JP6065221B2 - Laminated glass plate - Google Patents

Description

  The present invention relates to a laminated glass plate excellent in sound insulation used for sound insulation walls of roads and tracks. In detail, it is related with the transparency laminated glass plate excellent in sound insulation, transparency, heat resistance, and the scattering prevention property of the glass fragment at the time of being damaged.

  In order to reduce noise to the surrounding environment along the tracks of highways and high-speed railways, sound insulation walls are installed. Among sound insulation walls, a transparent sound insulation wall made of a polycarbonate resin plate, an acrylic resin plate, a glass plate, or the like is also used for daylighting or securing a field of view.

  Polycarbonate resin plates and acrylic resin plates are lighter and easier to install than glass, and have the advantage of excellent impact resistance, but sound insulation is inferior to glass of the same thickness, and is also inferior in weather resistance and scratch resistance. There was a problem. In addition, since the thermal deformation temperature and melting point are low, when a vehicle fire occurs near the sound insulation wall, it may melt and fall below the overpass.

  On the other hand, the glass plate is excellent in sound insulation, and is excellent in weather resistance, scratch resistance and nonflammability. On the other hand, glass is heavy and inferior in impact resistance, and there is a problem that humans may be injured by broken glass at the time of breakage, and it is a material with low damping performance, at a specific frequency according to the plate thickness due to the coincidence effect There is also a decrease in sound insulation performance. For this reason, in laminated glass plates, in order to prevent scattering of glass fragments at the time of breakage and improve sound insulation performance, a plurality of glass plates are laminated using a resin intermediate film having damping performance, and the glass fragments at breakage A method for improving the sound insulation performance by reducing the coincidence effect at the same time as preventing scattering of the sound is disclosed.

  As such a laminated glass plate, a laminated intermediate film in which a plasticizer is blended with two kinds of polyvinyl acetal is used as a resin intermediate film (for example, Patent Documents 1 to 3); Using an intermediate film in which rubber layers made of butyl rubber or thermoplastic block copolymer rubber are laminated (for example, Patent Document 4); Polyvinyl acetal resin on both sides of hydrogenated styrene / diene block copolymer layer, etc. (For example, patent documents 5 and 6) etc. which used the intermediate film which laminated the adhesive resin layer which consists of these are indicated.

  However, the polyvinyl acetal-based resin containing a large amount of plasticizer widely used as an interlayer film for laminating glass plates has a relatively low softening point. Due to the high hygroscopicity that occurs, if left in a high humidity atmosphere for a long period of time, whitening gradually begins to occur from the periphery and a decrease in adhesion to the glass is observed. In this state, the moisture content must be strictly managed for controlling the adhesive strength with glass (for example, Non-Patent Document 1).

  In addition, when the intermediate film includes a rubber layer, it has excellent problems such as prevention of scattering of glass fragments at the time of breakage and excellent penetration resistance and sound insulation performance, but poor transparency and heat resistance. .

  By the way, it is composed of at least two polymer blocks [A] and at least one polymer block [B] mainly composed of a repeating unit derived from a chain conjugated diene compound, and is a block of all polymer blocks [A]. When the weight fraction in the entire copolymer is wA and the weight fraction in the entire block copolymer [B] in the entire block copolymer is wB, the ratio of wA to wB (wA: wB) is A modification obtained by introducing an alkoxysilyl group into a block copolymer hydride [2] obtained by hydrogenating 90% or more of all unsaturated bonds of a block copolymer [1] having a ratio of 30:70 to 60:40 The block copolymer hydride [3] has low hygroscopicity, weather resistance, transparency and flexibility, and has strong adhesive strength with glass, and is used as a sealing material for solar cell elements. Can be patented It is disclosed in 7.

JP-A-4-254444 JP-A-6-000926 Japanese Patent Laid-Open No. 9-156967 JP-A-1-244443 JP 2007-91491 A JP 2009-256128 A International Publication No. WO2012 / 043708

Yasuyuki Fujisaki, JCIA Monthly Report, 35 (10), 28 (1982)

  An object of the present invention is to provide a laminated glass plate using a sheet made of a novel adhesive resin composition, which is excellent in sound insulation, transparency, heat resistance, and prevention of scattering of glass fragments upon breakage. .

  As a result of intensive studies in view of the above situation of a laminated glass plate excellent in sound insulation, the present inventors use an adhesive resin composition layer made of a specific modified block copolymer hydride [3]. And it discovered that a favorable laminated glass plate was obtained by bonding a pair of glass plates, and came to complete this invention.

Thus, according to the present invention, at least two polymer blocks [A] mainly composed of a repeating unit derived from an aromatic vinyl compound and a repeating unit derived from a chain conjugated diene compound are mainly disposed between a pair of glass plates. It comprises at least one polymer block [B] as a component, and the weight fraction of the entire polymer block [A] in the entire block copolymer is wA, and the block weight of all polymer blocks [B] The ratio of wA to wB (wA: wB) is 30:70 to 60:40, and the total unsaturated bond of the block copolymer [1] is 90%. % Of an adhesive resin composition containing a modified block copolymer hydride [3] obtained by introducing an alkoxysilyl group into a block copolymer hydride [2] having a hydrogen content of at least%. Sano At least one or more adhesive resin composition layers in which the ratio (tr / tg) of the total thickness (tr) of the adhesive resin composition layer to the total (tg) is 0.1 or more and 4.0 or less are interposed. A laminated glass plate laminated together is provided.
The adhesive resin composition is preferably one in which 1 to 50 parts by weight of a plasticizer is blended with 100 parts by weight of the modified block copolymer hydride [3]. The plasticizer is preferably a hydrocarbon polymer having a number average molecular weight of 300 to 3,000.

  The laminated glass plate of the present invention has characteristics excellent in sound insulation, transparency, heat resistance, and prevention of scattering of glass fragments when broken. Further, the modified block copolymer hydride [3] used in the present invention does not require any special treatment such as adjustment of the water content before being bonded to glass, and is used under a normal temperature and humidity environment for a long time. Can be used as they are, and is easy to store and handle.

The modified block copolymer hydride [3] used in the present invention contains at least two polymer blocks [A] having a repeating unit derived from an aromatic vinyl compound as a main component and a repeating derived from a chain conjugated diene compound. It is composed of at least one polymer block [B] having a unit as a main component, and the weight fraction of the entire polymer block [A] in the entire block copolymer is wA, and the total polymer block [B] Total unsaturation of block copolymer [1] in which the ratio of wA to wB (wA: wB) is 30:70 to 60:40, where wB is the weight fraction of the entire block copolymer This is a modified block copolymer hydride [3] in which 90% or more of the bonds are hydrogenated.
Such a modified block copolymer hydride [3] is obtained by alkoxysilylating a block copolymer hydride [2] obtained by hydrogenating a carbon-carbon unsaturated bond of a specific block copolymer [1]. Is obtained.

1. Block copolymer [1]
The block copolymer [1], which is a precursor of the modified block copolymer hydride [3] according to the present invention, contains at least two polymer blocks [A] and at least one polymer block [B]. .

The polymer block [A] is mainly composed of a structural unit derived from an aromatic vinyl compound, and the content of the structural unit derived from the aromatic vinyl compound in the polymer block [A] is usually 90% by weight. Above, preferably 95% by weight or more, more preferably 99% by weight or more. Further, the component other than the structural unit derived from the aromatic vinyl compound in the polymer block [A] can include a structural unit derived from a chain conjugated diene and / or a structural unit derived from another vinyl compound, The content is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less. When there are too few structural units derived from the aromatic vinyl compound in the polymer block [A], the heat resistance of the laminated glass plate of the present invention may be lowered.
The plurality of polymer blocks [A] may be the same as or different from each other as long as the above range is satisfied.

The polymer block [B] has a structural unit derived from a chain conjugated diene compound as a main component, and the content of the structural unit derived from the chain conjugated diene compound in the polymer block [B] is usually 90. % By weight or more, preferably 95% by weight or more, more preferably 99% by weight or more. When the structural unit derived from the chain conjugated diene compound is in the above range, the laminated glass of the present invention is excellent in thermal shock resistance and low temperature adhesiveness. Moreover, as a component other than the structural unit derived from the chain conjugated diene compound in the polymer block [B], a structural unit derived from an aromatic vinyl compound and / or a structural unit derived from another vinyl compound can be included, The content is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less. When the content of the structural unit derived from the aromatic vinyl compound in the polymer block [B] increases, the flexibility of the adhesive resin composition layer at a low temperature decreases, and the impact resistance of the laminated glass plate of the present invention decreases. May fall.
When there are a plurality of polymer blocks [B], the polymer blocks [B] may be the same as or different from each other as long as the above range is satisfied.

  Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4- Examples include t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-monochlorostyrene, dichlorostyrene, 4-monofluorostyrene, 4-phenylstyrene, and the like that do not contain polar groups in terms of hygroscopicity. Styrene is particularly preferred from the viewpoint of industrial availability.

  Specific examples of the chain conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc., and are polar in terms of hygroscopicity. Those containing no group are preferred, and 1,3-butadiene and isoprene are particularly preferred from the viewpoint of industrial availability.

  Examples of other vinyl compounds include chain vinyl compounds and cyclic vinyl compounds. Vinyl compounds having a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen group and / or an unsaturated cyclic acid anhydride or an unsaturated compound. Although a saturated imide compound may be included, specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, A chain olefin such as 1-eicosene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene; a cyclic olefin such as vinylcyclohexane, which does not contain a polar group is preferable in terms of hygroscopicity, A chain olefin is more preferable, and ethylene and propylene are particularly preferable.

  The number of polymer blocks [A] in block copolymer [1] is usually 5 or less, preferably 4 or less, more preferably 3 or less. When there are a plurality of polymer blocks [A] and / or polymer blocks [B], the weight average molecular weight of the polymer block having the maximum and minimum weight average molecular weight in the polymer block [A] is expressed as Mw (A1 ) And Mw (A2), and when the weight average molecular weight of the polymer block having the largest and smallest weight average molecular weight in the polymer block [B] is Mw (B1) and Mw (B2), respectively, the Mw ( The ratio between A1) and Mw (A2) (Mw (A1) / Mw (A2)) and the ratio between Mw (B1) and Mw (B2) (Mw (B1) / Mw (B2)) Each is 2.0 or less, preferably 1.5 or less, more preferably 1.2 or less.

  The block form of the block copolymer [1] may be a chain type block or a radial type block, but a block type block is preferred because of its excellent mechanical strength. The most preferable form of the block copolymer [1] is a triblock copolymer in which the polymer block [A] is bonded to both ends of the polymer block [B], and a polymer on both ends of the polymer block [A]. It is a pentablock copolymer in which the block [B] is bonded and the polymer block [A] is bonded to the other end of the both polymer blocks [B].

  In the block copolymer [1], the weight fraction of the entire polymer block [A] in the entire block copolymer is wA, and the weight fraction of the entire polymer block [B] in the entire block copolymer is wA. When wB is wB, the ratio of wA to wB (wA: wB) is 30: 70-60: 40, preferably 35: 65-55: 45, and more preferably 40: 60-50: 50. When wA is too high, the heat resistance of the modified block copolymer hydride [3] used in the present invention is increased, but the flexibility is low, and the sound insulation of the laminated glass plate may not be improved. If it is too low, the refractive index will be too small compared to the refractive index of general-purpose float glass, and total reflection at the interface between the glass and the adhesive resin composition layer will easily occur for incident light in an oblique direction. Is unfavorable because of lowering.

  The molecular weight of the block copolymer [1] is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC using tetrahydrofuran (THF) as a solvent, and is usually 30,000 to 200,000, preferably 40,000 to It is 150,000, More preferably, it is 50,000-100,000. Further, the molecular weight distribution (Mw / Mn) of the block copolymer [1] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less.

  The production method of the block copolymer [1] includes a monomer mixture (a) containing an aromatic vinyl compound as a main component and a monomer containing a chain conjugated diene compound as a main component by, for example, a method such as living anion polymerization. A method of alternately polymerizing the mixture (b); after sequentially polymerizing the monomer mixture (a) containing an aromatic vinyl compound as a main component and the monomer mixture (b) containing a chain conjugated diene compound as a main component And a method of coupling the ends of the polymer block [B] with a coupling agent.

2. Block copolymer hydride [2]
The block copolymer hydride [2] according to the present invention hydrogenates the carbon-carbon unsaturated bond of the main chain and side chain of the block copolymer [1] and the carbon-carbon unsaturated bond of the aromatic ring. The hydrogenation rate is usually 90% or more, preferably 97% or more, more preferably 99% or more. The higher the hydrogenation rate, the better the weather resistance and heat resistance of the molded body. The hydrogenation rate of the block copolymer hydride [2] can be determined by measurement by ¹ H-NMR.

  There are no particular restrictions on the hydrogenation method or reaction mode of the unsaturated bond, and it may be carried out according to a known method. However, a hydrogenation method that can increase the hydrogenation rate and has little polymer chain scission reaction is preferred. Examples of such a hydrogenation method include methods described in International Publication WO2011 / 096389, International Publication WO2012 / 043708, and the like.

  The block copolymer hydride [2] obtained by the above method is recovered from the reaction solution after removing the hydrogenation catalyst and / or the polymerization catalyst from the reaction solution containing the block copolymer hydride [2]. The Although the form of the recovered block copolymer hydride [2] is not limited, it can usually be formed into a pellet and used for the subsequent introduction reaction of alkoxysilyl groups.

  The molecular weight of the block copolymer hydride [2] is a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and is usually 35,000. To 200,000, preferably 40,000 to 150,000, more preferably 45,000 to 100,000. The molecular weight distribution (Mw / Mn) of the block copolymer hydride [2] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. When Mw and Mw / Mn are within the above ranges, the mechanical strength and heat resistance of the molded body are improved.

3. Modified block copolymer hydride [3]
The modified block copolymer hydride [3] used in the present invention is obtained by introducing an alkoxysilyl group into the block copolymer hydride [2]. The alkoxysilyl group may be directly bonded to the block copolymer hydride [2] or may be bonded via a divalent organic group such as an alkylene group.

  As the method for introducing an alkoxysilyl group, a method in which the above block copolymer hydride [2] is reacted with an ethylenically unsaturated silane compound in the presence of a peroxide is usually preferred.

The introduction amount of the alkoxysilyl group is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.3 to 100 parts by weight with respect to 100 parts by weight of the block copolymer hydride [2]. 3 parts by weight. If the amount of alkoxysilyl groups introduced is too large, cross-linking of alkoxysilyl groups decomposed with a small amount of moisture, etc., proceeds before melt molding into the desired shape, resulting in gel generation or poor fluidity at the time of melting. As a result, problems such as deterioration of moldability occur. If the introduction amount of the alkoxysilyl group is too small, it is not preferable because a problem that a sufficient adhesive force with the glass cannot be obtained occurs. The introduction of the alkoxysilyl group can be confirmed by IR spectrum, and the introduction amount can be determined by measurement by ¹ H-NMR.

  The ethylenically unsaturated silane compound is not particularly limited as long as it is graft-polymerized with the above-mentioned block copolymer hydride [2] and introduces an alkoxysilyl group into the block copolymer hydride [2]. For example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, and p-styryltrimethoxysilane are preferably used.

  These ethylenically unsaturated silane compounds may be used alone or in combination of two or more. The amount of the ethylenically unsaturated silane compound used is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0, per 100 parts by weight of the block copolymer hydride [2]. .3 to 3 parts by weight.

  As the peroxide, those having a one-minute half-life temperature of 170 to 190 ° C. are preferably used. For example, t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl -2,5-di (t-butylperoxy) hexane, di-t-butylperoxide and the like are preferably used.

  These peroxides may be used alone or in combination of two or more. The amount of peroxide used is generally 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, more preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the block copolymer hydride [2]. 0.5 weight.

  The method of reacting the block copolymer hydride [2] with the ethylenically unsaturated silane compound in the presence of a peroxide is not particularly limited. For example, a desired temperature at a desired temperature in a twin-screw kneader is used. An alkoxysilyl group can be introduced by kneading for a time. In the block copolymer hydride [2] of the present invention, the temperature is usually 180 to 220 ° C, preferably 185 to 210 ° C, more preferably 190 to 200 ° C. The heat kneading time is usually about 0.1 to 10 minutes, preferably about 0.2 to 5 minutes, and more preferably about 0.3 to 2 minutes. What is necessary is just to knead | mix and extrude continuously so that temperature and residence time may become the said range.

  The molecular weight of the modified block copolymer hydride [3] according to the present invention is substantially the same as the molecular weight of the block copolymer hydride [2] used as a raw material because the amount of alkoxysilyl groups introduced is small. Although it does not change, since it reacts with the ethylenically unsaturated silane compound in the presence of a peroxide, the cross-linking reaction and the cleavage reaction of the polymer occur together, and the molecular weight distribution becomes large. The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent is usually from 35,000 to 200,000, preferably from 40,000 to 150,000. Preferably, it is 45,000-100,000, and molecular weight distribution (Mw / Mn) is 3.5 or less normally, Preferably it is 2.5 or less, Most preferably, it is 2.0 or less. When Mw and Mw / Mn are within this range, the mechanical strength and heat resistance of the adhesive resin composition layer are maintained.

4). Plasticizer The adhesive resin composition that forms a laminated glass plate interposed between a pair of glass plates of the present invention can contain a plasticizer in order to improve adhesiveness and sound insulation performance. Examples of the plasticizer include low molecular weight polymers other than the modified block copolymer hydride [3]; organic acid ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters; Phosphoric ester plasticizers such as organic phosphite esters are preferably used. These plasticizers may be used independently and 2 or more types may be used together.

  The low molecular weight polymer is preferably one that can be uniformly dissolved or dispersed in the modified block copolymer hydride [3]. A hydrocarbon polymer having a number average molecular weight of 300 to 5,000 maintains transparency and is heat resistant. Is preferable because it does not significantly impair. Specific examples of the hydrocarbon polymer include polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, ethylene / α-olefin copolymer, aliphatic hydrocarbon resin and hydride thereof, and fat. Examples thereof include cyclic hydrocarbon resins and hydrides thereof, indene / styrene copolymer hydrides, polyisoprene and hydrides thereof. Among these, polyisobutylene and polybutene are preferable in that a laminated glass plate excellent in transparency can be obtained.

  Examples of the organic acid ester plasticizer include glycol such as triethylene glycol, tetraethylene glycol or tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, heptylic acid, and n-octylic acid. Glycol esters obtained by reaction with monobasic acid such as 2-ethylhexyl acid, pelargonic acid (n-nonyl acid) or decyl acid; and polybasic acids such as adipic acid, sebacic acid, azelaic acid, phthalic acid and the like , Polybasic acid esters obtained by reaction with linear or branched alcohols having 4 to 8 carbon atoms; and the like. Among these, butylbenzyl phthalate, dibenzyl phthalate, and the like are preferable from the viewpoint that the refractive index of the adhesive resin composition layer is close to the refractive index of float glass and an excellent translucent laminated glass plate is obtained.

  Examples of the phosphate ester plasticizer include tributoxyethyl phosphate, tri (2-ethylhexyl) phosphate, tricresyl phosphate, isodecyl diphenyl phosphate, and the like. Among these, tricresyl phosphate, trixylenyl phosphate, and the like are preferable in that the refractive index of the adhesive resin composition layer is close to the refractive index of float glass and an excellent translucent laminated glass plate is obtained.

  Although it does not specifically limit as a compounding quantity of a plasticizer, Preferably it is 1-50 weight part with respect to 100 weight part of modified block copolymer hydrides [3], More preferably, it is 5-40 weight part. When the amount is less than 1 part by weight, the plasticizing effect is small, and bubbles are likely to remain on the laminated glass plate bonded with the adhesive resin composition layer containing the modified block copolymer hydride [3] interposed therebetween. Conditions such as bonding at high temperatures are required. Moreover, when it exceeds 50 weight part, adhesiveness with glass tends to fall by bleeding out of a plasticizer.

5. Other compounding agents In the present invention, the adhesive resin composition can be blended with a light stabilizer, an ultraviolet absorber, an antioxidant, and the like in order to improve light resistance, light shielding property, heat resistance and the like.

[Light stabilizer]
As a light stabilizer for improving light resistance, a hindered amine light stabilizer is preferable, and a 3,5-di-t-butyl-4-hydroxyphenyl group, 2,2,6,6-tetramethyl in the structure. Examples thereof include compounds having a piperidyl group or a 1,2,2,6,6-pentamethyl-4-piperidyl group. Specific examples include N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N′-diformylalkylenediamines, N, N′-bis (2,2,6). , 6-tetramethyl-4-piperidinyl) -1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butanamine and N-butyl- Examples include reaction products with 2,2,6,6-tetramethyl-4-piperidineamine.

  The amount of the hindered amine light stabilizer added is usually 0.01 to 5 parts by weight, preferably 0.02 to 2.5 parts by weight, more preferably 100 parts by weight of the modified block copolymer hydride [3]. Is 0.04 to 1.0 part by weight. When the amount of the hindered amine light stabilizer is less than this, the light resistance of the adhesive layer of the laminated glass plate may be insufficient, and when it is more than this, the modified block copolymer hydride [3] is formed into a sheet form. At the time of the melt molding process to be molded, the dirt on the T-die of the extruder and the cooling roll may be severe and the workability may be inferior.

[Ultraviolet absorber]
As another means for improving the light resistance, an ultraviolet absorber such as a benzophenone ultraviolet absorber, a salicylic acid ultraviolet absorber, or a benzotriazole ultraviolet absorber can be blended.

  Specific examples of the ultraviolet absorber include benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecaloxy-2- Hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, etc .; As salicylic acid ultraviolet absorbers, 4-t-butylphenyl-2-hydroxybenzoate, phenyl 2-hydroxybenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like; With benzotriazole UV absorber 2- (2-hydroxy-5-methylphenyl) 2H-benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2 -(3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole 2- (3,5-dicumyl-2-hydroxyphenyl) -2H-benzotriazole, 5-chloro-2- (3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2 -(3,5-di-t-amyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzoto Azole, 2- (2-hydroxy-4-octylphenyl) -2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthali (Midylmethyl) phenol, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]] and the like.

  The compounding quantity of a ultraviolet absorber is 0.01-2 weight part normally with respect to 100 weight part of modified block copolymer hydrides [3], Preferably it is 0.02-1 weight part, More preferably, it is 0.04. -0.5 parts by weight. The ultraviolet absorber can further improve the light resistance when used in combination with a hindered amine light resistance stabilizer, but no further improvement is observed even if it is added in excess of the above range.

[Antioxidant]
Thermal stability can also be improved by mix | blending antioxidant. Examples of the antioxidant that can be added include phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, and the like, and phosphorus-based antioxidants with less coloring are preferred.

  Specific examples of phosphorus antioxidants include triphenyl phosphite, triisodecyl phosphite, diphenyl isodecyl phosphite, 2-ethylhexyl diphenyl phosphite tris (nonylphenyl) phosphite, tris (2,4-di-). monophos, such as t-butylphenyl) phosphite, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Phyto compounds; 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite), 4,4′-isopropylidene-bis (phenyl-di-alkyl (C12˜ Diphosphite compounds such as C15) phosphite); 6- [3- (3-t-butyl-4 -Hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetrakis-t-butyldibenzo [d, f] [1.3.2] dioxaphosphine, 6- [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propoxy] -2,4,8,10-tetrakis-t-butyldibenzo [d, f] [1.3.2] dioxaphosphine A compound can be mentioned.

  Specific examples of phenolic antioxidants include pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) proonyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, A compound such as 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene can be exemplified.

  Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, laurylstearyl- 3,3′-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [ 5,5] undecane and the like.

  The blending amount of the antioxidant is usually 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0.1 to 100 parts by weight of the modified block copolymer hydride [3]. -0.5 parts by weight. The antioxidant can be further improved in light resistance when used in combination with a hindered amine light stabilizer, but no further improvement is observed even if it is added in excess of the above range.

6). Adhesive Resin Composition A method for producing an adhesive resin composition by uniformly dispersing the above compounding agent in the modified block copolymer hydride [3] is, for example, by dissolving the compounding agent in an appropriate solvent. Block copolymer hydride containing a compounding agent after being added to a solution of block copolymer hydride [2] which is a precursor of block copolymer hydride [3] having an alkoxysilyl group And a modified block copolymer hydride using a twin-screw kneader, a roll, a Brabender, an extruder, or the like, in which the ethylenically unsaturated silane compound is reacted in the presence of a peroxide. A method in which [3] is melted and the compounding agent is kneaded; when the block copolymer hydride [2] is reacted with the ethylenically unsaturated silane compound in the presence of peroxide, the compounding agent is also kneaded at the same time. How to do; A mixture of the above compounding agent uniformly dispersed in a copolymer hydride [2] and a pellet of the modified block copolymer hydride [3] are mixed and melt-kneaded. For example, a method of uniformly dispersing.

7). Adhesive Resin Composition Layer The adhesive resin composition containing the modified block copolymer hydride [3] of the present invention is usually subjected to a process for producing a laminated glass plate by forming it into a sheet shape. At least one sheet is interposed between a pair of glass plates and bonded together, thereby forming at least one adhesive resin composition layer between the pair of glass plates to produce a laminated glass plate. The thickness of the adhesive resin composition layer is such that the ratio (tr / tg) of the total thickness (tr) of the adhesive resin composition layer to the total thickness (tg) of the pair of glass plates is 0. 1 or more and 4.0 or less. The adhesive resin composition layer may be a single layer or a plurality of layers. In the case of a plurality of layers, adhesive resin composition layers having different compositions may be combined, and another transparent resin layer may be laminated between the plurality of layers.

  The sheet made of the adhesive resin composition containing the modified block copolymer hydride [3] used in the present invention contains the modified block copolymer hydride [3] blended with the above-mentioned compounding agent as necessary. Even if it is a single-layer sheet made of the resin composition, the compounding agent is formed on both sides of the resin composition sheet made of the block copolymer hydride [2] blended with the compounding agent as necessary. It may be a multilayer sheet in which an adhesive resin composition layer containing a modified block copolymer hydride [3] is added.

  The sheet made of the adhesive resin composition containing the modified block copolymer hydride [3] used in the present invention maintains a strong adhesion to glass even after being exposed to a high humidity environment at room temperature for a long time. And since adjustment of water content etc. is insoluble before adhesion | attachment, it is excellent in workability | operativity and can be used conveniently for bonding of glass.

8). Laminated glass plate The laminated glass plate of the present invention has an adhesive resin composition layer containing a modified block copolymer hydride [3] having a specific thickness corresponding to the thickness of the glass plate interposed between the glass plates. The adhesive resin composition is bonded to glass and integrated.

  When a glass plate is used as a sound insulation plate, a transmission loss is reduced due to a coincidence effect in a specific frequency range of sound corresponding to the thickness. For example, when the thickness of the glass plate is 3 to 16 mm, the transmission loss is reduced in the frequency region of 4000 to 750 Hz. The laminated glass plate of the present invention suppresses a decrease in transmission loss in a specific frequency region due to such a coincidence effect and improves sound insulation.

In the laminated glass of the present invention, the total thickness ratio (tr / tg) of the total thickness (tr) of the adhesive resin composition layer to the total thickness (tg) of the pair of glass plates is: Since sufficient sound insulation and light transmittance can be secured, it is 0.1 or more and 4.0 or less, preferably 0.2 or more and 3.0 or less. From this viewpoint, the thickness of one glass plate used in the present invention is not particularly limited as long as it can be applied to the use of a sound insulating plate, but is usually 1.5 to 8 mm, and the thickness of a pair of glass plates The total sum is usually 3.0 to 16 mm. On the other hand, the total thickness of the adhesive resin composition layer of the present invention is usually 0.3 mm or more, preferably 0.5 mm or more. The thicker the adhesive resin composition layer is, the greater the sound insulation effect is and the better the penetration resistance and impact resistance. However, it is usually 10 mm or less, preferably 8 mm or less.
When the thickness of the adhesive resin layer is larger than this, the light transmittance of the adhesive resin composition layer is reduced, or the amount of the modified block copolymer hydride [3] used is increased, resulting in a reduction in economic efficiency. Therefore, it is not preferable.

  Although the kind of glass plate used for this invention is not specifically limited, Usually, the float glass plate shape | molded with soda glass, white plate glass, etc., type | mold plate glass, a tempered glass plate, etc. are used.

  In order to produce the laminated glass plate of the present invention, at least one sheet made of an adhesive resin composition containing a modified block copolymer hydride [3] is interposed between a pair of glass plates, and a vacuum laminator, A heat-resistant rubber bag that can be decompressed may be used and bonded under heat and pressure.

  The laminated glass plate of the present invention has an excellent transparency, but an article imparting a decorative property between a plurality of sheets made of an adhesive resin composition containing a modified block copolymer hydride [3]. Alternatively, an article that shields electromagnetic waves, radiation, infrared rays, heat rays, or the like can be sandwiched.

  The laminated glass plate of the present invention is excellent in transparency, heat resistance, sound insulation, anti-scattering properties when the glass is broken, etc., highway and railway sound insulation walls, building window glass and partition plates, glass doors It is useful as a sunroof material, window glass for automobiles, glass for show windows, design glass, and the like.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited only to these examples. In the following examples and comparative examples, parts and% are based on weight unless otherwise specified. The measurement methods for various physical properties are shown below.
(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
The molecular weights of the block copolymer and the hydride of the block copolymer were measured at 38 ° C. as standard polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent. As a measuring apparatus, HLC8020GPC manufactured by Tosoh Corporation was used.
(2) Hydrogenation rate The hydrogenation rate of the main chain, side chain, and aromatic ring of the block copolymer hydride [2] was calculated by measuring a ¹ H-NMR spectrum.
(3) Evaluation of adhesion to glass plate (peel strength)
A sheet of the adhesive resin composition [4] containing the modified block copolymer hydride [3], a soda glass plate having a thickness of 2 mm, a width of 100 mm, and a length of 75 mm provided with a non-adhesive site at the sheet end. A test piece for a peel test was prepared by vacuum degassing with a vacuum laminator at 150 ° C. for 5 minutes and then vacuum-pressure bonding for 10 minutes. The sheet surface was cut into a width of 15 mm, and a peel strength was measured from a non-adhered portion of the sheet at a peel rate of 50 mm / min based on JIS K 6854-2 by a 180 degree peel test. The peel strength was measured after the initial value after vacuum lamination and after 1000 hours exposure to a high temperature and high humidity environment of 85 ° C. and 85% RH. The greater the peel strength, the better the adhesion to glass.
(4) Evaluation of transparency A sheet made of an adhesive resin composition [4] containing a modified block copolymer hydride [3] is made of two soda glasses having a thickness of 3 mm, a width of 50 mm and a length of 50 mm. Using a vacuum laminator (product name “PVL0202S”, manufactured by Nisshinbo Mechatronics), vacuum degassing for 5 minutes at a temperature of 120 to 150 ° C., followed by vacuum pressure forming for 10 minutes and bonding glass A test piece was prepared, and the total light transmittance was measured with reference to the method of JIS K 7375.
(5) Evaluation of sound transmission loss One or a plurality of sheets made of the adhesive resin composition [4] containing the modified block copolymer hydride [3] are stacked to have a thickness of 1.7 to 3 mm and a width. A sound-insulating glass test plate is created by sandwiching between two soda glass plates of 600 mm and length of 600 mm, and by pressure bonding with a vacuum press machine at a temperature of 120 to 150 ° C. for 10 minutes under a reduced pressure atmosphere of 1 kPa or less. did. Using this sound insulation glass test plate, sound transmission loss was measured in the sound range of 400 to 5000 Hz according to the sound intensity method (JIS A 1441-1).
A general sound insulation board is required to have a larger sound transmission loss in a higher frequency sound range. For example, a sound insulation board for highways has a sound transmission loss of 25 dB or more at 400 Hz and 30 dB or more at 1000 Hz. Is required. Therefore, the higher the sound transmission loss, the better the sound insulation, and it is required to increase at a higher frequency.
(6) Evaluation of heat resistance Using the above sound-insulating glass test plate using glass with a thickness of 3 mm, in the oven, hold only one side of the glass plate using a frame, and do not hold the other glass plate. After standing upright as described above and storing at a temperature of 100 ° C. for 96 hours, the sound-insulating glass test plate was visually observed to evaluate the appearance such as misalignment, discoloration, bubbles, and peeling.
(7) Evaluation of anti-scattering property at the time of cracking Using the above sound-insulating glass test plate using a glass with a thickness of 3 mm, a steel ball with a weight of 2 kg was dropped from a height of 2 m onto the glass surface, and presence or absence of penetration The state of scattering of the broken glass was visually observed.

[Reference Example 1]
Modified block copolymer hydride [3] -1
(Synthesis of block copolymer [1] -1)
550 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene and 0.475 part of n-dibutyl ether were placed in a reactor equipped with a stirrer sufficiently purged with nitrogen, and n-butyllithium (15 Polymerization was started by adding 0.62 part of a% cyclohexane solution). The mixture was reacted at 60 ° C. for 60 minutes with stirring. Measured by gas chromatography. At this time, the polymerization conversion rate was 99.5%.
Next, 50.0 parts of dehydrated isoprene was added and stirring was continued for 30 minutes. At this time, the polymerization conversion rate was 99.5%.
Thereafter, 25.0 parts of dehydrated styrene was further added and stirred for 60 minutes. The polymerization conversion rate at this point was almost 100%. Here, 0.5 part of isopropyl alcohol was added to stop the reaction. The obtained block copolymer [1] -1 had a weight average molecular weight (Mw) of 78,000, a molecular weight distribution (Mw / Mn) of 1.03, and wA: wB = 50: 50.

(Synthesis of block copolymer hydride [2] -1)
Next, the polymer solution was transferred to a pressure-resistant reactor equipped with a stirrer, and diatomaceous earth-supported nickel catalyst (product name “T-8400RL”, manufactured by Zude Chemie Catalysts) as a hydrogenation catalyst and dehydration 100 parts of cyclohexane was added and mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution. A hydrogenation reaction was performed at a temperature of 190 ° C. and a pressure of 4.5 MPa for 6 hours. The weight average molecular weight (Mw) of the block copolymer hydride [2] -1 after the hydrogenation reaction was 78,800, and the molecular weight distribution (Mw / Mn) was 1.04.

After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and then the phenol-based antioxidant pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). ) Propionate] (product name “Songnox 1010”, manufactured by SONGWON) 1.0 part of xylene solution in which 0.1 part was dissolved was added and dissolved.
Next, the above solution was filtered with a metal fiber filter (pore size 0.4 μm, manufactured by Nichidai) to remove minute solids, and then a cylindrical concentration dryer (product name “Contro”, manufactured by Hitachi, Ltd.) ), The solvent cyclohexane, xylene and other volatile components were removed from the solution at a temperature of 260 ° C. and a pressure of 0.001 MPa or less. The molten polymer is continuously filtered at a temperature of 260 ° C. by a polymer filter (manufactured by Fuji Filter) equipped with a stainless sintered filter having a pore diameter of 5 μm connected to a concentration dryer, and then the molten polymer is extruded into a strand form from a die. After cooling, 96 parts of pellets of block copolymer hydride [2] -1 were prepared by a pelletizer. The resulting block copolymer hydride [2] -1 had a weight average molecular weight (Mw) of 77,800 and a molecular weight distribution (Mw / Mn) of 1.04. The hydrogenation rate was almost 100%.

(Synthesis of Modified Block Copolymer Hydride [3] -1)
To 100 parts of pellets of the obtained block copolymer hydride [2] -1, 2.0 parts of vinyltrimethoxysilane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane ( 0.2 parts of a product name “Perhexa (registered trademark) 25B” (manufactured by NOF Corporation) was added, and this mixture was mixed with a resin temperature using a twin screw extruder (product name “TEM37B”, manufactured by Toshiba Machine Co., Ltd.). After kneading at 200 ° C. and a residence time of 60 to 70 seconds, extruding into a strand shape, air cooling, and cutting with a pelletizer, 97 parts of pellets of modified block copolymer hydride [3] -1 having an alkoxysilyl group are obtained. It was.

The obtained block copolymer hydride [3] -1 pellets having an alkoxysilyl group were dissolved in 100 parts of cyclohexane, and then poured into 400 parts of dehydrated methanol to block the block copolymer having an alkoxysilyl group. The hydride [3] -1 was coagulated and filtered, and then vacuum dried at 25 ° C. to isolate 9.5 parts of crumb of the block copolymer hydride [3] -1 having an alkoxysilyl group. The FT-IR spectra, Si-OCH ₃ groups to 1090cm ^-1, 825cm ^-1 and 739cm new absorption band derived from Si-CH ₂ group at ^-1, their ^{1075 cm} -1 of vinyltrimethoxysilane, 808Cm ⁻¹ and 766 cm ⁻¹ were observed at different positions. In the ¹ H-NMR spectrum (in deuterated chloroform), an absorption band based on proton of methoxy group was observed at 3.6 ppm. From the peak area ratio, 100 parts of block copolymer hydride [2] -1 It was confirmed that 1.7 parts of vinyltrimethoxysilane was bound.

[Reference Example 2]
Modified block copolymer hydride [3] -2
(Synthesis of block copolymer hydride [2] -2)
Other than adding 22.5 parts of styrene, 0.54 parts of n-butyllithium (15% cyclohexane solution), 55.0 parts of isoprene and 22.5 parts of styrene in this order to the reaction system as monomers in the polymerization stage. Is polymerized in the same manner as in Reference Example 1 to obtain a block copolymer [1] -2 having wA: wB = 45: 55, which is hydrogenated to obtain a hydride of the block copolymer [2] -2. 96 parts of pellets were obtained. The resulting block copolymer hydride had a weight average molecular weight (Mw) of 88,700 and a molecular weight distribution (Mw / Mn) of 1.04. The hydrogenation rate was almost 100%.

(Synthesis of Modified Block Copolymer Hydride [3] -2)
A modified block copolymer having an alkoxysilyl group was prepared in the same manner as in Reference Example 1 except that 100 parts of the block copolymer hydride [2] -2 pellet was used instead of the block copolymer hydride [2] -1. 97 parts of pellets of polymer hydride [3] -2 were obtained.

  The obtained modified block copolymer hydride [3] -2 was analyzed in the same manner as in Reference Example 1. As a result, vinyltrimethoxysilane 1.3 was added to 100 parts of the block copolymer hydride [2] -2. It was confirmed that 8 parts were combined.

[Reference Example 3]
Modified block copolymer hydride [3] -3
(Synthesis of block copolymer hydride [2] -3)
As a monomer in the polymerization stage, 35.0 parts of styrene, 0.61 part of n-butyllithium (15% cyclohexane solution), 30.0 parts of isoprene and 35.0 parts of styrene were added to the reaction system in this order to polymerize. 95 parts of pellets of hydride of block copolymer [2] -3 were obtained in the same manner as in Reference Example 1 except that block copolymer [1] -3 of wA: wB = 70: 30 was obtained. The resulting block copolymer hydride had a weight average molecular weight (Mw) of 82,300 and a molecular weight distribution (Mw / Mn) of 1.04. The hydrogenation rate was almost 100%.

(Synthesis of Modified Block Copolymer Hydride [3] -3)
Instead of the block copolymer hydride [2] -1, 100 parts of the block copolymer hydride [2] -3 pellets were used, the resin temperature of the twin screw extruder was 210 ° C., and the residence time was 30 to 40 seconds. Except that, 92 parts of pellets of a modified block copolymer hydride [3] -3 having an alkoxysilyl group were obtained in the same manner as in Reference Example 1.

  The obtained modified block copolymer hydride [3] -3 was analyzed in the same manner as in Reference Example 1. As a result, vinyltrimethoxysilane 1.3 was added to 100 parts of the block copolymer hydride [2] -3. It was confirmed that 3 parts were combined.

[Reference Example 4]
Modified block copolymer hydride [3] -4
(Synthesis of block copolymer hydride [2] -4)
As a monomer in the polymerization stage, 12.5 parts of styrene, 0.49 part of n-butyllithium (15% cyclohexane solution), 75.0 parts of isoprene and 12.5 parts of styrene were added to the reaction system in this order for polymerization. 93 parts of pellets of block copolymer hydride [2] -4 were obtained in the same manner as in Reference Example 1 except that the block copolymer [1] -4 having wA: wB = 25: 75 was obtained. The obtained block copolymer hydride had a weight average molecular weight (Mw) of 95,000 and a molecular weight distribution (Mw / Mn) of 1.04. The hydrogenation rate was almost 100%.

(Synthesis of Modified Block Copolymer Hydride [3] -4)
The modified block copolymer having an alkoxysilyl group was prepared in the same manner as in Reference Example 1 except that 100 parts of the pellet of the block copolymer hydride [2] -4 was used instead of the block copolymer hydride [2] -1. 91 parts of pellets of polymer hydride [3] -4 were obtained.

  The obtained modified block copolymer hydride [3] -4 was analyzed in the same manner as in Reference Example 1. As a result, vinyltrimethoxysilane 1.3 was added to 100 parts of the block copolymer hydride [2] -4. It was confirmed that 8 parts were combined.

[Example 1]
(Sheet of Adhesive Resin Composition [4] -1 Containing Modified Block Copolymer Hydride [3] -1)
2-hydroxy-4-n-octoxybenzophenone (product name “Adekastab (registered trademark)) as an ultraviolet absorber was added to 100 parts by weight of the pellets of the modified block copolymer hydride [3] -1 obtained in Reference Example 1. 1413 "(manufactured by ADEKA) and adding a 0.5-mm T-die film melt extrusion molding machine (T-die width 1200 mm) having an extruder equipped with a 90 mmφ screw and a sheet take-up with a satin pattern embossing roll A sheet of the adhesive resin composition [4] -1 having a thickness of 1.2 mm and a width of 1000 mm under molding conditions of a molten resin temperature of 190 ° C., a T die temperature of 190 ° C., and a roll temperature of 50 ° C. Molded. The obtained sheet was wound up and collected on a roll.

(Evaluation of laminated glass plate)
Using a 1.2 mm thick sheet of adhesive resin composition [4] -1, one sheet of adhesive resin composition [4] -1 was placed between two 3 mm thick glass plates. A laminated glass plate was created. At the same time, test samples for the various tests described above were prepared and evaluated for adhesiveness, transparency, sound transmission loss, heat resistance, and anti-scattering property during cracking. The results are shown in Table 1.

[Example 2]
(Sheet of Adhesive Resin Composition [4] -2 Containing Modified Block Copolymer Hydride [3] -2)
Adhesive resin composition having a thickness of 1.2 mm and a width of 1000 mm in the same manner as in Example 1 except that 100 parts by weight of pellets of the modified block copolymer hydride [3] -2 obtained in Reference Example 2 were used. A sheet of product [4] -2 was extruded.
(Evaluation of laminated glass plate)
A test sample was prepared in the same manner as in Example 1 using the obtained sheet of the adhesive resin composition [4] -2, and various tests were performed. The results are shown in Table 1.

[Example 3]
(Sheet of adhesive resin composition “4” -3 obtained by blending a plasticizer with a modified block copolymer hydride [3] -1)
To 100 parts by weight of the pellet of the modified block copolymer hydride [3] -1 obtained in Reference Example 1, 0.5 part of 2-hydroxy-4-n-octoxybenzophenone, which is the same UV absorber as described above, was added. Then, it was extruded at a resin temperature of 190 ° C. using a twin screw extruder (product name “TEM37BS”, manufactured by Toshiba Machine Co., Ltd.) equipped with a side feeder to which a liquid material can be added.
On the other hand, polyisobutene (product name “Nisseki Polybutene LV-100”, number average molecular weight 500, manufactured by JX Nippon Oil & Energy Corporation) as a plasticizer from the side feeder is changed to 100 of the modified block copolymer hydride [3] -1. Continuously added so as to have a ratio of 10 parts by weight with respect to parts by weight, extruded into strands, air-cooled, and then cut with a pelletizer to add polyisobutene to the modified block copolymer hydride [3] -1. 102 parts of pellets of the adhesive resin composition [4] -3 obtained by blending were obtained.
The obtained adhesive resin composition [4] -3 pellets were 1.2 mm thick under the same molding conditions as in Example 1 using the same melt extrusion molding machine and sheet take-up machine as in Example 1. A sheet of the adhesive resin composition [4] -3 having a width of 1000 mm was extruded.
(Evaluation of laminated glass plate)
Using the obtained sheet of adhesive resin composition [4] -3, a test sample was prepared in the same manner as in Example 1, and various tests were performed. The results are shown in Table 1.

[Example 4]
(Sheet of adhesive resin composition “4” -4 obtained by blending a modified block copolymer hydride [3] -1 with a plasticizer)
The same polyisobutene as used in Example 3 was used as a plasticizer, and the amount of polyisobutene was changed to 20 parts by weight with respect to 100 parts by weight of the modified block copolymer hydride [3] -1. In this manner, 113 parts of pellets of the adhesive resin composition [4] -4 were obtained.
The pellets of the obtained adhesive resin composition [4] -4 were melt melt resin temperature 180 ° C., T die temperature 180 ° C., roll temperature 40 using the same melt extrusion molding machine and sheet take-up machine as in Example 1. A sheet of the adhesive resin composition [4] -4 having a thickness of 0.4 mm, 1.2 mm and 3.0 mm, and a width of 1000 mm was extruded and molded under the same molding conditions as in Example 1 except that the temperature was set to ° C.
(Evaluation of laminated glass plate)
Using the obtained sheet of the adhesive resin composition [4] -4 having a thickness of 1.2 mm, test samples were prepared in the same manner as in Example 1, and various tests were performed. The results are shown in Table 1.

[Example 5]
(Evaluation of laminated glass plate)
Using the 1.2 mm-thick sheet of the adhesive resin composition [4] -4 prepared in Example 4, the adhesive resin composition [4] -4 was placed between two 3 mm-thick glass plates. Two sheets were arrange | positioned and the laminated glass plate was created. At the same time, test samples for the various tests described above were prepared, and various tests were performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 6]
(Sheet of the adhesive resin composition “4” -5 obtained by blending a modified block copolymer hydride [3] -2 with a plasticizer)
Using the same polyisobutene as in Example 3 as pellets and plasticizer of the modified block copolymer hydride [3] -2 obtained in Reference Example 2, 100 weight of the modified block copolymer hydride [3] -2 104 parts of pellets of the adhesive resin composition [4] -5 were obtained in the same manner as in Example 3 except that the amount of polyisobutene was 10 parts by weight with respect to parts.
The pellets of the obtained adhesive resin composition [4] -5 were melt melt resin temperature 180 ° C., T die temperature 180 ° C., roll temperature 40 using the same melt extrusion molding machine and sheet take-up machine as in Example 1. A sheet of the adhesive resin composition [4] -5 having a thickness of 1.2 mm and a width of 1000 mm was extruded and molded under the same molding conditions as in Example 1 except that the temperature was set to ° C.
(Evaluation of laminated glass plate)
Using the obtained sheet of adhesive resin composition [4] -5, test samples were prepared in the same manner as in Example 1, and various tests were performed. The results are shown in Table 1.

[Example 7]
(Sheet of adhesive resin composition “4” -6 formed by blending a modified block copolymer hydride [3] -1 with a plasticizer)
The modified block copolymer hydride [3] -1 pellets obtained in Reference Example 1 and polyisobutene (product name “Nisseki Polybutene HV-300”, number average molecular weight 1400, manufactured by JX Nippon Oil & Energy Corporation) as a plasticizer. In the same manner as in Example 3 except that the amount of polyisobutene is 40 parts by weight with respect to 100 parts by weight of the modified block copolymer hydride [3] -1. 4] 132 parts of pellets of -6 were obtained.
The pellets of the resulting adhesive resin composition [4] -6 were melted at a resin temperature of 180 ° C., a T-die temperature of 180 ° C., and a roll temperature of 40 using the same melt extrusion molding machine and sheet take-up machine as in Example 1. A sheet of the adhesive resin composition [4] -6 having a thickness of 1.2 mm and a width of 1000 mm was extruded and molded under the same molding conditions as in Example 1 except that the temperature was set to ° C.
(Evaluation of laminated glass plate)
A test sample was prepared in the same manner as in Example 1 using the obtained sheet of the adhesive resin composition [4] -6, and various tests were performed. The results are shown in Table 1.

[Comparative Example 1]
(Sheet of adhesive resin composition “4” -7 formed by blending a plasticizer with a modified block copolymer hydride [3] -3)
Using the same polyisobutene as in Example 3 as pellets and plasticizer of the modified block copolymer hydride [3] -3 obtained in Reference Example 3, 100 weight of the modified block copolymer hydride [3] -3 In the same manner as in Example 3 except that the amount of polyisobutene was 20 parts by weight with respect to parts and the resin temperature of the twin screw extruder was 200 ° C., 112 parts of pellets of the adhesive resin composition [4] -7 were added. Obtained.
Using the same melt extrusion molding machine and sheet take-up machine as in Example 1, the resulting adhesive resin composition [4] -7 pellets were melted at a resin temperature of 195 ° C., a T-die temperature of 195 ° C., and a roll temperature of 60. A sheet of the adhesive resin composition [4] -7 having a thickness of 1.2 mm and a width of 1000 mm was extruded and molded under the same molding conditions as in Example 1 except that the temperature was set to ° C.
(Evaluation of laminated glass plate)
A test sample was prepared in the same manner as in Example 1 using the obtained sheet of the adhesive resin composition [4] -7, and various tests were performed. The results are shown in Table 1.

[Comparative Example 2]
(Sheet of adhesive resin composition “4” -8 formed by blending a modified block copolymer hydride [3] -4 with a plasticizer)
Using the same polyisobutene as in Example 3 as pellets of the modified block copolymer hydride [3] -4 obtained in Reference Example 4 and a plasticizer, 100 weight of the modified block copolymer hydride [3] -3 107 parts of the pellets of the adhesive resin composition [4] -8 were obtained in the same manner as in Example 3 except that the amount of polyisobutene was 20 parts by weight with respect to parts.
The obtained adhesive resin composition [4] -8 pellets were melted at a temperature of 185 ° C., T-die temperature of 185 ° C., and roll temperature of 45 using the same melt extrusion molding machine and sheet take-up machine as in Example 1. A sheet of the adhesive resin composition [4] -8 having a thickness of 1.2 mm and a width of 1000 mm was extruded and molded under the same molding conditions as in Example 1 except that the temperature was set to ° C.
(Evaluation of laminated glass plate)
Using the obtained sheet of the adhesive resin composition [4] -8, a test sample was prepared in the same manner as in Example 1, and various tests were performed. The results are shown in Table 1.

[Comparative Example 3]
(Evaluation of laminated glass plate)
The sheet of the adhesive resin composition [4] -4 having a thickness of 0.4 mm prepared in Example 4 was used, and the adhesive resin composition [4] -4 having a thickness of 2 mm between two glass plates was used. One sheet was placed to create a laminated glass plate. At the same time, test samples for the various tests described above were prepared, and various tests were performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 4]
(Evaluation of glass plate)
In place of the laminated glass plate, only a glass plate having a thickness of 6 mm, a width of 600 mm, and a length of 600 mm having the same thickness as the total thickness (6 mm) of the glass plates used for the laminated glass plate was used. Various tests were conducted as in 1. The results are shown in Table 1.

[Comparative Example 5]
(Evaluation of polycarbonate plate)
In place of the laminated glass plate, only a polycarbonate plate having a thickness of 8 mm, a width of 600 mm, and a length of 600 mm having a thickness substantially equal to the total thickness of the laminated glass plate (7.2 to 8.4 mm) is used. Various tests were performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 8]
(Evaluation of laminated glass plate)
Using the 1.2 mm thick sheet of the adhesive resin composition [4] -4 prepared in Example 4, the adhesive resin composition [4] − between two 1.7 mm thick glass plates. 4 sheets were laminated and the test sample of the various tests mentioned above was created, and the laminated glass plate was created. At the same time, various tests were conducted in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 6]
(Evaluation of glass plate)
Instead of the laminated glass plate, the laminated glass plate used in Example 8 has a weight per unit area substantially equal to a weight per unit area of 1.1 g / cm ² , a thickness of 4 mm, a width of 600 mm, and a length of 600 mm. Various tests were performed in the same manner as in Example 1 using a glass plate (weight per unit area = 1.0 g / cm ² ). The results are shown in Table 2.

[Example 9]
(Sheet of Adhesive Resin Composition [4] -9 Made by Mixing Plasticizer with Block Copolymer Hydride [2] -1)
The block copolymer hydride [2] -1 was used in place of the modified block copolymer hydride [3] -1, the same polyisobutene as in Example 3 was used as a plasticizer, and the block copolymer hydride [ 2] -1 pellets of adhesive resin composition [4] -9 were obtained in the same manner as in Example 3 except that the amount of polyisobutene was 20 parts by weight with respect to 100 parts by weight.
The obtained adhesive resin composition [4] -9 pellets were 1.6 mm thick under the same molding conditions as in Example 1 using the same melt extrusion molding machine and sheet take-up machine as in Example 1. A sheet of adhesive resin composition [4] -9 having a width of 1000 mm was extruded.

(Evaluation of laminated glass plate)
Using a sheet of adhesive resin composition [4] -9 and a 0.4 mm thick sheet of adhesive resin composition [4] -4 prepared in Example 4, two glass plates of 3 mm thickness were used. 1 sheet of 0.4 mm thick adhesive resin composition [4] -4/1 sheet of 1.6 mm thick adhesive resin composition [4] -9 / adhesive resin composition [ 4] -4 sheets having a thickness of 0.4 mm were laminated in this order, and a laminated glass plate was prepared in the same manner as in Example 1. tr / tg = 0.4. At the same time, test samples for the various tests described above were prepared, and various tests were performed in the same manner as in Example 1.
As a result, the adhesiveness with the glass plate is 10 N / cm or more, the total light transmittance is 91%, and the sound transmission loss of the laminated glass plate is 32 dB (500 Hz), 36 dB (1000 Hz), 36 dB (2000 Hz), It was 41 dB (4000 Hz). Moreover, there was no abnormality in the heat resistance test, and in the prevention of scattering at the time of cracking, there was no penetration and there was no scattering of the broken glass.

[Example 10]
(Evaluation of laminated glass plate)
The sheet of the adhesive resin composition [4] -4 created in Example 4 and having a thickness of 3.0 mm was used, and the adhesive resin composition [4] -4 was bonded between two glass sheets having a thickness of 1 mm. Two sheets were arranged to prepare a laminated glass plate having a total thickness of 8 mm. tr / tg = 3.0.
At the same time, test samples for the various tests described above were prepared, and various tests were performed in the same manner as in Example 1.
As a result, the total light transmittance was 91%, and the sound transmission loss of the laminated glass plate was 28 dB (500 Hz), 33 dB (1000 Hz), 37 dB (2000 Hz), and 39 dB (4000 Hz) at each frequency. Moreover, there was no abnormality in the heat resistance test, and in the prevention of scattering at the time of cracking, there was no penetration and there was no scattering of the broken glass.

From the results of Examples and Comparative Examples, the following can be understood.
A laminated glass plate having an adhesive resin composition layer containing the specific modified block copolymer hydride [3] of the present invention suppresses a decrease in sound transmission loss in a specific frequency range due to the coincidence effect of glass. It is advantageous for improving sound insulation. In the examples, a decrease in sound transmission loss around a frequency of 2000 Hz, which is characteristic of glass having a thickness of 6 mm, is suppressed by introducing the adhesive resin composition layer of the present invention. In addition, the glass and the adhesive resin composition layer have sufficient adhesive strength, and have excellent transparency, high heat resistance, penetration resistance and high scattering prevention effect when the glass is broken ( Examples 1-7, Example 9).

  When the content of the polymer block [A] containing as a main component a repeating unit derived from an aromatic vinyl compound is too large relative to the specific modified block copolymer hydride of the present invention [3], heat resistance is high. However, it is inferior in flexibility, and the effect of suppressing a decrease in sound transmission loss in a specific frequency range is low. Further, the penetration resistance of the laminated glass plate and the scattering prevention effect when the glass is broken are also low (Comparative Example 1).

  When there is too much content of polymer block [B] which has the repeating unit derived from a chain conjugated diene compound as a main component with respect to the specific modified block copolymer hydride of the present invention [3], flexibility is increased. It is excellent and advantageous in suppressing a decrease in sound transmission loss in a specific frequency range. Moreover, the penetration resistance and the scattering prevention effect when the glass is broken are also high. However, the heat resistance is insufficient (Comparative Example 2).

  Even when the adhesive resin composition containing the specific modified block copolymer hydride [3] of the present invention is used, when the thickness of the adhesive resin composition layer is thinner than a specific range, that is, on the laminated glass plate. When the ratio (tr / tg) of the total thickness (tr) of the adhesive resin composition layer to the total thickness (tg) of the glass plate to be used is less than 0.1, sound transmission in a specific frequency range It is insufficient to suppress the loss reduction (Comparative Example 3).

  The laminated glass plate of the present invention has superior transparency and high sound transmission loss in a low frequency range (1000 Hz or less) compared with the case where a polycarbonate plate having a total thickness is almost equal, and the glass plate has a coincidence effect. The generated sound transmission loss in the vicinity of 2000 Hz is equal to or higher than that of polycarbonate, and is excellent in sound insulation. (Examples 1-7, Example 9, Comparative Example 5)

  The laminated glass plate of the present invention suppresses a decrease in sound transmission loss in the frequency region where the coincidence effect occurs in the glass plate when the weight per unit area is substantially the same as that of the glass plate alone, and provides sound insulation. It can be improved. (Example 8, Comparative Example 6)

In the laminated glass plate of the present invention, when the weight per unit area is substantially equal to the weight per unit area of the polycarbonate plate (Example 10: total thickness 8 mm, weight per unit area 1.05 g / cm ² ). Shows sound transmission loss equivalent to that of a polycarbonate plate (Comparative Example 5: thickness 8 mm, weight per unit area 0.96 g / cm ² ). Since the surface layer is glass, scratch resistance and contamination resistance are as excellent as glass, and the weight is reduced by about 50% compared to a glass plate of the same thickness.

  The laminated glass plate of the present invention is a sound insulating wall for highways and railways, window glass and partition plates for buildings, glass doors, roof glass, automotive windshields and sunroof glass, show window glass, design glass, etc. Useful as.

Claims (3)

Between a pair of glass plates,
At least two polymer blocks [A] mainly composed of repeating units derived from an aromatic vinyl compound, and at least one polymer block [B] mainly composed of repeating units derived from a chain conjugated diene compound. When the weight fraction of the whole polymer block [A] in the entire block copolymer is wA and the weight fraction of the whole polymer block [B] in the whole block copolymer is wB, Block copolymer hydride [2] in which 90% or more of all unsaturated bonds of hydrogenated block copolymer [1] having a ratio of wA to wB (wA: wB) of 30:70 to 60:40 [2] ] Of the adhesive resin composition layer containing the modified block copolymer hydride [3], wherein the alkoxysilyl group is introduced, and the total thickness (tg) of the glass plate thickness Total (tr) of the ratio (tr / tg) is a glass plate combined with bonded by interposing at least one layer of the adhesive resin composition layer is 0.1 to 4.0. The laminated glass plate of Claim 1 which the said adhesive resin composition mix | blends 1-50 weight part of plasticizers with respect to 100 weight part of modified block copolymer hydrides [3]. The laminated glass sheet according to claim 2, wherein the plasticizer is a hydrocarbon polymer having a number average molecular weight of 300 to 3,000.