JP4956491B2 - Laminated glass interlayer film and laminated glass - Google Patents

Description

The present invention is excellent in performance for mitigating externally applied impact, and particularly when used as glass for vehicles, laminated glass and laminated glass excellent in impact mitigation performance when a human accident occurs and the head collides. The present invention relates to an interlayer film for glass.

In recent years, developed countries have been researching and developing research systems for evaluating pedestrian protection performance of vehicles in the event of a car-pedestrian collision. The most common part of a pedestrian that is fatally injured in a collision with a car is the head. For this reason, international standards (ISO / SC10 / WG2) and EU standards (EEVC / WG10, ECE-Regulation No. 43 Annex 3) are also established for the head impact test method for performing head impact protection evaluation. Yes.

For example, the European Enhanced Vehicle-safety Committee (EEVC / WG17) has proposed a head protection test as one of the pedestrian protection tests, and conforms to this head protection test. It has been proposed as a performance standard for vehicle safety that the head impact index (HIC value) obtained by the above method does not exceed 1000. Note that an HIC value of 1000 is a threshold for serious injury, and if the HIC value exceeds 1000, it is said that the normal human survival probability decreases.

In recent years, the front nose of vehicles tends to be shorter, and in recent accidents, the position where the head of an adult pedestrian collides with the vehicle has many windshields in addition to the hood.
However, since the EEVC / WG17 head protection test stipulates that the test range is only on the hood of a passenger car, the ongoing international research harmonization activities (IHRA) are at the forefront of the adult head protection test. We are considering including window glass.

Currently, laminated glass is widely used as glass for vehicles such as automobiles, aircraft, buildings, etc., even if it is damaged by an external impact, it is safe because the glass fragments do not scatter. Yes. Such laminated glass is obtained by interposing an interlayer film for laminated glass made of polyvinyl acetal resin such as polyvinyl butyral resin plasticized with a plasticizer between at least a pair of glass plates, etc. Is mentioned.

However, many of the conventional laminated glasses have HIC values exceeding 1000. In particular, in the windshield of an automobile, the HIC value is particularly high in the vicinity of the fixed outer peripheral portion, and in some cases, it may exceed 2000. The vicinity of the outer periphery of such a windshield is a place where there is a high probability that the head of an adult pedestrian will collide when an accident occurs. In order to avoid head injury when the pedestrian collides with the vehicle, more HIC A laminated glass having a low value has been demanded.

In view of the above situation, the present invention is excellent in the performance of mitigating externally applied impact, and particularly when used as glass for vehicles, the impact mitigation performance when a human accident occurs and the head collides. An object is to provide an excellent laminated glass and an interlayer film for laminated glass.

The present invention is a laminated glass in which at least an interlayer film for laminated glass and a glass plate are laminated and integrated, and is an European Enhanced Vehicle Safety Committee (EEVC / WG17) A head impact index (HIC) value measured in accordance with the regulations is 1000 or less, and the interlayer film for laminated glass includes a crosslinked polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%. , Including a layer having a thickness of 800 μm or more, containing 40 parts by weight or more of a plasticizer for an interlayer film with respect to 100 parts by weight of the polyvinyl acetal resin, and the interlayer film for laminated glass has a temperature of 20 ° C. , Pulling speed Stress at 500% / min - maximum stress obtained from strain curve σ is less 20 MPa, and a laminated glass break strain ε of 200% or more.
The present invention is described in detail below.

The laminated glass of the present invention has an HIC value (EEVC) measured in accordance with the EEVC / WG17 rule of 1000 or less. If it exceeds 1000, when the laminated glass of the present invention is used as glass for vehicles, head injury when a pedestrian collides with the vehicle cannot be avoided, and the survival probability becomes low. Preferably it is 600 or less, More preferably, it is 300 or less.
In the laminated glass of the present invention, the HIC value (EEVC) is 11.1 m / s at the center when a laminated glass having a size of 600 mm × 600 mm is fixed to a frame having an opening of 500 mm × 500 mm. Measured by impacting impactor head at speed.

FIG. 1 is an exploded perspective view schematically showing an example of an HIC value measuring apparatus used when measuring the HIC value (EEVC) of the laminated glass of the present invention.
As shown in FIG. 1, the HIC value measuring apparatus 10 mainly includes a box-shaped support portion 11 having a flange portion 12 on which an outer peripheral portion of a laminated glass is placed on the upper end, and the flange portion 12. The fixed portion 13 has the same shape, and an impactor head 14 having a shape imitating a human head.
A plurality of through holes (not shown) are formed at corresponding positions on the flange portion 12 and the fixing portion 13 of the support portion 11, and a laminated glass for measuring the HIC value is placed on the flange portion 12. And after arrange | positioning the fixing | fixed part 13 on this laminated glass, a laminated member can be hold | maintained and fixed by the outer peripheral part by screwing together fixing members, such as a screw, in a through-hole.
That is, in the HIC value measuring apparatus shown in FIG. 1, the sizes of the inner peripheral portions of the collar portion 12 and the fixing portion 13 are 500 mm × 500 mm.

The impactor head 14 has a hemispherical resin head skin attached to a metal core, and an acceleration sensor that measures acceleration in three axial directions is provided in the center of the core.
Such an impactor head 14 is disposed above the laminated glass held and fixed as described above, and the acceleration sensor senses and matches the impact when it collides with the surface of the laminated glass under the above-described conditions. Measure the HIC value of the glass.

The HIC value (EECV) can be calculated by the following formula (1) in accordance with the EEVC / WG17 regulations after being arranged as described above.

式（１）中、ａｒは、インパクタヘッドの合成加速度（Ｇ）を表し、ａＩは、インパクタヘッドの進行方向の加速度（Ｇ）を表し、ａＦは、インパクタヘッドの前後方向の加速度（Ｇ）を表し、ａＳは、インパクタヘッドの横方向の加速度（Ｇ）を表し、ｔ２−ｔ１は、ＨＩＣ値が最大になる時間間隔（最大０．０１５ｓ）を表す。

In Expression (1), ar represents the combined acceleration (G) of the impactor head, aI represents the acceleration (G) in the traveling direction of the impactor head, and aF represents the acceleration (G) in the longitudinal direction of the impactor head. AS represents the lateral acceleration (G) of the impactor head, and t2-t1 represents a time interval (maximum 0.015 s) at which the HIC value becomes maximum.

The laminated glass of the present invention has an ECE-Regulation No. The HIC value (ECE) measured by dropping the impactor head from a height of 4 m from the surface of the laminated glass in accordance with the rule of 43 Annex 3 is 300 or less. When the HIC value (ECE) is 300 or less, it becomes possible to reduce the HIC value even in the peripheral portion where the windshield is fixed, thereby avoiding head problems when a pedestrian collides with the vehicle. And the survival probability is higher. Preferably it is 250 or less.
In the laminated glass of the present invention, when the laminated glass having a size of 1100 mm × 500 mm is fixed to a frame having an opening of 1070 mm × 470 mm, the impactor has a drop height of 4 m at the center. It is measured by hitting the head. The impact speed of the impactor head at this time is 8.9 m / s.

FIG. 2 is a diagram schematically showing an example of an HIC value measuring apparatus used when measuring the HIC value (ECE) of the laminated glass of the present invention.
As shown in FIG. 2, the HIC value measuring apparatus includes a laminated glass support base 21 having a structure similar to the above-described HIC value (EECV), an impactor head 22 shaped like a human head, and an impactor head. The guide system 23 is configured to drop vertically.

The structure of the impactor head is described in detail in the provisions of ECE-Regulation 43 Annex 3. For example, metal plates are assembled on the top and bottom of a wooden component, and a hemisphere made of polyamide resin is assembled as shown in the figure. It is assembled in a pear shape, and an acceleration sensor for measuring acceleration in three axial directions is provided on a base plate, and a rubber head skin is attached to the bottom half of the polyamide resin. The weight of the impactor head is 10 kg.

The guide system 23 includes a mechanism for carrying / separating the impactor head 22 and drops the impactor head 22 from a predetermined height (4 m in the present invention). The state of the fall at this time is observed with the optical sensor 24, and when the impactor head 22 passes through the position of the optical sensor, it is cut off. The impactor head separated from the guide system 23 falls freely and collides with the central portion of the laminated glass fixed to the laminated glass support 21. The acceleration sensor senses the impact at this time and measures the HIC value (ECE) of the laminated glass.
Similarly to the HIC value (EECV), the HIC value (ECE) can be calculated by the above formula (1).

The HIC value (EEVC) and the HIC value (ECE) are both standards defined by European public institutions. HIC value (EEVC) and HIC value (ECE) are different in their measurement methods and standards and are difficult to compare directly, but in general, HIC value (EEVC) is 1000 or less It can be said that the strict standard is that the HIC value (ECE) is 300 or less. Therefore, even a laminated glass that can achieve an HIC value (EEVC) of 1000 or less may not achieve an HIC value (ECE) of 300 or less. The laminated glass of the present invention includes those having an HIC value (EEVC) of 1000 or less and those having an HIC value (ECE) of 300 or less, but the HIC value (ECE) of 300 or less. preferable.

Although it does not specifically limit as laminated glass which can achieve such a low HIC value, (1) The thing which absorbs an impact by the interlayer film for laminated glass, (2) The glass part is thinned, and the glass is easily deformed and (3) Those that absorb impact by cracking, (3) Impact of the entire laminated glass by using one side of the laminated glass (the side that becomes the inner side when used as vehicle glass) as a resin plate instead of glass What improved the absorptivity etc. are mentioned.
Each case will be described in detail below.

First, (1) the case where an impact is absorbed by the interlayer film for laminated glass will be described.
Although it does not specifically limit as an intermediate film for laminated glasses used in this case, The thing containing 30 weight part or more of plasticizers for intermediate films with respect to 100 weight part of polyvinyl acetal resin is used suitably. By using the interlayer film for laminated glass in which such a large amount of plasticizer for interlayer film is blended, the HIC value of the laminated glass can be lowered. The blending amount of the plasticizer for the interlayer film is more preferably 40 parts by weight or more, further preferably 45 parts by weight or more, and particularly preferably 60 parts by weight or more.
When the interlayer film for laminated glass has a multilayer structure of two or more layers, the HIC value can be lowered by having at least one resin layer having the above structure.

Although it does not specifically limit as said polyvinyl acetal resin, A thing with an acetalization degree of 60-85 mol% is suitable. More preferably, it is 65-80 mol%.
In the present specification, the “degree of acetalization” means that the acetal group of the polyvinyl acetal resin is formed by acetalizing two hydroxyl groups of the polyalcohol resin as a raw material. Calculated by the method of counting.

As the polyvinyl acetal resin, a polyvinyl acetal resin having a half-value width of a hydroxyl group peak of 250 cm ⁻¹ or less when an infrared absorption spectrum is measured is preferable. More preferably, it is 200 cm ⁻¹ or less.
In addition, as a measuring method of the infrared absorption spectrum of the said interlayer film for laminated glasses, for example, "FT-IR" manufactured by HORIBA is used to obtain an infrared absorption spectrum, and corresponds to a hydroxyl group among the obtained peaks. It can be measured from the peak.

As a method for producing the polyvinyl acetal resin, for example, polyvinyl alcohol is dissolved in warm water, and the obtained polyvinyl alcohol aqueous solution is kept at 0 to 90 ° C., preferably 10 to 20 ° C. The acetalization reaction is allowed to proceed with stirring, the reaction temperature is raised to 70 ° C. to complete the reaction, followed by neutralization, washing with water and drying to obtain a polyvinyl acetal resin powder. Can be mentioned.

The aldehyde is not particularly limited, and for example, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, n-heptylaldehyde, n-octylaldehyde, n-nonylaldehyde , N-decylaldehyde, benzaldehyde, cinnamaldehyde and the like aliphatic, aromatic, alicyclic aldehyde and the like. Preferred are n-butyraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde and n-octylaldehyde having 4 to 8 carbon atoms. The n-butyraldehyde having 4 carbon atoms is more preferable because it is excellent in weather resistance and can be easily produced by using the obtained polyvinyl acetal resin. These may be used alone or in combination of two or more.

The polyvinyl acetal resin may be cross-linked. By using the crosslinked polyvinyl acetal resin, bleeding out of the plasticizer for the intermediate film can be suppressed.
As a method of cross-linking the polyvinyl acetal resin, for example, when polyvinyl alcohol is acetalized with an aldehyde such as butyraldehyde, a dialdehyde such as glutaraldehyde is used to lightly cross-link between molecules by a diacetal bond. In the acetalization reaction of polyvinyl alcohol, at least 90% of the desired degree of acetalization is reached, and then an acid catalyst is added thereto and reacted at 60 to 95 ° C. to crosslink the polyvinyl acetal molecules by monobutyral bonds. A method of adding a crosslinking agent that reacts with a hydroxyl group remaining in the obtained polyvinyl acetal resin and crosslinking the hydroxyl group; a method of crosslinking a hydroxyl group remaining in the polyvinyl acetal resin with diisocyanate and polyvalent epoxy, and the like.

Examples of the crosslinking agent that reacts with the hydroxyl group include glyoxazal, dialdehyde containing a sulfur atom in the molecular chain, glyoxazal-ethylene glycol reaction product, polyvinyl alcohol modified with aldehyde at both ends, and dialdehyde starch. , Dialdehydes such as polyacrolein, methylols such as N-methylol urea, N-methylol melamine, trimethylol melamine, hexamethylol melamine, α-hydroxyethylsulfonic acid, epichlorohydrin, polyethylene glycol diglycidyl ether, diglycidyl etherification Bisphenol A type epoxy resin, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl etherified glycerin, 3 or more in the molecular chain Polyglycol having a glycidyl ether group, polyglycidyl ether modified product of trimethylolpropane, polyglycidyl ether modified product of sorbitol, polyglycidyl ether modified product of sorbitan, polyglycidyl ether modified product of polyglycerol, dicarboxylic acid , Michael adducts of triethylene glycol and methyl acrylate, polyacrylic acid, polycarboxylic acids such as a mixture of methyl vinyl ether-maleic acid copolymer and isobutylene-maleic anhydride copolymer, tolylene diisocyanate, phenylene diisocyanate , 4,4'-diphenylmethane diisocyanate, aromatic diisocyanates such as 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate Anisate, lysine diisocyanate, aliphatic diisocyanate such as 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, polyphenol, acetylacetone, malonic acid diethyl ester, lactam, oxime, amide, polyisocyanate blocked with tertiary alcohol, etc. Can be mentioned.

When the interlayer film for laminated glass is made of a crosslinked polyvinyl acetal resin, the interlayer film for laminated glass preferably has a thickness of 800 μm or more. If it is less than 800 μm, a sufficiently low HIC value may not be obtained.

The plasticizer for the intermediate film is not particularly limited as long as it is usually used for a polyvinyl acetal resin, and a known plasticizer generally used as a plasticizer for the intermediate film can be used. Examples of such a plasticizer for an intermediate film include organic ester plasticizers such as monobasic acid esters and polybasic acid esters; phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid. It is done. These plasticizers may be used alone or in combination of two or more, and are used properly according to the type of the polyvinyl acetal resin in consideration of compatibility with the resin.

The monobasic acid ester plasticizer is not particularly limited. For example, glycol such as triethylene glycol, tetraethylene glycol or tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n -Glycol-type ester obtained by reaction with organic acids, such as octylic acid, 2-ethylhexyl acid, pelargonic acid (n-nonyl acid), or decyl acid. Among them, triethylene glycol-dicaproate, triethylene glycol-di-2-ethylbutyrate, triethylene glycol-di-n-octylate, triethylene glycol-di-2-ethylhexyl ester, etc. A monobasic organic acid ester of glycol is preferably used.

The polybasic acid ester plasticizer is not particularly limited. For example, a polybasic organic acid such as adipic acid, sebacic acid or azelaic acid, and a linear or branched alcohol having 4 to 8 carbon atoms. Examples include esters. Of these, dibutyl sebacic acid ester, dioctyl azelaic acid ester, dibutyl carbitol adipic acid ester and the like are preferably used.

The organic ester plasticizer is not particularly limited. For example, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexoate, triethylene glycol dicaprylate, triethylene glycol di- n-Octate, triethylene glycol di-n-heptate, tetraethylene glycol di-n-heptate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate and the like are preferably used.

In addition, for example, ethylene glycol di-2-ethyl butyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2 -Ethyl butyrate, 1,2-butylene glycol di-2-ethylene butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethylhexoate, dipropylene glycol di-2-ethyl butyrate, tri Ethylene glycol di-2-ethylpentoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicapryate and the like can also be used as the plasticizer.

The phosphoric acid plasticizer is not particularly limited, and for example, tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate and the like are suitable.

Among these plasticizers for interlayer films, diester compounds composed of dicarboxylic acid and monohydric alcohol or composed of monocarboxylic acid and dihydric alcohol are particularly preferably used.

In addition, as the interlayer film for laminated glass, those in which rubber particles are dispersed are also suitable. Even when such rubber particles are dispersed, an impact can be absorbed when a force is applied to the interlayer film for laminated glass.
Although it does not specifically limit as said rubber particle, For example, since the visible light transmittance | permeability etc. of the intermediate film for laminated glasses which can obtain near refractive resin and a refractive index are hard to deteriorate, a polyvinyl acetal crosslinked body etc. are suitable. The particle size of the rubber particles is not particularly limited, but is preferably 1.0 μm or less, and the amount of the rubber particles is not particularly limited, and is 100 parts by weight of a resin such as a polyvinyl acetal resin. A preferred lower limit is 0.01 parts by weight and a preferred upper limit is 10 parts by weight.

As the interlayer film for laminated glass, storage elasticity in a linear dynamic viscoelasticity test measured at a temperature of 20 ° C. and a frequency range of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz while changing the frequency by a shear method. A rate G ′ of 3 × 10 ⁷ Pa or less; a temperature of 20 ° C., a frequency range of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz, and at least one tan δ of 0.6 or more; It is preferable that the maximum stress σ obtained from the stress-strain curve at a temperature of 20 ° C. and a pulling speed of 500% / min is 20 MPa or less and the strain at break ε is 200% or more.

The storage elastic modulus G ′ is a value representing the softness of the interlayer film for laminated glass. By using a sufficiently soft interlayer film for laminated glass, the resulting laminated glass has a low HIC value. When storage elastic modulus G 'exceeds 3.0 * 10 < ⁷ > Pa, the HIC value (EEVC) of the laminated glass obtained may exceed 1000, or the HIC value (ECE) may exceed 300. More preferably, it is 1.0 * 10 < ⁷ > Pa or less, More preferably, it is 5.0 * 10 < ⁶ > Pa or less.

The interlayer film for laminated glass has a storage elastic modulus E in a viscoelasticity test measured while changing the frequency by a tension method in a temperature range of 20 ° C. and a frequency range of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz. It is preferable that 'is 1.0 × 10 ⁹ Pa or less. The storage elastic modulus E ′ is also a value representing the softness of the interlayer film for laminated glass. By using a sufficiently soft interlayer film for laminated glass, the resulting laminated glass has a low HIC value. When the storage elastic modulus E ′ exceeds 1.0 × 10 ⁹ Pa, the HIC value (EEVC) of the obtained laminated glass may exceed 1000 or the HIC value (ECE) may exceed 300. More preferably, it is 0.5 * 10 < ⁹ > Pa or less, More preferably, it is 5.0 * 10 < ⁶ > Pa or less.

The tan δ is the ratio (G ″ / G ′) of the storage elastic modulus G ′ and the loss elastic modulus G ″ measured while changing the frequency by the shear method, and the dynamic viscoelasticity of the interlayer film for laminated glass, and hence the impact It is a value indicating energy absorption. By using an interlayer film for laminated glass having a sufficiently high impact energy absorption property, the obtained laminated glass has a low HIC value. When it is less than 0.6, the HIC value (EEVC) of the obtained laminated glass may exceed 1000, or the HIC value (ECE) may exceed 300. More preferably, it is 0.7 or more.

The measurement frequency of the storage elastic modulus G ′, storage elastic modulus E ′ and tan δ is in the range of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz, which corresponds to a deformation of 10 to ²⁰ msec. , Is a measurement result of a region including a maximum time interval of 15 msec for HIC value measurement. In the measurement of the HIC value, deformation of a short time interval of less than 10 msec may be dominant with respect to the measurement value, but 1.0 × 10 ^{2 to} 3.0 × 10 ² Hz (equivalent to 3.3 to 10 msec) ) Can be easily inferred from the measured values of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz. Therefore, the measured values of the storage elastic modulus G ′, storage elastic modulus E ′ and tan δ in the frequency range of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz satisfy the above conditions, thereby sufficiently reducing the HIC value. It is considered possible.

When the maximum stress σ and the strain at break ε are within the above ranges, the interlayer film for laminated glass can absorb impact energy by extending within 15 msec at the time of collision. Laminated glass using an interlayer film has a low HIC value. The maximum stress σ is more preferably 18 MPa or less, and further preferably 16 MPa or less. The breaking strain ε is more preferably 300% or more, and further preferably 400% or more.

In addition, the stress-strain curve of the interlayer film for laminated glass is, for example, in accordance with JIS K 6771, using a tensile tester, the test piece of the interlayer film for laminated glass is dumbbell No. 1, at a temperature of 20 ° C., It can be drawn by measuring the resistance (kg / cm ² ) by pulling at a pulling speed of 500% / min. Further, the maximum stress σ is the maximum value of the resistance force, and the strain at break ε is a value of strain when the test piece is broken.

When the maximum stress σ and the strain at break ε thus obtained satisfy the above conditions, the breaking energy U of the interlayer film for laminated glass is preferably 1.0 J / mm ² or more. The breaking energy U can be calculated by the following formula (2) from the stress σ and strain ε of the interlayer film for laminated glass in the tensile test under the above conditions.
U = ∫σdε (2)

The interlayer film for laminated glass may be composed of only a layer composed of a resin composition containing 30 parts by weight or more of the plasticizer for interlayer film with respect to 100 parts by weight of the polyvinyl acetal resin. A multilayer structure including such a layer is preferable.
When the interlayer film for laminated glass consists only of a layer composed of a resin composition containing 30 parts by weight or more of the plasticizer for interlayer film with respect to 100 parts by weight of the polyvinyl acetal resin, the HIC value can be lowered, Basic performances required for vehicle glass such as penetration resistance may be inferior. For example, the laminated glass of the present invention preferably has a falling ball height measured by a falling ball height measurement test of 4 m or more. If it is less than 4 m, the penetration resistance of the laminated glass as a whole will be insufficient, and it may not be used as vehicle glass. More preferably, it is 5 m or more, More preferably, it is 7 m or more.
By adopting a multilayer structure, the HIC value is lowered by a layer composed of a resin composition containing 30 parts by weight or more of the plasticizer for the interlayer film with respect to 100 parts by weight of the polyvinyl acetal resin, and at the same time, the layer is made resistant by other layers. Performances such as penetrability can be added to achieve different functions.
Although it does not specifically limit as an intermediate film for laminated glasses which has a multilayer structure, A preferable structure is explained in full detail below.

When the interlayer film for laminated glass has a two-layer structure, the storage elastic modulus G ′ at a temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz of one layer is It is preferable that it is 1/2 or less of the storage elastic modulus G ′ at a temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz. At this time, the storage elastic modulus G ′ at a temperature of one layer of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz is 2 × 10 ⁶ Pa or less, and the temperature of the other layer is 20 ° C. and the frequency. More preferably, the storage elastic modulus G ′ at 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz is 1 × 10 ⁷ Pa or more, the temperature is 20 ° C., and the frequency is 5.0 × 10 ^{1 to} 1.0. × storage modulus G ¹⁰ 2 Hz 'is 2 × ¹⁰ 6 Pa or less layers, temperature 20 ° C., tan [delta at a frequency ^{5.0 × 10 1 ~1.0 × 10 2} Hz is 0.7 or more More preferably.
In such an interlayer film for laminated glass, the thickness of the layer having the storage elastic modulus G ′ of 2 × 10 ⁶ Pa or less is preferably 10% or more of the entire thickness of the interlayer film for laminated glass. . If it is less than 10%, a low HIC value may not be realized. More preferably, it is 14% or more, and further preferably 20% or more.
If an interlayer film for laminated glass having such a two-layer structure is used, both a low HIC value and penetration resistance can be achieved.

When the interlayer film for laminated glass has a three-layer structure, the storage elastic modulus G ′ at an intermediate layer temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz constitutes the outermost layer. It is preferable that it is 1/2 or less of the storage elastic modulus G ′ at one or both of the two layers at a temperature of 20 ° C. and at a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz. At this time, the storage elastic modulus G ′ at an intermediate layer temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz is 2 × 10 ⁶ Pa or less, and one of the two layers constituting the outermost layer. Or, it is more preferable that the storage elastic modulus G ′ at a temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz is 1 × 10 ⁷ Pa or more, and the intermediate layer has a temperature of 20 ° C. It is more preferable that tan δ at a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz is 0.7 or more.
The storage elastic modulus G ′ of the intermediate layer may be ½ or less of the storage elastic modulus G ′ of one of the two layers constituting the outermost layer, but any of the two layers constituting the outermost layer may be stored. More preferably, it is ½ or less of the elastic modulus G ′.
In such an interlayer film for laminated glass, the thickness of the intermediate layer is preferably 10% or more of the entire thickness of the interlayer film for laminated glass. If it is less than 10%, a low HIC value may not be realized. More preferably, it is 14% or more, and further preferably 20% or more.
If the interlayer film for laminated glass having such a three-layer structure is used, both low HIC value and penetration resistance can be achieved, and further performance such as blocking resistance between the interlayer films for laminated glass can be exhibited.

When the interlayer film for laminated glass has a multilayer structure of four or more layers, the storage elastic modulus at a temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz of at least one of the interlayers. G ′ is equal to or less than ½ of the storage elastic modulus G ′ at one or any of the two layers constituting the outermost layer at a temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz. preferable. At this time, the storage elastic modulus G ′ at a temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz of the intermediate layer is 2 × 10 ⁶ Pa or less, and the two layers constituting the outermost layer More preferably, the storage elastic modulus G ′ at one or any of the temperatures of 20 ° C. and the frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz is 1 × 10 ⁷ Pa or more, and the storage elastic modulus G ′ is It is more preferable that tan δ at an intermediate layer temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz of 2 × 10 ⁶ Pa or less is 0.7 or more.
The storage elastic modulus G ′ of at least one of the intermediate layers may be ½ or less of the storage elastic modulus G ′ of one of the two layers constituting the outermost layer, but constitutes the outermost layer. It is more preferable that it is 1/2 or less of the storage elastic modulus G ′ of any of the two layers.
In such an interlayer film for laminated glass, the thickness of the intermediate layer having the storage elastic modulus G ′ of 2 × 10 ⁶ Pa or less is 10% or more of the entire thickness of the interlayer film for laminated glass. preferable. If it is less than 10%, a low HIC value may not be realized. More preferably, it is 14% or more, and further preferably 20% or more.

When the interlayer film for laminated glass has a multilayer structure of three layers and four layers or more, the interlayer having a storage elastic modulus G ′ of 2 × 10 ⁶ Pa or less is relative to the thickness direction of the interlayer film for laminated glass. Thus, it is preferably unevenly distributed on any surface layer side. If such an interlayer film for laminated glass is attached to a vehicle or the like so that the side on which the intermediate layer having a storage elastic modulus G ′ of 2 × 10 ⁶ Pa or less is uneven is located on the outside of the vehicle, a lower HIC value in this direction is obtained. can do.
As a method for unevenly distributing an intermediate layer having a storage elastic modulus G ′ of 2 × 10 ⁶ Pa or less to one of the surface layers as described above, for example, the thickness of one outermost layer is changed to the thickness of the other outermost layer. For example, a method of 1.2 times or more, more preferably 1.5 times or more, still more preferably 2 times or more.
If an interlayer film for laminated glass having such a multilayer structure of three layers and four or more layers is used, both low HIC value and penetration resistance can be achieved.

Further, when the interlayer film for laminated glass has a three-layer structure, storage at a temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz of one or any of the two layers constituting the outermost layer. The elastic modulus G ′ is preferably ½ or less of the storage elastic modulus G ′ at a temperature of the intermediate layer of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz.
At this time, the storage elastic modulus G ′ at one or any of the two layers constituting the outermost layer at a temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz is 2 × 10 ⁶ Pa or less, The storage elastic modulus G ′ at an intermediate layer temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz is preferably 1 × 10 ⁷ Pa or more, and one of the two layers constituting the outermost layer Alternatively, it is more preferable that tan δ at a temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz is 0.7 or more.
The storage elastic modulus G ′ of one of the two layers constituting the outermost layer may be ½ or less of the storage elastic modulus G ′ of the intermediate layer, but any of the two layers constituting the outermost layer is stored. The elastic modulus G ′ is more preferably ½ or less of the storage elastic modulus G ′ of the intermediate layer.
In such an interlayer film for laminated glass, the total thickness of the outermost layers is preferably 10% or more of the entire thickness of the interlayer film for laminated glass. If it is less than 10%, a low HIC value may not be realized. More preferably, it is 14% or more, and further preferably 20% or more.
If an interlayer film for laminated glass having such a three-layer structure is used, both a low HIC value and penetration resistance can be achieved.

Moreover, when the interlayer film for laminated glass has a multilayer structure of four or more layers, one or any of the two layers constituting the outermost layer has a temperature of 20 ° C., and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ^2. The storage elastic modulus G ′ at Hz is 1/2 of the storage elastic modulus G ′ at a temperature of 20 ° C. and a frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz of at least one of the layers constituting the intermediate layer. The following is preferable. At this time, the storage elastic modulus G ′ at the outermost layer temperature of 20 ° C. and the frequency of 5.0 × 10 ^{1 to} 1.0 × 10 ² Hz is 2 × 10 ⁶ Pa or less, the intermediate layer temperature of 20 ° C., and the frequency of 5 More preferably, the storage elastic modulus G ′ at 1.0 × 10 ^{1 to} 1.0 × 10 ² Hz is 1 × 10 ⁷ Pa or more, and the outermost layer has a temperature of 20 ° C. and a frequency of 5.0 × 10 ¹ to 1. More preferably, tan δ at 0.0 × 10 ² Hz is 0.7 or more.
Note that the storage elastic modulus G ′ of one of the two layers constituting the outermost layer may be ½ or less of the storage elastic modulus G ′ of at least one of the layers constituting the intermediate layer. It is more preferable that the storage elastic modulus G ′ of any of the two layers constituting the layer is ½ or less of the storage elastic modulus G ′ of the intermediate layer.
In such an interlayer film for laminated glass, the total thickness of the outermost layers is preferably 10% or more of the entire thickness of the interlayer film for laminated glass. If it is less than 10%, a low HIC value may not be realized. More preferably, it is 14% or more, and further preferably 20% or more.

In the case where the interlayer film for laminated glass has a multilayer structure of three layers and four layers or more, the interlayer having a storage elastic modulus G ′ of 1 × 10 ⁷ Pa or more is relative to the thickness direction of the interlayer film for laminated glass. Thus, it is preferably unevenly distributed on any surface layer side. If such an interlayer film for laminated glass is attached to a vehicle or the like so that the side on which the intermediate layer having a storage elastic modulus G ′ of 1 × 10 ⁷ Pa or more is unevenly located becomes the inside of the vehicle, a lower HIC value is obtained in this direction. can do.
As a method for unevenly distributing the intermediate layer having the storage elastic modulus G ′ of 1 × 10 ⁷ Pa or more to one of the surface layers in this way, for example, the thickness of one outermost layer is changed to the thickness of the other outermost layer. For example, a method of 1.2 times or more, more preferably 1.5 times or more, still more preferably 2 times or more.
If an interlayer film for laminated glass having such a multilayer structure of three layers and four or more layers is used, both low HIC value and penetration resistance can be achieved.

In the case where the interlayer film for laminated glass has a multilayer structure, in order to realize the above-described configuration, each resin layer has a different adhesive force as the resin layer constituting the interlayer film for laminated glass having the multilayer structure. For example, when each resin layer is mainly composed of a polyvinyl acetal resin, the plasticizer content is different by 5 parts by weight or more with respect to 100 parts by weight of the polyvinyl acetal resin; a layer composed of a polyethylene terephthalate film and a polyvinyl acetal resin Combinations such as those in which each resin layer is made of a resin having a different composition; those in which the compounding amount of the adhesive strength modifier blended in each resin layer is different; those in which the degree of acetalization of each resin layer is different are conceivable.

Although it does not specifically limit as said adhesive force regulator, By making the said resin layer contain the metal salt of a C2-C6 carboxylic acid, the adhesive force of the intermediate film for laminated glasses and a glass plate is made into a preferable range. While adjusting, it is possible to prevent deterioration with time, and it is possible to achieve both prevention of whitening and prevention of deterioration of adhesive strength with time.
Examples of the metal salt of carboxylic acid include pentanoic acid metal salt (carbon number 5), hexanoic acid (2-ethylbutanoic acid) metal salt (carbon number 6), heptanoic acid metal salt (carbon number 7), and octanoic acid metal. Salt (carbon number 8) etc. are mentioned. These may be used independently and 2 or more types may be used together. The carboxylic acid may be a straight chain type or a side chain type.

Although it does not specifically limit as thickness of the said interlayer film for laminated glasses, A preferable minimum is 300 micrometers and a preferable upper limit is 3 mm. A more preferable lower limit is 500 μm, and a more preferable upper limit is 2 mm.

The interlayer film for laminated glass may be embossed on the surface of the layer in contact with the glass. By performing embossing, the adhesive force between the interlayer film for laminated glass and the glass plate can be adjusted to a preferred range.

The interlayer film for laminated glass preferably has a length of 10 mm or more when the HIC value (EEVC) or HIC (ECE) is measured. Since the generation of the crack requires energy more than the elongation, the energy of the impactor head can be absorbed by the tear and the HIC value can be reduced. In addition, when the tearing is not a single line but occurs in a plurality and in a branched manner, the total length of each tear is preferably 10 mm or more. A more preferable tear length is 20 mm or more, and further preferably 50 mm or more.
The method for obtaining such an interlayer film for laminated glass is not particularly limited, but besides appropriately adjusting the breaking strength, breaking elongation rate, and breaking energy of the interlayer film for laminated glass, a part of the interlayer film for laminated glass is torn. For example, there are a method of providing a break which is easily generated or a weak portion such as a thin portion.

By using the interlayer film for laminated glass described above, a laminated glass realizing a low HIC value can be obtained.
These interlayer films for laminated glass are also one aspect of the present invention.

Next, (2) the case where the glass portion is thinned and the impact is absorbed by the glass being easily broken at the time of collision will be described. In this case, a glass sheet having a thickness of at least 1.8 mm is preferably used. Such a laminated glass can absorb an impact by easily deforming and / or breaking the glass at the time of collision. The HIC value of laminated glass has a strong relationship with the deformation at the time of collision, and the HIC value of laminated glass decreases as the amount of deformation at the time of collision increases. That is, the greater the deformation of the laminated glass, the lower the HIC value. Further, by making the thickness of the other glass plate thicker than 1.8 mm, it becomes possible to achieve both durability as a laminated glass and an HIC value.
In addition, when using a laminated glass having a structure using glass plates having different thicknesses as glass for a vehicle, the thicker one may be used for either the vehicle outer side or the vehicle inner side, In order to increase the durability of the laminated glass, it is preferable that the thicker side be the outside of the vehicle.

Next, (3) the case where the impact absorption of the entire laminated glass is improved by using one side of the laminated glass (the side that becomes the inner side when used as vehicle glass) as a resin plate instead of glass. To do. As such a laminated glass, for example, a laminated glass interlayer film is preferably sandwiched between a glass plate and a transparent resin plate. Moreover, when it is set as a laminated glass, it is preferable that haze is 2.0% or less and falling ball height is 4 m or more. Such a laminated glass has a sufficiently high impact absorption performance compared with that made of glass plates on both sides, and can have an HIC value (EEVC) of 1000 or less and an HIC value (ECE) of 300 or less.

Although it does not specifically limit as said transparent resin board, For example, since it is excellent in visible light transmittance | permeability, a haze, etc., what consists of a polycarbonate, an acrylic resin, an acrylic copolymer resin, or a polyester resin is preferable, and the falling ball height is 4 m. It is preferable to have such a thickness.
Moreover, since the said transparent resin board is easy to be damaged generally, in order to use as glass for vehicles, it is preferable to coat | cover with the transparent elastomer etc.
The transparent elastomer is not particularly limited, and examples thereof include urethane elastomers, nylon elastomers, and linear low density polyethylene.

In the laminated glass of the present invention, the method for producing the interlayer film for laminated glass is not particularly limited. For example, a resin component such as the above-mentioned polyvinyl acetal resin, a plasticizer, and other additives as necessary are blended uniformly. And a method of forming a film into a sheet by a conventionally known method such as an extrusion method, a calendering method, a pressing method, a casting method, and an inflation method.
The method for producing the interlayer film for laminated glass having a multilayer structure is not particularly limited. For example, a resin component such as the above-mentioned polyvinyl acetal resin, a plasticizer, and other additives as necessary are blended and mixed uniformly. Examples thereof include a method of extruding each layer in a lump after kneading, and a method of laminating two or more resin films prepared by the above-described method by a pressing method, a laminating method, or the like. The resin film before lamination used in a method of laminating by a press method, a laminating method or the like may have a single layer structure or a multilayer structure.

Moreover, it does not specifically limit as a method to manufacture the laminated glass of this invention, The manufacturing method of a conventionally well-known laminated glass is employable. For example, when the laminated glass of the present invention has a structure in which an interlayer film for laminated glass is sandwiched between two glass plates, the interlayer film for laminated glass is sandwiched between two glass plates, and this is put into a rubber bag. And pre-adhering at about 70 to 110 ° C. while sucking under reduced pressure, and then using an autoclave or pressing to perform main bonding at a temperature of about 120 to 150 ° C. and a pressure of about 10 to 15 kg / cm ^2. It can be manufactured by doing.

In the method for producing a laminated glass, an interlayer film for laminated glass made of a plasticized polyvinyl butyral resin is interposed between at least a pair of glass plates, and at the same time, the temperature is 60 to 100 ° C. You may heat-press with. More specifically, the glass plate / intermediate film / glass plate laminate is put in a rubber bag and, for example, at a temperature of about 60 to 100 ° C. while sucking and degassing under a reduced pressure of about −500 to −700 mmHg in an autoclave. And it is carried out by performing thermocompression bonding for about 10 to 30 minutes at a pressure of about 1 to 10 kg / cm ² and simultaneously performing deaeration and adhesion.
In this manufacturing method, as described above, the temperature at the time of thermocompression bonding is limited to a range of 60 to 100 ° C., and various conditions such as the pressure for pressure bonding, the time for pressure bonding and the degree of pressure reduction at the time of suction deaeration By appropriately setting within the range, the adhesive force between the interlayer film for laminated glass and the glass plate can be adjusted so as to be within a desired suitability range.

Since the laminated glass of the present invention has an HIC value (EEVC) of 1000 or less or an HIC value (ECE) of 300 or less, the laminated glass is excellent in performance of mitigating an externally applied impact, and used particularly as glass for vehicles. In some cases, the shock mitigation performance is excellent when a human accident occurs and the head collides.
When the laminated glass of the present invention is used as a vehicle glass and is fixed to a window frame, the HIC value tends to be high particularly in a portion close to the window frame or the lower end. Moreover, when a personal accident occurs, the location where the head of a pedestrian or the like collides has a high probability of the lower end portion of the vehicle glass (particularly the windshield). Therefore, adjustment may be made so that the HIC value in the portion close to the window frame or the lower end portion is lowered. That is, a laminated glass having a wedge-shaped interlayer in which the interlayer film for laminated glass is gradually thickened from one end to the other end, or a laminated glass having a shape in which the thickness of the peripheral portion is thicker than that of the central portion. If the use is used, it is possible to lower the HIC value particularly in the portion close to the window frame and the lower end.

In such a laminated glass, a wedge-shaped interlayer film for laminated glass consisting of only one layer may be used. For example, the laminated glass has a multilayer structure of three or more layers, and each layer is wedge-shaped and stored. It is preferable to use an interlayer film for laminated glass in which the wedge-shaped layers having a small elastic modulus G ′ are alternately stacked and the wedge-shaped layers are alternately stacked to make the entire thickness constant. If a windshield made of laminated glass using an interlayer film for laminated glass having such a multilayer structure is arranged so that the wedge-shaped base of the intermediate layer having a low storage elastic modulus G ′ is at the lower end, The HIC value of the lower end portion of the windshield, which is highly feared, can be lowered, and the upper portion with a low risk of collision can ensure the strength.
The interlayer film for laminated glass having such a configuration can be manufactured by using a mold that can be shaped by extrusion and multilayer extrusion so that any layer has a wedge shape.

The laminated glass of the present invention has an electromagnetic wave shielding performance at a frequency of 0.1 to 26.5 GHz of 10 dB or less, a haze of 1.0% or less, a visible light transmittance of 70% or more, and a wavelength region of 300 nm to 2100 nm. It is preferable that the solar radiation transmittance is 85% or less of the visible light transmittance. Moreover, it is preferable that the solar radiation transmittance in a wavelength range of 300 nm to 2100 nm is 80% or less of the visible light transmittance. The laminated glass of the present invention that satisfies such conditions satisfies the pedestrian protection performance with a low HIC value, and at the same time, it is possible to reduce the amount of hot rays from sunlight reaching the inside of the vehicle, and the temperature inside the automobile increases. A comfortable interior space can be realized. In addition, by having electromagnetic wave permeability in a frequency band of 0.1 to 26.5 GHz, amateur radio 3.5 MHz band, 7 MHz band, frequency band of emergency communication frequency of 10 MHz or less, VICS (car information communication) The system can transmit electromagnetic waves in a frequency band indispensable for information communication, such as 2.5 GHz of the system), 5.8 GHz of ETC (automatic toll collection system for toll roads), and 12 GHz band of satellite broadcasting.

In order to impart such performance to the laminated glass of the present invention, the polyvinyl acetal resin constituting the interlayer film for laminated glass preferably contains metal oxide fine particles having a heat ray cutting function. When the interlayer film for laminated glass has a multilayer structure, it is sufficient that at least one polyvinyl acetal resin contains metal oxide fine particles having a heat ray cutting function.

Although it does not specifically limit as said metal oxide microparticles | fine-particles, For example, a tin dope indium oxide and / or antimony dope tin oxide etc. are suitable. The tin-doped indium oxide particles and / or antimony-doped tin oxide has an average secondary agglomerated particle size of 80 nm or less, and a polyvinyl acetal having a density of 1 particle / μm ² or less of particles having a secondary agglomerated particle size of 100 nm or more. It is preferably dispersed in the resin. When the dispersion state is out of the above range, visible light transmittance of the obtained laminated glass may be lowered or haze may be increased.

As content of the said metal oxide microparticles | fine-particles, a preferable minimum is 0.05 weight part with respect to 100 weight part of polyvinyl acetal resin, and a preferable upper limit is 5.0 weight part. When the amount is less than 0.05 parts by weight, a sufficient heat ray cutting effect may not be obtained. When the amount exceeds 5.0 parts by weight, the visible light transmittance of the obtained laminated glass is reduced or the haze is large. Sometimes it becomes.
When the interlayer film for laminated glass has a multilayer structure, the preferable lower limit is 0.05 parts by weight and the preferable upper limit is 5.0 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin of all layers.

According to the present invention, the laminated glass is excellent in the performance of mitigating the impact applied from the outside, and particularly in the performance of mitigating the impact when a human accident occurs and the head collides when used as a glass for a vehicle. And an interlayer film for laminated glass.

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

(Reference Example 1)
Manufacture of interlayer film for laminated glass Polyvinyl butyral resin having a half-value width of a peak corresponding to a hydroxyl group obtained by measuring an infrared absorption spectrum of 245 cm ⁻¹ (degree of acetalization 68.0 mol%, ratio of vinyl acetate component 0.6 mol%) 100 parts by weight and 38 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer are mixed and sufficiently melt-kneaded with a mixing roll, followed by press molding. The resin film having a thickness of 800 μm was obtained by press molding at 150 ° C. for 30 minutes using a machine, and this was used as an interlayer film for laminated glass.

Next, the obtained interlayer film for laminated glass is sandwiched between two transparent float glass sheets having a thickness of 2 mm, put in a rubber bag, deaerated at a vacuum degree of 2660 Pa for 20 minutes, and then deaerated. It moved to oven and vacuum-pressed, hold | maintaining at 90 degreeC for 30 minutes. The laminated glass preliminarily pressure-bonded in this manner was pressure-bonded for 20 minutes in an autoclave at 135 ° C. and a pressure of 118 N / cm ² to obtain a laminated glass.

The obtained interlayer film for laminated glass and laminated glass were evaluated by the following methods.
The results are shown in Table 1.

(Measurement of HIC value (EEVC))
The HIC value (EEVC) of the laminated glass was measured using the HIC measuring apparatus having the structure shown in FIG. The case where the HIC value was 1000 or less was evaluated as acceptable (◯), and the case where the HIC value exceeded 1000 was evaluated as unacceptable (x).

(Measurement of HIC value (ECE))
Using the HIC measuring device having the structure shown in FIG. 2, the impactor head was dropped from a height of 4 m from the surface of the laminated glass and collided with the laminated glass, and the HIC value (ECE) of the laminated glass was measured.
In addition, about the thing which the tear generate | occur | produced in the interlayer film for laminated glass in the case of a measurement, the length of tear was measured.

(Measurement of maximum stress σ, breaking strain ε and breaking energy U of interlayer film for laminated glass)
The interlayer film for laminated glass is a test piece having a shape of dumbbell No. 1 (conforming to JIS K 6771), and is pulled using a tensile tester at a pulling rate of 500% / min, and the tensile strength at break at a measurement temperature of 20 ° C. (kg / cm ² ). Was measured. A stress σ (MPa) -strain ε (%) curve was obtained from the obtained value. Note that 500% / min means a speed at which a distance of 5 times the distance between the chucks of the test piece is moved per minute.
Next, the maximum stress σ and the breaking strain ε were obtained from the obtained stress-strain curve, and the breaking energy U was calculated by the above formula (2).

(Measurement of storage elastic modulus G ′ and tan δ of resin film and interlayer film for laminated glass)
Using a dynamic viscoelasticity measuring device (device name: DVA-200, manufacturer: IT Measurement Control Co., Ltd.), shear viscoelasticity measurement in the range of 50 to 100 Hz was performed at 20 ° C., and obtained by measurement. The maximum value of the storage elastic modulus was G ′ (max), the minimum value was G ′ (min), and the maximum value of tan δ obtained by the measurement was tan δ (max).

(Reference Example 2)
100 parts by weight of polyvinyl butyral resin (degree of acetalization 68.0 mol%, vinyl acetate component ratio 0.6 mol%) and 38 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer After being sufficiently melt-kneaded with a mixing roll, it was press-molded at 150 ° C. for 30 minutes with a press molding machine to obtain a resin film having a thickness of 1500 μm, which was used as an interlayer film for laminated glass. Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1.

(Reference Example 3)
100 parts by weight of polyvinyl butyral resin (degree of acetalization 68.0 mol%, vinyl acetate component ratio 0.6 mol%) and 45 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer The mixture was sufficiently melt-kneaded with a mixing roll, and then press molded at 150 ° C. for 30 minutes with a press molding machine to obtain a 760 μm thick resin film, which was used as an interlayer film for laminated glass. Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1.

(Reference Example 4)
100 parts by weight of polyvinyl butyral resin (degree of acetalization 68.0 mol%, vinyl acetate component ratio 0.6 mol%) and 38 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer Were mixed and sufficiently melt-kneaded with a mixing roll, and then press molded at 150 ° C. for 30 minutes with a press molding machine to obtain a resin film (1) having a thickness of 340 μm.
Next, 100 parts by weight of polyvinyl butyral resin (degree of acetalization 65.0 mol%, vinyl acetate component ratio 14 mol%) and 62 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer Were mixed and sufficiently melt-kneaded with a mixing roll, and then press molded at 150 ° C. for 30 minutes with a press molding machine to obtain a resin film (2) having a thickness of 120 μm.
With respect to the obtained resin film, the storage elastic modulus G ′ and tan δ were measured by the method described above. The results are shown in Table 2.

The obtained resin film (2) was sandwiched between two resin films (1), subjected to heat pressing and thermocompression bonded to obtain a three-layer interlayer film for laminated glass. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1.

(Reference Example 5)
100 parts by weight of polyvinyl butyral resin (degree of acetalization 68.0 mol%, vinyl acetate component ratio 0.6 mol%) and 38 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer The mixture was sufficiently melt-kneaded with a mixing roll and then press molded at 150 ° C. for 30 minutes with a press molding machine to obtain a resin film (3) having a thickness of 250 μm.
Next, 100 parts by weight of polyvinyl butyral resin (degree of acetalization 65.0 mol%, vinyl acetate component ratio 14 mol%) and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer After being sufficiently melt-kneaded with a mixing roll, it was press molded at 150 ° C. for 30 minutes with a press molding machine to obtain a resin film (4) having a thickness of 250 μm.
With respect to the obtained resin film, the storage elastic modulus G ′ and tan δ were measured by the method described above. The results are shown in Table 2.

The obtained resin film (4) was sandwiched between two resin films (3), heat-pressed and thermocompression bonded to obtain a three-layer interlayer film for laminated glass. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1.

(Reference Example 6)
100 parts by weight of polyvinyl butyral resin (degree of acetalization 68.0 mol%, vinyl acetate component ratio 0.6 mol%) and 38 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer Were mixed and sufficiently melt-kneaded with a mixing roll, and then press molded at 150 ° C. for 30 minutes with a press molding machine to obtain a resin film (5) having a thickness of 300 μm.
Next, 100 parts by weight of polyvinyl butyral resin (degree of acetalization 65.0 mol%, vinyl acetate component ratio 14 mol%) and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer Were mixed sufficiently with a mixing roll and then press molded at 150 ° C. for 30 minutes with a press molding machine to obtain a resin film (6) having a thickness of 300 μm.
With respect to the obtained resin film, the storage elastic modulus G ′ and tan δ were measured by the method described above. The results are shown in Table 2.

The obtained resin film (6) was sandwiched between two resin films (5), heat-pressed and thermocompression bonded to obtain a three-layer interlayer film for laminated glass. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1.

(Reference Example 7)
100 parts by weight of polyvinyl butyral resin (degree of acetalization 68.0 mol%, vinyl acetate component ratio 0.6 mol%) and 38 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer The mixture was sufficiently melt-kneaded with a mixing roll, and then press molded at 150 ° C. for 30 minutes with a press molding machine to obtain a resin film (7) having a thickness of 500 μm and a resin film (8) having a thickness of 200 μm. Obtained.
With respect to the obtained resin film, the storage elastic modulus G ′ and tan δ were measured by the method described above. The results are shown in Table 2.

The resin film (4) obtained in Reference Example 5 is sandwiched between the obtained resin film (7) and the resin film (8), heated and pressed to obtain an intermediate film for laminated glass having a three-layer structure. It was. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1. However, the HIC value (EEVC) and the HIC value (ECE) were measured by causing the impactor head to collide with the glass surface bonded to the resin film (8) side.

(Reference Example 8)
Mixing 100 parts by weight of polyvinyl butyral resin (degree of acetalization 65.0 mol%, vinyl acetate component ratio 14 mol%) and 50 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer This was sufficiently melt-kneaded with a mixing roll and then press molded at 150 ° C. for 30 minutes with a press molding machine to obtain a resin film (9) having a thickness of 450 μm.
With respect to the obtained resin film, the storage elastic modulus G ′ and tan δ were measured by the method described above. The results are shown in Table 2.

The resin film (5) obtained in Reference Example 6 and the obtained resin film (9) were superposed and subjected to heat pressing and thermocompression bonding to obtain an interlayer film for laminated glass having a two-layer structure. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1. However, the HIC value (EEVC) and the HIC value (ECE) were measured by causing the impactor head for HIC measurement to collide with the glass surface bonded to the resin film (5) side.

(Reference Example 9)
The resin film (7) obtained in Reference Example 7 is sandwiched between the two resin films (2) obtained in Reference Example 3, and heated and pressed to obtain an intermediate film for laminated glass having a three-layer structure. It was. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1.

(Reference Example 10)
The resin film (7) obtained in Reference Example 7 is sandwiched between the resin film (2) obtained in Reference Example 3 and the resin film (5) obtained in Reference Example 6, and heat-pressed to perform thermocompression bonding. Thus, an interlayer film for laminated glass having a three-layer structure was obtained. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1. However, the HIC value (EEVC) and the HIC value (ECE) were measured by causing the impactor head for HIC measurement to collide with the glass surface bonded to the resin film (5) side.

(Reference Example 11)
100 parts by weight of polyvinyl butyral resin (degree of acetalization 65.0 mol%, ratio of vinyl acetate component 14 mol%) having a half-value width of 190 cm ⁻¹ corresponding to a hydroxyl group obtained when measuring an infrared absorption spectrum And 45 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer are sufficiently melt-kneaded with a mixing roll and then press-molded at 150 ° C. for 30 minutes with a press molding machine. Thus, a resin film having a thickness of 760 μm was obtained, and this was used as an interlayer film for laminated glass. Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1.

(Reference Example 12)
A polyvinyl alcohol aqueous solution in which polyvinyl alcohol having an average polymerization degree of 1500 and a saponification degree of 99.5 mol% was dissolved in pure water so as to have a concentration of 10% by weight was prepared. To 100 parts by weight of this aqueous polyvinyl alcohol solution, 0.8 parts by weight of 10% hydrochloric acid and 5.73 parts by weight of butyraldehyde were added as an acid catalyst, and then reacted at 85 to 95 ° C. with stirring for 1 hour. Thereafter, 3.5 parts by weight of 10% hydrochloric acid was added as an acid catalyst, and the mixture was reacted for 2 hours while stirring at 85 ° C. to obtain particles of a crosslinked polyvinyl butyral resin. The average particle diameter of the obtained crosslinked polyvinyl butyral resin particles was 1.0 μm.

100 parts by weight of polyvinyl butyral resin (degree of acetalization 65.0 mol%, vinyl acetate component ratio 0.6 mol%), 30 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer and obtained After being mixed with 5 parts by weight of the crosslinked polyvinyl butyral resin particles, this was sufficiently melt-kneaded with a mixing roll, and then press molded at 150 ° C. for 30 minutes to obtain a 760 μm thick resin film. Was used as an interlayer film for laminated glass. Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1.

(Example 13)
After mixing 100 parts by weight of the crosslinked polyvinyl butyral resin prepared in Reference Example 12 and 40 parts by weight of triethylene glycol di-2-ethylbutyrate as a plasticizer, this was sufficiently melt-kneaded with a kneader and then pressed with a press molding machine. It was press-molded at 150 ° C. and a pressure of 980 N / cm ² for 20 minutes to obtain a resin film having a thickness of 860 μm, which was used as an interlayer film for laminated glass. Moreover, the laminated glass was obtained by the method similar to the reference example 1 using the obtained intermediate film for laminated glasses.
The obtained interlayer film for laminated glass and laminated glass were evaluated in the same manner as in Reference Example 1.

(Reference Example 14)
An interlayer film for laminated glass obtained by the same method as in Reference Example 1 was sandwiched between two transparent float glasses having a thickness of 1.8 mm and 4 mm, respectively, and this was put in a rubber bag, with a vacuum of 2660 Pa. After deaeration for 20 minutes, it was transferred to an oven while being deaerated, and further vacuum-pressed while being kept at 90 ° C. for 30 minutes. The laminated glass preliminarily pressure-bonded in this manner was pressure-bonded for 20 minutes in an autoclave at 135 ° C. and a pressure of 118 N / cm ² to obtain a laminated glass.
About the obtained laminated glass, the impactor head for HIC measurement was made to collide from the 4 mm float glass side by the above-mentioned method, and the HIC value (EEVC) and the HIC value (ECE) were measured.
The results are shown in Table 3.

(Reference Example 15)
For the laminated glass obtained by the same method as in Reference Example 14, the HIC value (EEVC) and the HIC value (ECE) are measured by colliding the impactor head for HIC measurement from the 1.8 mm float glass side by the above method. did.
The results are shown in Table 3.

(Reference Example 16)
An interlayer film for laminated glass obtained by the same method as in Reference Example 1 was prepared with float glass having a thickness of 2.5 mm and polymethyl methacrylate having a scratch-resistant layer made of a transparent elastomer provided on a surface having a thickness of 1.0 mm. After sandwiching, this was put in a rubber bag, deaerated at a vacuum degree of 2660 Pa for 20 minutes, transferred to an oven while being deaerated, and further vacuum pressed while being held at 90 ° C. for 30 minutes. The laminated glass preliminarily pressure-bonded in this manner was pressure-bonded for 20 minutes in an autoclave at 135 ° C. and a pressure of 118 N / cm ² to obtain a laminated glass.
About the obtained laminated glass, the impactor head for HIC measurement was made to collide from the float glass side by the above-mentioned method, and the HIC value (EEVC) and the HIC value (ECE) were measured.
The results are shown in Table 3.

(Reference Example 17)
100 parts by weight of polyvinyl butyral resin (degree of acetalization 65.0 mol%, vinyl acetate component ratio 0.6 mol%) and 30 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer Were mixed and sufficiently melt-kneaded with a mixing roll, and then press molded at 150 ° C. for 30 minutes with a press molding machine. In press molding, a wedge-shaped resin film was obtained by setting the thickness of one side edge to 660 μm and the thickness of the other side opposite to this to 860 μm, and this was used as an interlayer film for laminated glass .
A laminated glass was produced in the same manner as in Reference Example 1 except that the obtained interlayer film for laminated glass was used.
About the obtained laminated glass, the HIC value (EEVC) and the HIC value (ECE) were measured by the above-mentioned method.
The results are shown in Table 3.

(Reference Example 18)
A resin film made of polyethylene terephthalate having a thickness of 100 μm is sandwiched between two sheets of the resin film (1) obtained in Reference Example 4, and is subjected to heat pressing and thermocompression bonding to form an interlayer film for laminated glass having a three-layer structure. Obtained. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
A laminated glass was produced in the same manner as in Reference Example 1 except that the obtained interlayer film for laminated glass was used.
About the obtained laminated glass, the HIC value (EEVC) and the HIC value (ECE) were measured by the above-mentioned method.
The results are shown in Table 3.

(Reference Example 19)
100 parts by weight of polyvinyl butyral resin (degree of acetalization 65.0 mol%, vinyl acetate component ratio 0.6 mol%) and 30 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer Were mixed and sufficiently melt-kneaded with a mixing roll, and then press molded at 150 ° C. for 30 minutes with a press molding machine. In press molding, a wedge-shaped resin film (10) having a right triangle cross section with a base of 430 μm and a height of 500 mm was obtained.

Further, 100 parts by weight of polyvinyl butyral resin (degree of acetalization 65.0 mol%, vinyl acetate component ratio 14 mol%) and 50 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer The mixture is sufficiently melt-kneaded with a mixing roll and then press-molded at 150 ° C. for 30 minutes with a press molding machine to form a wedge-shaped resin film having an isosceles cross section with a base of 860 μm and a height of 500 mm ( 11) was obtained.

Two wedge-shaped resin films (10) having a right-angled triangular cross section were laminated on a wedge-shaped resin film (11) having an isosceles triangular cross section to obtain an intermediate film for laminated glass having a constant thickness.
A laminated glass was produced in the same manner as in Reference Example 1 except that the obtained interlayer film for laminated glass was used. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
About the obtained laminated glass, the HIC value (EEVC) and the HIC value (ECE) were measured by the above-mentioned method.
The results are shown in Table 3.

(Reference Example 20)
In a resin film made of polyethylene terephthalate having a thickness of 100 μm, cuts having a length of 5 mm were linearly formed at a pitch of 20 mm. Furthermore, the same straight cut was put on the entire surface of the resin film made of polyethylene terephthalate so that each straight line was 100 mm in parallel with each other.
The resin film (1) obtained in Reference Example 4 is sandwiched between two sheets of the obtained resin film made of polyethylene terephthalate having a thickness of 100 μm, and heated and pressed to form a three-layer structure. An interlayer film for laminated glass was obtained. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
A laminated glass was produced in the same manner as in Reference Example 1 except that the obtained interlayer film for laminated glass was used.
About the obtained laminated glass, the HIC value (EEVC) and the HIC value (ECE) were measured by the above-mentioned method.
The results are shown in Table 3.

(Reference Example 21)
(Preparation of ITO dispersion plasticizer)
2.5 parts by weight of tin-doped indium oxide (ITO) powder is added to 100 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO), and a polyphosphoric acid ester salt is used as a dispersant. ITO fine particles were dispersed in 3GO with a bead mill. Thereafter, 0.25 parts by weight of acetylacetone was added to the obtained dispersion under stirring to obtain an ITO dispersion plasticizer.

Laminated glass having a thickness of 800 μm by the same method as in Reference Example 1 except that 38 parts by weight of the obtained ITO dispersion plasticizer was used instead of 38 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO). An interlayer film for the production was produced, and a laminated glass was produced using the interlayer film.

(Reference Example 22)
Reference was made except that 38 parts by weight of the ITO dispersion plasticizer obtained in Reference Example 20 was used instead of 38 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) in the production of the resin film (1). In the same manner as in Example 4, a resin film (12) having a thickness of 340 μm was obtained.
Further, in the production of the resin film (2), instead of 62 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO), 62 parts by weight of the ITO dispersion plasticizer obtained in Reference Example 20 was used. Obtained a resin film (13) having a thickness of 120 μm in the same manner as in Reference Example 4.
With respect to the obtained resin films (12) and (13), the storage elastic modulus G ′ and tan δ were measured by the method described above, and the dispersion state of the ITO fine particles was evaluated by the following method. The results are shown in Table 4.

(Evaluation of dispersion state of ITO fine particles)
An ultrathin piece having a cross section of the interlayer film for laminated glass was prepared, and a photograph was taken using a transmission electron microscope (TEM: manufactured by Hitachi, Ltd., H-7100FA type). The photo was taken in a 3 μm × 4 μm range at a magnification of × 20000, and was enlarged 3 times by printing the photo.
The major axis of the particle diameter of all ITO fine particles in the photographing range of 3 μm × 4 μm was measured, and the average particle diameter was determined by the average in terms of deposition. Further, the number of fine particles having a particle diameter of 100 nm or more existing in the photographing range was obtained and divided by the photographing area of 12 μm ² to calculate the number per 1 μm ² .

The resin film (13) was sandwiched between the two resin films (12), heat-pressed and thermocompression bonded to obtain a three-layer interlayer film for laminated glass. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
A laminated glass was obtained in the same manner as in Reference Example 1 using the obtained interlayer film for laminated glass.

(Reference Example 23)
The resin film (2) obtained in Reference Example 4 is sandwiched between the two resin films (12) obtained in Reference Example 21, and heated and pressed to obtain an intermediate film for laminated glass having a three-layer structure. It was. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
A laminated glass was obtained in the same manner as in Reference Example 1 using the obtained interlayer film for laminated glass.

(Reference Example 24)
(Preparation of ATO dispersion plasticizer)
With respect to 100 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO), 3.0 parts by weight of antimony-doped tin oxide (ATO) powder is charged, and a polyphosphoric acid ester salt is used as a dispersant. ATO fine particles were dispersed in 3GO with a bead mill. Thereafter, 0.25 parts by weight of acetylacetone was added to the obtained dispersion under stirring to obtain an ATO dispersion plasticizer.

In the production of the resin film (2), the same procedure as in Reference Example 4 was conducted except that 62 parts by weight of the obtained ATO dispersion plasticizer was used instead of 62 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO). Thus, a resin film (14) having a thickness of 120 μm was obtained.
With respect to the obtained resin film (14), the storage elastic modulus G ′ and tan δ were measured by the method described above, and the dispersion state of the ATO fine particles was evaluated in the same manner as in the case of the ITO fine particles. The results are shown in Table 4.

The obtained resin film (14) was sandwiched between the two resin films (1) obtained in Reference Example 4, and heat-pressed and thermocompression bonded to obtain an interlayer film for laminated glass having a three-layer structure. A schematic diagram showing the structure of the obtained interlayer film for laminated glass is shown in FIG.
A laminated glass was obtained in the same manner as in Reference Example 1 using the obtained interlayer film for laminated glass.

Evaluation similar to Reference Example 1 was performed on the interlayer film for laminated glass and laminated glass obtained in Reference Examples 21 to 24.
Further, the obtained laminated glass was evaluated for electromagnetic wave permeability, visible light transmittance, solar transmittance, and haze by the following methods.
The results are shown in Table 5.

(Evaluation of electromagnetic shielding properties at a frequency of 0.1 to 26.5 GHz)
By the KEC method measurement (electromagnetic wave shielding effect measurement in the near field), the reflection loss value (dB) in the range of 0.1 to 2 GHz is compared with a normal float glass single plate having a thickness of 2.5 nm, and the difference at the above frequency. The minimum and maximum values are described. The reflection loss value (dB) in the range of 2 to 26.5 GHz is obtained by setting a sample 600 mm square between a pair of antennas for transmission and reception, and receiving radio waves from the radio signal generator with a spectrum analyzer. Was evaluated (far-field electromagnetic wave measurement method).

(Measure haze)
The measurement was performed according to JIS K 6714.

(Measurement of visible light transmittance and solar transmittance in a wavelength region of 300 nm to 2100 nm)
Using a direct spectrophotometer (manufactured by Shimadzu Corporation, UV3100), a transmittance of 300 to 2100 nm was measured, and a visible light transmittance Tv of 380 to 780 nm according to JIS Z 8722 and JIS R 3106 (1998), and 300 The solar transmittance Ts of ˜2100 nm was determined.

According to the present invention, the laminated glass is excellent in the performance of mitigating the impact applied from the outside, and particularly in the performance of mitigating the impact when a human accident occurs and the head collides when used as a glass for a vehicle. And an interlayer film for laminated glass.

It is a disassembled perspective view which shows typically an example of the HIC measuring apparatus which measures the HIC value (EEVC) of the laminated glass of this invention. It is a schematic diagram which shows an example of the HIC measuring apparatus which measures the HIC value (ECE) of the laminated glass of this invention. 6 is a schematic diagram showing a configuration of an interlayer film for laminated glass obtained in Reference Example 4. FIG. 6 is a schematic diagram illustrating a configuration of an interlayer film for laminated glass obtained in Reference Example 5. FIG. 6 is a schematic diagram showing a configuration of an interlayer film for laminated glass obtained in Reference Example 6. FIG. 6 is a schematic diagram showing a configuration of an interlayer film for laminated glass obtained in Reference Example 7. FIG. 10 is a schematic diagram illustrating a configuration of an interlayer film for laminated glass obtained in Reference Example 8. FIG. 10 is a schematic diagram illustrating a configuration of an interlayer film for laminated glass obtained in Reference Example 9. FIG. 6 is a schematic diagram illustrating a configuration of an interlayer film for laminated glass obtained in Reference Example 10. FIG. 16 is a schematic diagram illustrating a configuration of an interlayer film for laminated glass obtained in Reference Example 18. FIG. 16 is a schematic diagram showing a configuration of an interlayer film for laminated glass obtained in Reference Example 19. FIG. 6 is a schematic diagram showing a configuration of an interlayer film for laminated glass obtained in Reference Example 20. FIG. 6 is a schematic diagram showing a configuration of an interlayer film for laminated glass obtained in Reference Example 22. FIG. 6 is a schematic diagram showing a configuration of an interlayer film for laminated glass obtained in Reference Example 23. FIG. 6 is a schematic diagram showing a configuration of an interlayer film for laminated glass obtained in Reference Example 24. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 HIC value (EEVC) measuring apparatus 11 Support part 12 Eaves part 13 Fixing part 14 Impactor head 20 HIC value (ECE) measuring apparatus 21 Laminated glass support stand 22 Impactor head 23 Guide system 24 Optical sensor

Claims (4)

A laminated glass in which at least an interlayer film for laminated glass and a glass plate are laminated and integrated,
A head impact index (HIC) value measured in accordance with the provisions of the European Enhanced Vehicle-safety Committee (EEVC / WG17) is 1000 or less.
The interlayer film for laminated glass contains a cross-linked polyvinyl acetal resin having a degree of acetalization of 60 to 85 mol%, and 40 parts by weight or more of the plasticizer for the interlayer film is contained with respect to 100 parts by weight of the polyvinyl acetal resin. The laminated film includes a layer having a thickness of 800 μm or more , and the interlayer film for laminated glass has a maximum stress σ obtained from a stress-strain curve at a temperature of 20 ° C. and a tensile rate of 500% / min of 20 MPa or less. The laminated glass is characterized by having a breaking strain ε of 200% or more. The laminated glass according to claim 1, wherein the crosslinked polyvinyl acetal resin is obtained by crosslinking between polyvinyl acetal molecules by monobutyral bonds. A layer having a thickness of 800 μm or more , comprising a crosslinked polyvinyl acetal resin having a degree of acetalization of 60 to 85 mol% and containing 40 parts by weight or more of an intermediate film plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin. The maximum stress σ determined from the stress-strain curve at a temperature of 20 ° C. and a tensile rate of 500% / min is 20 MPa or less, and the strain at break ε is 200% or more. An interlayer film for laminated glass. The interlayer film for laminated glass according to claim 3, wherein the cross-linked polyvinyl acetal resin is obtained by cross-linking polyvinyl acetal molecules by monobutyral bonds.

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