to produce a 0.75 mm thick intermediate film as a composite film having a three-layer structure. Using the obtained interlayer film, according to the evaluation method described above, the loss coefficient and bending stiffness of the laminated glass at the third resonance frequency, the third resonance frequency, and the sound transmission loss at 4000 Hz, 5000 Hz, 6300 Hz, 8000 Hz, and 10000 Hz. Calculated. The results are shown in Table 1 and FIG.

<Example 2>
In the B layer, an intermediate film was prepared in the same manner as in Example 1 except that a polyvinyl butyral resin composition was used instead of the ionomer film, and physical properties were evaluated. A polyvinyl butyral resin composition having a viscosity average polymerization degree of about 1700, an acetalization degree of 70 mol%, and a vinyl acetate unit content of 0.9 mol% of 100 parts by mass of a polyvinyl butyral resin as a plasticizer manufactured by Kuraray Co., Ltd. The polyester polyol “Kuraray polyol P-510” (melting point: −77 ° C., hydroxyl value: 213.0-235.0 mgKOH / g) of 38.8 parts by mass was used. The results are shown in Table 1 and FIG.

<Example 3>
In the layer A, instead of the linear hydrogenated styrene-isoprene-styrene triblock copolymer used in Example 1, the peak height of tan δ containing 4% by mass of styrene units and 96% by mass of isoprene units is Example except that a linear hydrogenated styrene-isoprene-styrene triblock copolymer having a maximum peak temperature of −11.1 ° C. (based on the dynamic viscoelasticity measurement at a frequency of 1 Hz described above) was used. An interlayer film was prepared using the same method as in Example 1, and physical properties were evaluated. The results are shown in Table 1 and FIG.

<Example 4>
An intermediate film was produced by using the same method as in Example 3 except that the thickness of the A layer was changed from 250 μm to 350 μm, and the thickness of the B layer was changed from 250 μm to 200 μm, and physical properties were evaluated. The results are shown in Table 1 and FIG.

<Example 5>
In the B layer, an intermediate film was prepared in the same manner as in Example 3 except that a polyvinyl butyral resin composition was used instead of the ionomer film, and physical properties were evaluated. A polyvinyl butyral resin composition having a viscosity average polymerization degree of about 1700, an acetalization degree of 70 mol%, and a vinyl acetate unit content of 0.9 mol% of 100 parts by mass of a polyvinyl butyral resin as a plasticizer manufactured by Kuraray Co., Ltd. A composition comprising 38.8 parts by mass of the polyester polyol “Kuraray polyol P-510” was used. The evaluation results are shown in Table 1 and FIG.

<Example 6>
An intermediate film was prepared using the same method as in Example 5 except that the film thickness of the A layer was changed from 250 μm to 350 μm, and the film thickness of the B layer was changed from 250 μm to 200 μm, and physical properties were evaluated. The results are shown in Table 1 and FIG.

<Example 7>
An intermediate film was produced using the same method as in Example 5 except that the thickness of the A layer was changed from 250 μm to 225 μm, and the thickness of the B layer was changed from 250 μm to 275 μm, and physical properties were evaluated. The results are shown in Table 1 and FIG.

<Comparative Example 1>
According to the composition shown in Table 2, in layer A, instead of the linear hydrogenated styrene-isoprene-styrene triblock copolymer used in Example 1, 34% by mass of styrene units, isoprene units and styrene units (isoprene: Containing 66% by mass of styrene (molar ratio) = 88: 12) The peak temperature at which the peak height of tan δ is maximum is 2.6 ° C. (based on the dynamic viscoelasticity measurement at the frequency of 1 Hz described above). An intermediate film was prepared and evaluated for physical properties using the same method as in Example 1 except that a linear hydrogenated styrene- (isoprene / styrene) -styrene triblock copolymer was used. The results are shown in Table 1 and FIG.

<Comparative Example 2>
In the layer A, instead of the linear hydrogenated styrene-isoprene-styrene triblock copolymer used in Example 2, the peak height of tan δ containing 4% by mass of styrene units and 96% by mass of isoprene units is Example except that a linear hydrogenated styrene-isoprene-styrene triblock copolymer having a maximum peak temperature of −3.2 ° C. (based on the dynamic viscoelasticity measurement at a frequency of 1 Hz described above) was used. An interlayer film was prepared using the same method as in No. 2, and physical properties were evaluated. The results are shown in Table 1 and FIG.

<Comparative Example 3>
In layer A, instead of the linear hydrogenated styrene-isoprene-styrene triblock copolymer used in Example 1, 12% by mass of styrene units, isoprene units and butadiene units (isoprene: butadiene (molar ratio) = 50) : 50) Linear hydrogenated styrene containing 88% by mass and having a peak tan δ peak height of −21.0 ° C. (based on dynamic viscoelasticity measurement at a frequency of 1 Hz). -An intermediate film was prepared in the same manner as in Example 1 except that a butadiene-styrene triblock copolymer was used, and physical properties were evaluated. The results are shown in Table 1 and FIG.

<Comparative example 4>
In the layer A, instead of the linear hydrogenated styrene-isoprene-styrene triblock copolymer used in Example 1, the peak height of tan δ containing 12% by mass of styrene units and 88% by mass of butadiene units has a peak height of tan δ. Example except that a linear hydrogenated styrene-butadiene-styrene triblock copolymer having a maximum peak temperature of −34.3 ° C. (based on the dynamic viscoelasticity measurement at a frequency of 1 Hz described above) was used. An interlayer film was prepared using the same method as in Example 1, and physical properties were evaluated. The results are shown in Table 1 and FIG.

<Comparative Example 5>
An intermediate film was produced using the same method as in Comparative Example 4 except that the thickness of the A layer was changed from 250 μm to 100 μm, and the thickness of the B layer was changed from 250 μm to 330 μm, and physical properties were evaluated. The results are shown in Table 1 and FIG.

<Comparative Example 6>
In the layer A, instead of the linear hydrogenated styrene-isoprene-styrene triblock copolymer used in Example 1, the peak height of tan δ containing 18% by mass of styrene units and 82% by mass of isoprene units has a peak height of tan δ. Except that a linear hydrogenated styrene-isoprene-styrene triblock copolymer having a maximum peak temperature of −52.7 ° C. (based on the dynamic viscoelasticity measurement at the frequency of 1 Hz described above) was used. An interlayer film was prepared using the same method as in Example 1, and physical properties were evaluated. The results are shown in Table 1 and FIG.

<Comparative Example 7>
An intermediate film was produced using the same method as Comparative Example 6 except that the thickness of the A layer was changed from 250 μm to 100 μm, and the thickness of the B layer was changed from 250 μm to 330 μm, and the physical properties were evaluated. The results are shown in Table 1 and FIG.

  As shown in Tables 1 and 2 and FIGS. 2 to 15, Examples 1 to 7 show 37 dB or more in the range of 4000 Hz to 6299 Hz and 40 dB or more in the range of 6300 Hz to 10000 Hz, which is high in the high frequency range. It can be seen that high sound insulation is exhibited in the practically important frequency range of 4000 Hz to 6000 Hz while maintaining the sound insulation.

1 A layer 2a B layer 2b B layer

Claims (20)

An interlayer film for laminated glass comprising at least one layer A composed of a composition containing a thermoplastic elastomer,
A block copolymer in which the thermoplastic elastomer has a polymer block (a) containing 60 mol% or more of aromatic vinyl monomer units and a polymer block (b) containing 60 mol% or more of conjugated diene monomer units. A hydrogenated polymer,
The content of the polymer block (a) in the hydrogenated product of the block copolymer is 15% by mass or less based on the total mass of the hydrogenated product of the block copolymer,
The composition containing the thermoplastic elastomer has a peak at which tan δ measured by conducting a complex shear viscosity test under a frequency of 1 Hz in accordance with JIS K 7244-10 is -20 ° C or higher and -6 ° C or lower. The shear storage modulus at −5 ° C. is 0.7 MPa or more and less than 10 MPa, and the value of tan δ at −5 ° C. is 1.0 or more,
An interlayer film for laminated glass, wherein the thickness of the A layer is 100 μm or more and 400 μm or less.   The peak value of tan δ measured by conducting a complex shear viscosity test under the condition of a frequency of 1 Hz according to JIS K 7244-10 of the thermoplastic elastomer-containing composition constituting the A layer is 2.0 or more. Item 16. The interlayer film for laminated glass according to Item 1.   The content of the polymer block (a) in the hydrogenated product of the block copolymer is 3% by mass or more and 15% by mass or less based on the total mass of the hydrogenated product of the block copolymer. Or the intermediate film for laminated glasses of 2.   An interlayer film for laminated glass having an A layer and a B layer laminated on both surfaces of the A layer, the laminated glass having two float glasses having a length of 300 mm, a width of 25 mm, and a thickness of 1.9 mm In the laminated glass sandwiching the interlayer film, the loss factor at the third resonance frequency measured by the central vibration method at 20 ° C. is 0.25 or more, and the 3 calculated according to ISO 16940 (2008). The interlayer film for laminated glass according to any one of claims 1 to 3, wherein the bending rigidity at the next resonance frequency is 90 N · m or more and 180 N · m or less.   The interlayer film for laminated glass according to claim 4, wherein the B layer is composed of a resin composition containing a polyvinyl acetal resin or an ionomer resin.   The layer according to claim 4, wherein the B layer is composed of a resin composition containing a polyvinyl acetal resin and a plasticizer, and the content of the plasticizer is 50 parts by mass or less with respect to 100 parts by mass of the polyvinyl acetal resin. Intermediate film for glass.   The interlayer film for laminated glass according to claim 6, wherein the plasticizer is an ester plasticizer or an ether plasticizer having a melting point of 30 ° C or lower and a hydroxyl value of 15 to 450 mgKOH / g.   The shear storage elastic modulus at -5 ° C. measured by conducting a complex shear viscosity test under the condition of a frequency of 1 Hz in accordance with JIS K 7244-10 of the resin composition constituting the B layer is 100 MPa or more. The interlayer film for laminated glass according to any one of 4 to 7.   The resin composition constituting the B layer has a peak at which tan δ measured by conducting a complex shear viscosity test under the condition of a frequency of 1 Hz according to JIS K 7244-10 in a range of 20 ° C. or more. Item 9. The interlayer film for laminated glass according to any one of Items 4 to 8.   The interlayer film for laminated glass according to any one of claims 4 to 9, wherein each of the B layers has a thickness of 100 µm or more and 600 µm or less.   The interlayer film for laminated glass according to any one of claims 1 to 10, wherein the total thickness of the interlayer film for laminated glass is 1.5 mm or less.   Loss factor at the third-order resonance frequency measured by the central vibration method at 20 ° C in a laminated glass in which an interlayer film for laminated glass is sandwiched between two float glasses having a length of 300 mm, a width of 25 mm, and a thickness of 1.9 mm And the sound transmission loss calculated from the bending rigidity at the third resonance frequency calculated according to ISO 16940 (2008) is 37 dB or more in the range of 4000 to 6299 Hz, and in the range of 6300 to 10,000 Hz. The interlayer film for laminated glass according to any one of claims 1 to 11, which is 40 dB or more.   Loss factor at the third-order resonance frequency measured by the central vibration method at 20 ° C in a laminated glass in which an interlayer film for laminated glass is sandwiched between two float glasses having a length of 300 mm, a width of 25 mm and a thickness of 1.9 mm And the value of (acoustic transmission loss at 6300 Hz) / (acoustic transmission loss at 4000 Hz) calculated from the bending rigidity at the third resonance frequency calculated according to ISO 16940 (2008) is 0.9 or more and 1 The interlayer film for laminated glass according to any one of claims 1 to 12, which is 2 or less.   Loss factor at the third-order resonance frequency measured by the central vibration method at 20 ° C in a laminated glass in which an interlayer film for laminated glass is sandwiched between two float glasses having a length of 300 mm, a width of 25 mm, and a thickness of 1.9 mm And the value of (acoustic transmission loss at 8000 Hz) / (acoustic transmission loss at 4000 Hz) calculated from the bending rigidity at the third resonance frequency calculated according to ISO 16940 (2008) is 1.1 or more and 1 The interlayer film for laminated glass according to any one of claims 1 to 13, which is .4 or less.   The interlayer film for laminated glass according to claim 1, wherein at least one layer contains a heat shielding material.   Thermal barrier materials are tin-doped indium oxide, antimony-doped tin oxide, zinc antimonate, metal-doped tungsten oxide, phthalocyanine compounds, diimonium dyes, aminium dyes, phthalocyanine dyes, anthraquinone dyes, polymethine dyes, benzenedithiol type 16. At least one selected from the group consisting of ammonium compounds, thiourea derivatives, thiol metal complexes, aluminum-doped zinc oxide, tin-doped zinc oxide, silicon-doped zinc oxide, lanthanum hexaboride, and vanadium oxide. The interlayer film for laminated glass described.   The interlayer film for laminated glass according to any one of claims 1 to 16, wherein at least one layer contains an ultraviolet absorber.   The ultraviolet absorber is at least one selected from the group consisting of benzotriazole compounds, benzophenone compounds, triazine compounds, hindered amine compounds, benzoate compounds, malonic acid ester compounds, indole compounds, and oxalic acid anilide compounds. The interlayer film for laminated glass according to claim 17, wherein   Laminated glass in which the interlayer film for laminated glass according to any one of claims 1 to 18 is disposed between at least two glasses.   The laminated glass according to claim 19, which is an automotive windshield, automotive side glass, automotive sunroof, automotive rear glass, or head-up display glass.

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