JP4644440B2 - Glass for vehicles - Google Patents

Description

  The present invention is excellent in performance to relieve impact applied from the outside, vehicle glass that can exhibit particularly high impact mitigation performance in the vicinity of the outer peripheral portion where there is a high probability that a pedestrian's head will collide when an accident occurs, and the glass The present invention relates to laminated glass suitable for vehicle 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) have also been established for the head impact test method for impact protection evaluation of the head. 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 it is said that when the HIC value exceeds 1000, the normal human survival probability decreases.

In recent years, the front nose of automobiles tends to be shorter, and in recent accidents, the position of the head of an adult pedestrian colliding with the automobile 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 an automobile, the international research harmonization activities (IHRA) currently in front of the adult head protection test range. We are considering including glass.

  At present, laminated glass is widely used as glass for vehicles used in vehicles such as automobiles and trains because even if it is damaged by external impact, glass fragments are not scattered and are safe. 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.

  The vehicle glass has performance such as penetration resistance from the viewpoint of protecting the driver, but the current situation is that little consideration is given to impact mitigation performance. In general, since penetration resistance and impact relaxation performance are difficult to achieve at the same time, most of the glass for vehicles currently used has an HIC value 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, the HIC value may exceed 2000. The vicinity of the outer periphery of such vehicle glass is a place where the pedestrian's head has a high probability of colliding in the event of an accident, and measures are required to avoid head injury when the pedestrian collides with the vehicle. It was done.

  On the other hand, Patent Document 1 discloses a method for protecting a pedestrian by attaching an airbag outside the vehicle and activating the airbag when the pedestrian collides with the vehicle. Yes. However, since it is impossible to predict which part of the windshield the pedestrian will collide with, very large airbags are necessary to achieve satisfactory results. Such large airbags are expensive. In addition, there is a problem in that the weight of the vehicle body is increased and fuel consumption is deteriorated, and the design of the vehicle body is remarkably restricted, which is not practical.

Japanese Patent Laid-Open No. 2003-182485

  In view of the above-described situation, the present invention is excellent in performance for mitigating externally applied impact, and for vehicles capable of exhibiting particularly high impact mitigation performance in the vicinity of an outer peripheral portion having a high probability that a pedestrian's head will collide when an accident occurs. An object is to provide glass and laminated glass suitable for the vehicle glass.

The present invention relates to a glass for a vehicle made of laminated glass in which at least an interlayer film for laminated glass and a glass plate are laminated and integrated, and in any part, Economic Commission for Europe (Economic Commission for Europe) The head impact index (hereinafter, also referred to as HIC) value measured in accordance with the provisions of Europe; ECE-Regulation No. 43 Annex 3) is 1000 or less, and all the outer peripheral parts or at least one side The vehicle glass has a head impact index at a peripheral portion that is 50 or more lower than the head impact index at a central portion.
In addition, in this specification, the glass for vehicles means the glass used for the window of vehicles, such as a car, a train, and a train. For example, in a car, it is a windshield for cars, a side glass for cars, a rear glass for cars. Etc.

The present invention is described in detail below.
As a result of intensive studies, the present inventors have a vehicle whose HIC value as a whole is 1000 or less and whose HIC value in all the outer peripheral parts or at least one edge is 50 or more lower than the HIC value in the central part. The glass for glass maintains various performances such as penetration resistance required for glass for vehicles, and also has excellent impact mitigation performance, and can effectively avoid head injury even when a pedestrian collides with the vehicle. The present inventors have found that this can be done and have completed the present invention.

  The vehicle glass of the present invention has ECE-Regulation No. 43 The HIC value measured according to the specification of Annex 3 is 1000 or less. If it exceeds 1000, when a pedestrian collides with a vehicle using the vehicle glass of the present invention, head injury cannot be avoided and the probability of survival decreases. Preferably it is 600 or less, More preferably, it is 300 or less.

In the vehicle glass of the present invention, the HIC value in all the outer peripheral parts or at least one side edge part is 50 or more lower than the HIC value in the central part. As described above, in the glass for vehicles having different HIC values depending on the part, the part having a relatively high HIC value is the central part and the part having a relatively low HIC value is the outer peripheral part, so that the glass for vehicles is required. While ensuring various performance such as penetration resistance, it is possible to improve the impact absorption performance of the outer peripheral portion of the glass for vehicles, which is a place where the pedestrian's head is highly likely to collide when an accident occurs.
In the glass for vehicles of this invention, it is preferable that the HIC value in all the outer peripheral parts or the edge part of at least one side is 250 or less. If it exceeds 250, sufficient shock absorbing performance may not be exhibited.

The meaning of the outer peripheral part or edge part of the glass for vehicles in this specification is demonstrated using FIG. FIG. 1 is a schematic view showing an example of a windshield for an automobile.
When the vehicle glass of the present invention is the windshield 1 of the automobile shown in FIG. 1, the side edges are parts of the ceiling side edge 2, the hood side edge 3, and the A pillar side edge 4. All of these correspond to the outer periphery.
In addition, although it does not specifically limit as a range of an outer peripheral part or a peripheral part, It is preferable that it is 50 mm or more from the fixed position when glass for vehicles is mounted | worn with the vehicle main body. In the laminated glass of this invention, it is preferable that the area of the part from which the said HIC value differs 50 or more is 50% or less of the whole area.
When the vehicle glass of the present invention is an automotive windshield, it is preferable that the HIC value is low in all parts of the ceiling side edge 2, the bonnet side edge 3, and the A pillar side edge 4. However, it is particularly important that the HIC value of the bonnet side edge 3 is low. In the windshield 1, the bonnet side edge 3 is a portion having the highest probability that the pedestrian's head will collide particularly when an accident occurs.

The HIC value is the ECE-Regulation No. 43 When a laminated glass having a size of 500 × 1100 mm is fixed to a frame having an opening of 470 × 1070 mm in accordance with the provisions of 43 Annex 3 paragraph 3.2, the impactor head (weight 10.0 + 0. 2 / -0.0 kg).
FIG. 2 is an exploded perspective view schematically showing an example of an HIC value measuring apparatus used when measuring the HIC value of the laminated glass of the present invention.

As shown in FIG. 2, 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. 2, the sizes of the inner peripheral portions of the collar portion 12 and the fixing portion 13 are 470 × 1070 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.

  After the HIC value is arranged as described above, the ECE-Regulation No. It can be calculated by the following formula (1) based on the rule of 43 Annex3 paragraph3.

式（１）中、ａ_rは、インパクタヘッドの合成加速度（Ｇ）を表し、ａ_Iは、インパクタヘッドの進行方向の加速度（Ｇ）を表し、ａ_Fは、インパクタヘッドの前後方向の加速度（Ｇ）を表し、ａ_S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), a _r represents the resultant acceleration (G) of the impactor head, a _I represents the acceleration (G) in the traveling direction of the impactor head, and a _F represents the longitudinal acceleration (G G), a _S represents the acceleration (G) in the lateral direction of the impactor head, and t ₂ -t ₁ represents a time interval (maximum 0.015 s) at which the HIC value becomes maximum.

A laminated glass in which at least an interlayer film for laminated glass and a glass plate are laminated and integrated, and in any part, Economic Commission for Europe (ECE-Regulation No. 43 Annex 3). A laminated glass having a head impact index (HIC) value measured in accordance with the definition of) of 1000 or less and having a head impact index different by 50 or more is also 1 of the present invention. One.
Further, in the laminated glass of the present invention, the interlayer film for laminated glass laminated with the glass plate is laminated with the glass plate in the central portion of the laminated glass at all the outer peripheral portions or at least one edge portion of the laminated glass. It is preferable to use an interlayer film for laminated glass that is different from the interlayer film for laminated glass, and the HIC values in all the outer peripheral parts or at least one edge of the laminated glass are in the central part of the laminated glass. More preferably, it is 50 or more lower than the head impact index.
By using the laminated glass having the above configuration for a windshield for an automobile, the HIC value can be reduced even in the outer peripheral portion where the windshield is fixed, and the pedestrian safety in a collision accident is improved.
The width from the outermost periphery of the interlayer film for laminated glass laminated on a part or all of the outer peripheral portion of the laminated glass is preferably 50 mm or more.
In the laminated glass of this invention, it is preferable that the area of the part from which the said HIC value differs 50 or more is 50% or less of the whole area.
If such a laminated glass is used and processed so that the portion having a low HIC value becomes the outer peripheral portion or at least one edge portion, the vehicle glass of the present invention can be obtained.
In the laminated glass of this invention, it is preferable that the HIC value in a part with a low HIC value is 250 or less.
As a method for measuring the HIC value of each part, the interlayer film for laminated glass laminated with the glass plate in all the outer peripheral portions or at least one side edge portion of the laminated glass is formed with the glass plate in the central portion of the laminated glass. When using an interlayer film for laminated glass that is different from the laminated interlayer film for laminated glass, a method for evaluating the central portion of the laminated glass that has been created separately using the interlayer film used at each location Etc. are used.

  According to the present invention, the glass for vehicles capable of exhibiting particularly high impact mitigation performance in the vicinity of the outer peripheral portion that is excellent in the performance of mitigating externally applied impact and has a high probability that the pedestrian's head will collide when an accident occurs, and A laminated glass suitable for the vehicle glass can be provided.

The vehicle glass and laminated glass of the present invention will be specifically described below.
The method of achieving a low HIC value in laminated glass is not particularly limited. For example, (1) a method of absorbing an impact with an interlayer film for laminated glass, (2) a glass portion is thinned, and the glass is easily deformed at the time of collision. And / or a method of absorbing impact by cracking, and (3) a method of using one side of laminated glass (the side that becomes the inner side when used as vehicle glass) as a resin plate instead of glass. In order to obtain the glass for a vehicle of the present invention showing the above-mentioned HIC value, these methods or a combination of these methods reduce the HIC value as a whole, and particularly concentrate on the outer peripheral portion or at least one side edge portion. In particular, by applying these methods or a combination of these methods, a difference in the HIC value between the central portion and the outer peripheral portion is developed.

First, (1) the case where an impact is absorbed by the interlayer film for laminated glass will be described.
As such a vehicle glass or laminated glass of the present invention, for example, an interlayer film for laminated glass having a storage elastic modulus G ′ of a certain value or less and a tan δ having a value of a certain value or more can be considered.
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 obtained vehicle glass or laminated glass has a low HIC value. In particular, the storage elastic modulus G ′ in a viscoelasticity test measured while changing the frequency in a region of a temperature of 20 ° C. and a frequency of 50 to 100 Hz is 1.0 × 10 ⁶ Pa or less, more preferably 5.0 × 10 ⁵ Pa or less. Is included in a portion corresponding to the outer peripheral portion of the vehicle glass of the interlayer film for laminated glass, the HIC value at that portion can be made 250 or less.

  Further, tan δ is a ratio (G ″ / G ′) between the storage elastic modulus G ′ and the loss elastic modulus G ″, and is a value indicating the dynamic viscoelasticity of the interlayer film for laminated glass, and hence the impact energy absorption. . By using an interlayer film for laminated glass having a sufficiently high impact energy absorption property, the obtained vehicle glass or laminated glass has a low HIC value. In particular, if a temperature 20 ° C., a frequency of 50 to 100 Hz or more and at least one tan δ is 0.7 or more are included in the portion corresponding to the outer peripheral portion of the vehicle glass of the interlayer film for laminated glass, The HIC value at the site can be 250 or less.

  As an interlayer film for laminated glass whose storage elastic modulus G ′ and tan δ satisfy the above-mentioned conditions, specifically, a polyvinyl acetal resin is a main component, and a plasticizer is 35 parts by weight or more with respect to 100 parts by weight of the polyvinyl acetal resin. The thing to contain is mentioned. By blending a large amount of plasticizer, an interlayer film for laminated glass satisfying the above-described storage elastic modulus G ′ and tan δ can be obtained. As a compounding quantity of a plasticizer, 45 weight part or more is further more preferable, and 60 weight part or more is especially preferable.

  However, when an interlayer film for laminated glass containing such a large amount of plasticizer is used, the plasticizer may bleed out or the resulting vehicle glass may have poor penetration resistance or the like. . Therefore, the entire interlayer film for laminated glass is not uniformly made to contain such a large amount of plasticizer, but the content of the plasticizer is particularly increased at a portion where a low HIC value is required. That is, the plasticizer content is adjusted according to the required HIC value, and in particular for laminated glass with a higher plasticizer content in the part corresponding to all the outer peripheral parts or at least one side edge part of the vehicle glass. An interlayer film is used.

  In addition, the thickness of the interlayer film for laminated glass also affects the absorption of impact by the interlayer film for laminated glass. Generally, a thin interlayer film for laminated glass has higher impact absorbing ability than a thick interlayer film for laminated glass. Therefore, the thickness of the interlayer film for laminated glass is adjusted in accordance with the required HIC value, and in particular, the thickness of the interlayer film for laminated glass in the portion corresponding to all the outer peripheral parts or at least one edge of the vehicle glass. An interlayer film for laminated glass that is made thin is used. For example, the interlayer film for laminated glass may have a wedge shape in which the thickness is gradually increased from one end to the other end, or a shape in which the outer peripheral portion is thinner than the central portion. It is done.

  Such an interlayer film for laminated glass may be a single layer, but as a multilayer structure, a layer containing a particularly large amount of plasticizer is arranged on the outer peripheral part, or the thickness is particularly reduced. It is preferable to make it. For example, a multi-layer structure of three or more layers, each layer having a wedge shape, and a wedge-shaped layer having a small storage elastic modulus G ′ being used as an intermediate layer, the wedge-shaped layers are alternately stacked, and the total thickness is An interlayer film for laminated glass that is constant can be mentioned. If a windshield made of laminated glass using such an interlayer film for laminated glass is arranged so that the wedge-shaped base portion of the intermediate layer having a small storage elastic modulus G ′ is on the bonnet side, 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 secure strength.

The thickness of the interlayer film for laminated glass is not particularly limited, but is preferably 700 μm or more from the viewpoint of penetration resistance.
When the interlayer film for laminated glass has a multilayer structure and a layer satisfying the above-described storage elastic modulus G ′ and tan δ is partially arranged, the thickness of such a layer is the thickness of the entire interlayer film for laminated glass. It is preferable to be 10% or more. If it is less than 10%, sufficient impact absorption performance may not be exhibited.

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 polyvinyl acetal resin, an infrared absorption spectrum is calculated | required, for example using "FT-IR" by HORIBA, From the peak corresponding to a hydroxyl group among the obtained peaks. Can be measured.

  The said polyvinyl acetal resin can be manufactured by a conventionally well-known method. For example, polyvinyl alcohol is dissolved in warm water, and the obtained aqueous solution is kept at a predetermined temperature, for example, 0 to 90 ° C., preferably 10 to 20 ° C., and the required acid catalyst and aldehyde are added and stirred. The acetalization reaction proceeds. Then, 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.

  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. N-Butylaldehyde having 4 carbon atoms is more preferable because the use of the obtained polyvinyl acetal resin increases the adhesive strength of each resin film, is excellent in weather resistance, and facilitates the production of the resin. These may be used alone or in combination of two or more.

The polyvinyl acetal resin may be cross-linked. Bleed out of the plasticizer can be suppressed by using the cross-linked polyvinyl acetal resin.
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 reactant, 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 Aliphatic diisocyanates such as anate, lysine diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, polyisocyanate blocked with polyphenol, acetylacetone, malonic acid diethyl ester, lactam, oxime, amide, tertiary alcohol, etc. Can be mentioned.

  The plasticizer is not particularly limited as long as it is usually used for a polyvinyl acetal resin, and examples thereof include known plasticizers generally used as a plasticizer for an interlayer film. For example, monobasic acid ester And organic ester plasticizers such as polybasic acid esters; phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid. 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.
Moreover, it is preferable that the diester type compound which consists of a dicarboxylic acid and a monohydric alcohol or consists of a monocarboxylic acid and a dihydric alcohol is mix | blended among the said plasticizers.

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.

The method for producing the interlayer film for laminated glass is not particularly limited. For example, after blending a resin component such as the above-mentioned polyvinyl acetal resin, a plasticizer and other additives as necessary, and uniformly kneading, Examples thereof include a method of forming a film into a sheet by a conventionally known method such as an extrusion method, a calendar 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.
Further, the interlayer film for laminated glass having a multilayer structure in which the above wedge-shaped layers are alternately stacked is manufactured by using a mold that can be shaped by extrusion and multilayer extrusion so that all the layers have a wedge shape. be able to.

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 vehicle glass can absorb an impact by easily deforming and / or breaking the glass at the time of a collision. In addition, the HIC value of the glass for vehicles has a strong relationship with the deformation at the time of collision, and decreases as the deformation amount at the time of collision increases. That is, the greater the deformation of the vehicle glass, the lower the HIC value. Moreover, by making the thickness of the other glass plate thicker than 1.8 mm, it becomes possible to achieve both durability and HIC value as vehicle glass.
In addition, in the glass for vehicles having such a structure using glass plates having different thicknesses, the thicker one may be used for either the vehicle outer side or the vehicle inner side. It is preferable that the thicker one is the outside of the vehicle.

  Next, (3) the case where the whole impact absorption property is improved by using one side of laminated glass (the side which becomes the inside of the glass for vehicles) as a resin plate instead of glass will be described. 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 vehicle glass or laminated glass has a sufficiently high impact absorbing performance as compared with a glass plate on both sides, and can greatly reduce the HIC value.

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.

  It does not specifically limit as a method to manufacture the glass for vehicles or laminated glass of this invention, The manufacturing method of a conventionally well-known laminated glass is employable. For example, when the vehicle glass or 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, Is put into a rubber bag and pre-adhered at about 70 to 110 ° C. while sucking under reduced pressure, and then using an autoclave or pressing, at a temperature of about 120 to 150 ° C. and a pressure of about 1 to 1.5 MPa. It can manufacture by performing this adhesion | attachment.

Further, in the method for producing vehicle glass or laminated glass described above, an interlayer film for laminated glass made of plasticized polyvinyl butyral resin is interposed between at least a pair of glass plates, and at the same time the suction degassing is performed under reduced pressure. You may heat-press at 60-100 degreeC. More specifically, the laminated body of glass plate / intermediate film / glass plate is put in a rubber bag, for example, about 60 to 60 in an autoclave while sucking and degassing under a reduced pressure of about −66.7 to −99.3 MPa. It is carried out by performing thermocompression bonding for about 10 to 30 minutes at a temperature of 100 ° C. and a pressure of about 1 to 10 MPa, and performing deaeration and adhesion at the same time.
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.

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

(Manufacture of interlayer film for laminated glass)
(Production Example 1)
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 having a thickness of 750 μm, which was combined with the interlayer film for laminated glass (1). did.

(Production 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 (1) 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 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 (2) 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 (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 (2).

(Manufacture of laminated glass)
The obtained interlayer film for laminated glass (1) and (2) was sandwiched between two transparent float glasses having a thickness of 2 mm, placed in a rubber bag, and deaerated at a vacuum of 2660 Pa for 20 minutes. It moved to oven with deaeration, and also vacuum-pressed, hold | maintaining at 90 degreeC for 30 minutes. The thus preliminarily bonded laminated glass was pressure bonded for 20 minutes in an autoclave at 135 ° C. and a pressure of 118 N / cm ² to obtain laminated glasses (1) and (2).

(Measurement of HIC value)
ECE-Regulation No. Based on the method conforming to 43 Annex 3, using the HIC measuring device having the structure shown in FIG. 2, the impactor head is dropped from a height of 4 m from the surface of the laminated glass and collided with the laminated glass, and the laminated glass (1) and The HIC value of (2) was measured.
The HIC values were 275 for laminated glass (1) and 180 for laminated glass (2).

Example 1
An intermediate film for laminated glass (1) having a length of 300 mm and a width of 900 mm is placed in the center of a transparent float glass having a thickness of 2 mm, a length of 500 mm, and a width of 1100 mm. An interlayer film for laminated glass (2) having a thickness of 100 mm and an interlayer film for laminated glass (2) having a length of 100 mm and a width of 900 mm are placed on both sides in the lateral direction. Float glass was put on top, placed 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 thus preliminarily pressure-bonded laminated glass was pressure-bonded in an autoclave at 135 ° C. and a pressure of 118 N / cm ² for 20 minutes to obtain a laminated glass (3) having portions having different HIC values.

  According to the present invention, the glass for vehicles capable of exhibiting particularly high impact mitigation performance in the vicinity of the outer peripheral portion that is excellent in the performance of mitigating externally applied impact and has a high probability that the pedestrian's head will collide when an accident occurs, and A laminated glass suitable for the vehicle glass can be provided.

It is a schematic diagram which shows an example of the windshield for motor vehicles. It is a disassembled perspective view which shows typically an example of the HIC measuring apparatus which measures the HIC value of the glass for vehicles of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Automobile windshield 2 Ceiling side edge part 3 Bonnet side edge part 4 A pillar side edge part 10 HIC value measuring apparatus 11 Support part 12 Gutter part 13 Fixing part 14 Impactor head

Claims (6)

An automotive glass made of laminated glass in which at least an interlayer film for laminated glass and a glass plate are laminated and integrated, and in any part, Economic Commission for Europe (ECE-) The head impact index (HIC) value measured in accordance with the regulation of Regulation No. 43 Annex 3) is 1000 or less, and the head impact at all outer peripheral portions or at least one side edge portion. The index is 50 or more lower than the head impact index in the central part ,
For the head impact index, a laminated glass having a size of 500 × 1100 mm is produced by changing the size of the interlayer film using the interlayer film used at the site where the head impact index is measured. the measured values der Ru vehicle glass with.   2. The vehicle glass according to claim 1, wherein the head impact index at all outer peripheral portions or at least one side edge portion is 250 or less.   The vehicle glass according to claim 1 or 2, wherein the vehicle glass is an automobile windshield, an automobile side glass, or an automobile rear glass. A laminated glass in which at least an interlayer film for laminated glass and a glass plate are laminated and integrated, and in any part, Economic Commission for Europe (ECE-Regulation No. 43 Annex 3). ) Head impact index (Heic In Criteria; HIC) value measured in accordance with the provisions of), and having a portion where the head impact index differs by 50 or more ,
For the head impact index, a laminated glass having a size of 500 × 1100 mm is produced by changing the size of the interlayer film using the interlayer film used at the site where the head impact index is measured. the measured values der Ru laminated glass using. The interlayer film for laminated glass laminated with the glass plate in all the outer peripheral parts or at least one edge of the laminated glass is the interlayer film for laminated glass laminated with the glass plate in the central part of the laminated glass. Uses a different interlayer film for laminated glass ,
The head impact index in the portion using the different laminated glass interlayer film on all the outer peripheral parts or at least one side edge of the laminated glass is 50 or more than the head impact index in the central part of the laminated glass. 4. the laminated glass of wherein Rukoto different. The combined head impact index at edges of each of the peripheral portion or at least one side of the glass (Head Injury Criteria; HIC) values, combined features 50 that more lower than the head impact index in the central portion of the glass ,
For the head impact index, a laminated glass having a size of 500 × 1100 mm is produced by changing the size of the interlayer film using the interlayer film used at the site where the head impact index is measured. the measured values der Ru claim 4 or 5 laminated glass according with.

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