JP2007253469A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate excellent in transparency, sound insulation, penetration resistance and impact resistance and suitable for a laminated glass and the like improved further in penetration resistance and impact resistance. <P>SOLUTION: The laminate is the one in which an intermediate film is sandwiched between two sheets of transparent substrates and glued into integrity to form the laminate. The intermediate film comprises a laminated film between a layer of a composition containing a polyvinyl butyral (PVB layer) and a crosslinked layer of a composition containing an ethylene/vinyl acetate copolymer containing an organic peroxide (EVA layer), the thickness of the PVB layer is ≥0.1 mm, and the thickness of the EVA layer is ≥0.1 mm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a laminate used for laminated glass, film tempered glass, and the like excellent in impact resistance, penetration resistance, crime prevention and the like used for automobiles, railway vehicles, buildings, showcases and the like.

  Generally, laminated glass having a structure in which a transparent adhesive layer (intermediate film) is sandwiched between glass plates is used for glass used for automobiles, particularly windshields. The transparent adhesive layer is formed of, for example, a PVB film, an EVA film, or the like, and the presence of the transparent adhesive layer improves the penetration resistance of the laminated glass. In addition, broken glass fragments remain attached to the transparent adhesive layer in response to an impact from the outside, thus preventing scattering. For this reason, for example, even if a laminated glass of an automobile is broken for the purpose of theft or intrusion, the window cannot be opened freely, so that it is useful as a security glass. Such a laminated glass is described in Patent Document 1, for example.

  On the other hand, for example, automobile door glass and fitted glass are generally less likely to be destroyed in an accident, and therefore do not require the penetration resistance or the like of the windshield, so a slightly reinforced low-strength glass. A board is used. However, when only such a single glass plate is used, there are the following drawbacks. That is, (1) Inferior to laminated glass in terms of impact resistance, penetration resistance, etc. (2) If broken for the purpose of theft or intrusion, it breaks into many pieces and the window is opened freely And so on. For this reason, it is also considered to use glass having characteristics such as laminated glass for the door glass and the fitted glass. As glass suitable for such applications, film tempered glass in which a glass plate and a plastic film are bonded via a transparent adhesive layer is described in Patent Documents 2 and 3, for example.

  Such an interlayer film (transparent adhesive layer) that bonds the two glass plates of laminated glass or the glass plate of the film tempered glass and the plastic film has excellent adhesion and penetration resistance as described above. It has been demanded. In particular, high performance is required for laminated glass using two glass plates. Furthermore, recently, high sound insulation is also required to block noise outside the vehicle.

  However, a laminated glass using a PVB film as an interlayer film for laminated glass has good penetration resistance and impact resistance. However, since moisture resistance is not sufficient, transparency and adhesiveness may deteriorate due to long-term use. is there.

  On the other hand, a laminated glass using an EVA film can obtain good sound insulation and excellent water resistance, adhesion and penetration resistance, but the transparency may not be sufficient.

  In Patent Document 4 (Japanese Patent Application Laid-Open No. 2004-50750), since it has excellent moisture resistance, transparency and adhesiveness can be maintained over a long period of time, and sound insulation, penetration resistance, and impact resistance are remarkably good. As a glass laminate, a glass having a first adhesive resin layer mainly composed of polyvinyl butyral resin and a second adhesive resin layer mainly composed of ethylene-vinyl acetate copolymer resin between substrates. Laminates have been proposed.

JP 2002-187746 A JP 2002-046217 A JP 2002-068785 A JP 2004-50750 A

  Laminated glass having a composite film including a PVA layer and an EVA layer described in Patent Document 4 is relatively excellent in transparency, sound insulation, penetration resistance, impact resistance, etc., but under low temperature conditions or severely It has become clear that sufficient impact resistance may not be exhibited with respect to impact, and further improvement is necessary.

  An object of the present invention is to provide a laminate suitable for laminated glass and the like which are excellent in transparency, sound insulation, penetration resistance and impact resistance, and further improved in penetration resistance and impact resistance.

  In addition, the present invention is not only excellent in transparency, sound insulation, adhesion, penetration resistance and impact resistance, but also suitable for laminated glass and the like having further improved penetration resistance at low temperatures and impact resistance. The purpose is to provide a body.

  The present inventor further investigated the viscoelastic properties of the PVB layer and the EVA layer, which are the materials of the intermediate film, in order to obtain a laminated body suitable for laminated glass and the like having further improved penetration resistance and impact resistance. When the tan δ of the PVB layer and the tan δ of the EVA layer were measured from a high temperature to a low temperature, a graph as shown in FIG. 4 was obtained. That is, the PVB layer has a high tan δ at normal temperature (that is, high vibration absorption characteristics), and the EVA layer has a high tan δ at low temperature (that is, high vibration absorption characteristics). Based on these findings, further studies have been made and the present invention has been achieved.

The above purpose is
An intermediate film is sandwiched between two transparent substrates and bonded and integrated,
The intermediate film includes a laminated film of a layer of a composition containing polyvinyl butyral (PVB layer) and a cross-linked layer (EVA layer) of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide, and,
A laminate in which the PVB layer has a thickness of 0.1 mm or more and the EVA layer has a thickness of 0.1 mm or more;
A laminated body in which an intermediate film is sandwiched between two transparent substrates and bonded and integrated,
The intermediate layer is a crosslinked layer (EVA layer) of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide, a layer of a composition containing polyvinyl butyral (PVB layer), and an EVA layer in this order. Including a laminated three-layer laminated film, and
A laminate characterized in that the PVB layer has a thickness of 0.1 mm or more and the total thickness of the EVA layer is 0.1 mm or more; and an intermediate film is sandwiched between two transparent substrates It is a laminate that is bonded and integrated,
The interlayer is a layer of a composition containing polyvinyl butyral (PVB layer), a crosslinked layer of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide (EVA layer), and a PVB layer in this order. Including a laminated three-layer laminated film, and
A laminate in which the total thickness of the PVB layers is 0.1 mm or more and the thickness of the EVA layers is 0.1 mm or more;
Is achieved.

Preferred embodiments of the interlayer film for laminated glass of the present invention are as follows.
(1) The total thickness of all PVB layers is in the range of 0.1 to 2.0 mm. If the thickness exceeds 2.0 mm, the thickness of the interlayer film is too large, the resulting laminate is bulky, and the transparency is also unfavorable. It is not preferable. On the other hand, when the thickness is less than 0.1 mm, the contribution of PVB characteristics (eg, high viscoelasticity at room temperature) is not sufficient. It is particularly preferred that the total thickness of all PVB layers is in the range of 0.1 to 0.6 mm.
(2) The total thickness of all EVA layers is in the range of 0.1 to 1.0 mm. If the thickness exceeds 1.0 mm, the thickness of the interlayer film is too large, the resulting laminate is bulky, and the transparency is also unfavorable. It is not preferable. On the other hand, in the case of less than 0.1 mm, the contribution of EVA characteristics (eg, high viscoelasticity at low temperature, moisture resistance, sound insulation) is not sufficient. The total thickness of all EVA layers is preferably in the range of 0.6 to 1.0 mm.
(3) The ratio of the total thickness of all EVA layers to the total thickness of all PVB layers (total EVA layer / all PVB layers) is 1 to 6 (particularly 1 to 4). The small total thickness of all PVB layers and all EVA layers can be a measure for obtaining excellent penetration resistance.
(4) The total thickness of all PVB layers and all EVA layers is in the range of 0.3 to 3.0 mm (preferably in the range of 0.7 to 1.5 mm, particularly in the range of 0.7 to 1.0 mm). is there. A thickness suitable for laminated glass and the like can be obtained.
(5) The vinyl acetate unit of the ethylene / vinyl acetate copolymer is in the range of 23 to 38% by mass with respect to 100 parts by mass of the ethylene vinyl acetate copolymer. Excellent transparency.
(6) The ethylene / vinyl acetate copolymer has an organic peroxide of 0.05 to 4.0 parts by mass (particularly 0.05 to 1.0 part by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer) Part).
(7) The two transparent substrates are both glass plates. Thereby, a general laminated glass is comprised.
(8) One of the two transparent substrates is a glass plate and the other is a plastic film. Generally, film reinforced (laminated) glass is constituted.
(9) The two transparent substrates are both plastic films.

  The laminated body suitable for the laminated glass and the like of the present invention has a laminated film of an EVA layer and a PVB layer with a layer thickness within a specific range, respectively, and thereby, transparency, adhesion, sound insulation, penetration resistance In addition to having good impact resistance, excellent penetration resistance and impact resistance can be obtained even under severe conditions (low temperature or severe impact), so that the penetration resistance and impact resistance have been further improved. It can be said that the laminate is suitable for glass or the like. That is, the inventor pays attention to mutually different viscoelasticity of the EVA layer and the PVB layer, finds a combination of layer thicknesses in which the respective characteristics are exhibited synergistically, and further improves the penetration resistance and impact resistance. A laminated body suitable for the laminated glass and the like obtained is obtained.

  A laminate suitable for the laminated glass and the like of the present invention includes a layer of a composition containing polyvinyl butyral (PVB layer) and a crosslinked layer of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide (EVA). A basic structure in which a laminated film including a layer is sandwiched between transparent substrates.

  The laminated body suitable for the laminated glass of the present invention will be described in detail below with reference to the drawings.

  FIG. 1 is a cross-sectional view showing an example of an embodiment of a laminate according to the present invention. The laminated body 10 in FIG. 1 is obtained by bonding and integrating two glass plates 11A and 11B with an intermediate film 12. The intermediate film 12 is a two-layer laminated film in which an EVA layer 13 and a PVB layer 14 are laminated, and the glass plate 11A and the EVA layer 13 and the glass plate 11B and the PVB layer 14 are in contact with each other. The intermediate film 12 includes a PVB layer 14 having good transparency, penetration resistance and impact resistance, and an EVA layer 13 for compensating for the defects (moisture resistance, adhesion), and is particularly resistant to low temperatures. In order to improve the penetrability, the layer thickness of the EVA layer 13 and the PVB layer 14 is set to a specific range. That is, since the thickness of the PVB layer is set to 0.1 mm or more and the thickness of the EVA layer is set to 0.1 mm or more (preferably 0.6 mm or more), the obtained laminate has transparency, adhesiveness, In addition to good sound insulation, penetration resistance and impact resistance, it also excels in penetration resistance and impact resistance under more severe conditions (low temperature or severe impact). As described above, the PVB layer has a high tan δ at room temperature (that is, high vibration absorption characteristics), and the EVA layer has a high tan δ at low temperature (that is, high vibration absorption characteristics). Each layer thickness is set so that these characteristics contribute synergistically.

  FIG. 2 is a cross-sectional view showing an example of a preferred embodiment of the laminate of the present invention. The laminated body 20 of FIG. 2 is obtained by bonding and integrating two glass plates 21 </ b> A and 21 </ b> B with an intermediate film 22. The intermediate film 22 is a three-layer laminated film in which an EVA layer 23A, a PVB layer 24, and an EVA layer 23B are laminated in this order. The EVA layers 23A and 23B are in contact with both the glass plate 21A and the glass plate 21B, respectively. Yes. Since both of the glass plates 21A and 21B are in contact with the EVA layers 23A and 23B, the adhesion and water resistance between the glass plates 21A and 21B and the intermediate film 22 are greatly improved. Is greatly suppressed and durability is also improved. In the intermediate film of this three-layer laminated film, the thickness of the PVB layer is set to 0.1 mm or more, and the total thickness of the two EVA layers is set to 0.1 mm or more (preferably 0.6 mm or more). As a result, the resulting laminate has not only good transparency, adhesion, sound insulation, penetration resistance and impact resistance, but also penetration resistance and impact resistance under more severe conditions (low temperature or severe impact). Also excellent.

  FIG. 3 is a cross-sectional view showing an example of a preferred embodiment of the laminate of the present invention. The laminated body 30 in FIG. 3 is obtained by bonding and integrating two glass plates 31A and 31B with an interlayer film 32 for laminated glass. The intermediate film 32 is a three-layer laminated film in which a PVB layer 34A, an EVA layer 33, and a PVB layer 34B are laminated in this order, and the PVB layer 34A and the PVB layer 34B are placed on both the glass plate 31A and the glass plate 31B, respectively. It touches. For this reason, the laminated glass which transparency improved especially is obtained. In the intermediate film of the three-layer laminated film, the total thickness of the two PVB layers is set to 0.1 mm or more, and the thickness of the EVA layer is set to 0.1 mm or more (preferably 0.6 mm or more). As a result, the resulting laminate has not only good transparency, adhesion, sound insulation, penetration resistance and impact resistance, but also penetration resistance and impact resistance under more severe conditions (low temperature or severe impact). Also excellent.

  1 to 3, one of the glass plates may be a transparent plastic film. In that case, it may be called film tempered glass. Alternatively, both of the glass plates may be transparent plastic films. Moreover, although the example of 2 layer structure and 3 layer structure was shown as an intermediate film for laminated glasses, as long as at least 1 layer of EVA layer and PVB layer is used, respectively, a structure of 4 layers or more may be used.

  In the laminate of the present invention, the total thickness of all PVB layers is preferably in the range of 0.1 to 2.0 mm (particularly in the range of 0.1 to 0.6 mm). If the thickness exceeds 2.0 mm, the thickness of the interlayer film is too large, the resulting laminate is bulky, and the transparency is also unfavorable. On the other hand, when the thickness is less than 0.1 mm, the contribution of PVB characteristics (eg, high viscoelasticity at room temperature) is not sufficient. Further, the total thickness of all EVA layers is preferably in the range of 0.1 to 1.0 mm (particularly in the range of 0.6 to 1.0 mm). If the thickness exceeds 1.0 mm, the thickness of the interlayer film is too large, the resulting laminate is bulky, and the transparency is also unfavorable. On the other hand, when the thickness is less than 0.1 mm, the contribution of the EVA characteristics EVA characteristics (eg, high viscoelasticity at low temperature, moisture resistance, sound insulation) is not sufficient.

  Furthermore, the ratio (total EVA layer / total PVB layer) of the total thickness of all EVA layers to the total thickness of all PVB layers is 1 to 6 (particularly 1 to 4). This is a measure for reducing the total thickness of all PVB layers and all EVA layers in order to obtain excellent penetration resistance. The total thickness of all PVB layers and all EVA layers is in the range of 0.3 to 3.0 mm (preferably in the range of 0.7 to 1.5 mm, particularly in the range of 0.7 to 1.0 mm). . A thickness suitable for laminated glass or the like can be obtained without the resulting laminate being bulky.

  The laminated glass of the present invention can be designed to have appropriate performance in terms of impact resistance, penetration resistance, transparency, etc. when one of the glass plates is plastic film (film reinforced glass). For example, it can be used for glass such as window glass provided in various vehicle bodies and buildings, or glass such as showcases and show windows. Both glass plates can be designed to exhibit particularly excellent impact resistance and improved penetration resistance, and can be used for various applications including laminated glass.

  The glass plate used in the present invention is usually silicate glass. In the case of film tempered glass, the glass plate thickness varies depending on the place where it is installed. For example, when it is used for a side glass and a fitted glass of an automobile, it is not necessary to make it thick like a windshield, generally 0.1 to 10 mm, and preferably 0.3 to 5 mm. The one glass plate 1 is reinforced chemically or thermally.

  In the case of a laminated glass that is both a glass plate suitable for an automobile windshield or the like, the thickness of the glass plate is generally 0.5 to 10 mm, and preferably 1 to 8 mm.

  The interlayer film for laminated glass of the present invention is a film having at least one EVA layer and PVB layer as described above.

  The PVB resin composition constituting the PVB layer generally contains a PVB resin, a plasticizer, an ultraviolet absorber, and the like. As the PVB resin, those having a polyvinyl acetal unit of 70 to 95% by weight, a polyvinyl acetate unit of 1 to 15% by weight and an average degree of polymerization of 200 to 3000, particularly 300 to 2500 are preferred.

  Examples of the plasticizer for the PVB resin composition include organic plasticizers such as monobasic acid esters and polybasic acid esters, and phosphoric acid plasticizers.

  Monobasic acid esters include organic acids such as butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid), decylic acid, and tris. Esters obtained by reaction with ethylene glycol are preferred, in particular triethylene-di-2-ethylbutyrate, triethylene glycol-di-2-ethylhexoate, triethylene glycol-di-capronate, triethylene glycol- Di-n-octoate is preferred. An ester of the above organic acid with tetraethylene glycol or tripropylene glycol can also be used.

  As the polybasic acid ester plasticizer, for example, an ester of an organic acid such as adipic acid, sebacic acid or azelaic acid and a linear or branched alcohol having 4 to 8 carbon atoms is preferable. Kate, dioctyl azelate and dibutyl carbitol adipate are preferred.

  As the phosphoric acid plasticizer, tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate and the like are preferable.

  In the PVB resin composition, if the amount of the plasticizer is small, the film formability is deteriorated, and if it is too large, the durability during heat resistance is impaired. It is preferable to include 10 parts by mass, particularly 10 to 40 parts by mass.

  In the PVB resin composition of the present invention, a benzophenone compound, a triazine compound, a benzoate compound, a hindered amine compound, or the like can be used as an ultraviolet absorber (UV absorber). Benzophenone compounds are preferred because yellowing is suppressed.

  Preferred examples of the benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-n-octylbenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, particularly 2-hydroxy-4-n-octylbenzophenone, 2,2'-dihydroxy- 4,4′-dimethoxybenzophenone is preferred.

  In a PVB layer, it is preferable to use the said ultraviolet absorber 0.05-1.0 mass part (especially 0.1-0.2 mass part) with respect to 100 mass parts of PVB.

  Furthermore, the PVB resin composition may contain an alkali or alkaline earth metal salt of a fatty acid (generally used as an adhesion modifier).

  Examples of alkaline earth metal salts of the above fatty acids include magnesium formate, magnesium acetate, magnesium lactate, magnesium stearate, magnesium octylate, calcium formate, calcium acetate, calcium lactate, calcium stearate, calcium octylate, barium formate, acetic acid Barium, barium lactate, barium stearate, barium octylate and the like; and examples of alkali metal salts of fatty acids include potassium formate, potassium acetate, potassium lactate, potassium stearate, potassium octylate, sodium formate, sodium acetate, sodium lactate , Sodium stearate, sodium octylate and the like.

  Additives such as stabilizers and antioxidants may be added to the PVB resin composition to further prevent deterioration.

  EVA used for the EVA resin composition constituting the EVA layer generally has a vinyl acetate content of 23 to 38% by mass, more preferably 23 to 38% by mass, and particularly preferably 23 to 28% by mass. When the vinyl acetate content is less than 23% by mass, the transparency of the resin obtained when crosslinked and cured at a high temperature is not sufficient. Conversely, when the vinyl acetate content exceeds 38% by mass, the impact resistance when a security glass is obtained. The penetration resistance tends to be insufficient. Moreover, it is preferable that the melt flow index (MFR) of EVA is 4.0-30.0 g / 10min, especially 8.0-18.0g / 10min. Pre-crimping becomes easy.

  The EVA resin composition contains an organic peroxide and an ultraviolet absorber in the EVA, and may further contain various additives such as a crosslinking aid, an adhesion improver, and a plasticizer as necessary. it can.

  Examples of the ultraviolet absorber include benzophenone compounds, triazine compounds, benzoate compounds, and hindered amine compounds. From the viewpoint of suppressing yellowing, benzophenone compounds are preferred.

  In the EVA layer, it is preferable to use 0.05 to 1.0 parts by mass (particularly 0.1 to 0.2 parts by mass) of the ultraviolet absorber with respect to 100 parts by mass of EVA.

  In the present invention, any organic peroxide can be used in combination as long as it decomposes at a temperature of 100 ° C. or higher to generate radicals. The organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing (bonding) temperature, the heat resistance of the adherend, and the storage stability. In particular, those having a decomposition temperature of 70 hours or more with a half-life of 10 hours are preferred.

  Examples of this organic peroxide include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3-di- t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α, α′-bis (t-butylperoxy) Isopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) valerate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3 , 3,5-trimethylcyclohexane, t-butyl peroxybenzoate, benzoyl peroxide, t-butyl peroxyacetate, methyl ethyl ketone pero Oxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, butyl hydroperoxide, p-menthane hydroperoxide, p-chlorobenzoyl peroxide, hydroxyheptyl peroxide, chlorohexanone peroxide, octanoyl peroxide Oxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octoate, succinic acid peroxide, acetyl peroxide, m-toluoyl peroxide, t-butyl peroxyisobutylene and 2,4-dichlorobenzoyl peroxide Can be mentioned.

  The EVA layer is used to improve or adjust various physical properties of the film (optical properties such as mechanical strength, adhesiveness, transparency, heat resistance, light resistance, crosslinking speed, etc.), and in particular to improve mechanical strength. It preferably contains a group-containing compound, a methacryloxy group-containing compound and / or an epoxy group-containing compound.

  The acryloxy group-containing compound and methacryloxy group-containing compound to be used are generally acrylic acid or methacrylic acid derivatives, and examples thereof include acrylic acid or methacrylic acid esters and amides. Examples of ester residues include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group. Group, 3-chloro-2-hydroxypropyl group. In addition, polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane, and pentaerythritol, and esters of acrylic acid or methacrylic acid can also be used.

  Examples of amides include diacetone acrylamide.

  Examples of polyfunctional compounds (crosslinking aids) include esters obtained by esterifying a plurality of acrylic acid or methacrylic acid with glycerin, trimethylolpropane, pentaerythritol, and the like, and the aforementioned triallyl cyanurate and triallyl isocyanurate. it can.

Examples of epoxy-containing compounds include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and phenol. (Ethyleneoxy) ₅ glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, glycidyl methacrylate, butyl glycidyl ether can be mentioned.

  In the present invention, a silane coupling agent can be added as an adhesion improver in order to further enhance the adhesive force between the EVA layer and the glass plate or plastic film.

  Examples of this silane coupling agent include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltri Methoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- Mention may be made of β- (aminoethyl) -γ-aminopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Moreover, it is preferable that content of the said compound is 5 mass parts or less with respect to 100 mass parts of EVA.

  The plasticizer is not particularly limited, but polybasic acid esters and polyhydric alcohol esters are generally used. Examples thereof include dioctyl phthalate, dihexyl adipate, triethylene glycol-di-2-ethylbutyrate, butyl sebacate, tetraethylene glycol diheptanoate, and triethylene glycol dipelargonate. One type of plasticizer may be used, or two or more types may be used in combination. The content of the plasticizer is preferably in the range of 5 parts by mass or less with respect to 100 parts by mass of EVA.

  The EVA layer of the present invention is produced, for example, by a method of obtaining a layered product by molding a composition containing the above-mentioned EVA, organic peroxide, ultraviolet absorber, etc. by ordinary extrusion molding, calendar molding (calendering) or the like. can do. In the same manner as described above, the PVB layer of the present invention is formed by, for example, a method of obtaining a layered product by molding a composition containing PVB, an ultraviolet absorber, etc. by ordinary extrusion molding, calendar molding (calendering), or the like. Can be manufactured.

  Alternatively, a layered product can be obtained by dissolving the above composition in a solvent and coating the solution on a suitable support with a suitable coating machine (coater) and drying to form a coating film.

  The PVB layer and the EVA layer may be formed using respective resin films, or may be formed by using a PVB / EVA composite resin film by two-layer extrusion molding of PVB resin and EVA resin or the like. Moreover, the other resin composition is applied to any one of the resin films, for example, the EVA resin composition is applied to a PVB resin film formed in advance to form a two-layer laminated film. You may do it. A three-layer laminated film for bonding can be formed in the same manner.

  In order to produce a laminated glass as the laminate of the present invention, for example, first, a PVB resin film and an EVA resin film are formed, and a necessary number of PVB resin films and EVA resin films are laminated between glass plates. After interposing and degassing the laminate, it may be bonded and integrated by pressing under heating. Such a laminate can be obtained, for example, by a vacuum bag method or a nip roll method. Such lamination can be performed by pressure bonding by a nip roll method because the EVA layer is soft, and the production of the laminate becomes easy. It is preferable that the temperature of a nip roll is 80-140 degreeC. Further, in the case of the EVA layer / PVB layer / EVA layer configuration, since the residual air is reduced, the deprocessing step (by autoclave) can be omitted.

  When the laminate (laminated glass) is produced, the EVA layer is generally crosslinked at 100 to 150 ° C. (particularly around 130 ° C.) for 10 minutes to 1 hour. Such cross-linking is carried out at the temperature of 80 to 120 ° C., for example, at 100 to 150 ° C. (especially around 130 ° C.) after degassing while being sandwiched between the glass plates when the laminate is produced. The heat treatment is performed for 10 minutes to 1 hour. Cooling after crosslinking is generally performed at room temperature, and in particular, the faster the cooling, the better.

  As described above, one glass plate of the laminate of the present invention may be a film reinforced glass as a plastic film, and as the plastic film used at that time, a polyethylene terephthalate (PET) film or a polyethylene aphthalate (PEN) film is used. And polyethylene butyrate film, and PET film is preferred.

  When the hard coat layer is formed on the surface of the plastic film, an ultraviolet curable resin or a thermosetting resin is used as the resin used for that purpose. The hard coat layer generally has a thickness of 1 to 50 μm, preferably 3 to 20 μm.

  As the ultraviolet curable resin, a known ultraviolet curable resin can be used, and any other low molecular weight and multifunctional resin suitable for hard coat treatment is not particularly limited. Examples of the ultraviolet curable resin include urethane oligomers having a plurality of ethylenic double bonds, oligomers such as polyester oligomers and epoxy oligomers, pentaerythritol tetraacrylate (PETA), pentaerythritol tetramethacrylate, and dipentaerythritol hexaacrylate (DPEHA). The monofunctional or polyfunctional oligomers and the like are generally composed of a reactive diluent and a photopolymerization initiator. Furthermore, various additives can be contained. As the reactive diluent, the acryloxy group-containing compound, methacryloxy group-containing compound and / or epoxy group-containing compound used in the transparent adhesive layer can be used, and the transparent adhesive layer can also be used as a photopolymerization initiator. The compounds used in can be used.

  One kind of each of the oligomer, the reactive diluent and the initiator may be used, or two or more kinds thereof may be used in combination. As for content of a reactive diluent, 0.1-10 mass parts is common with respect to 100 mass parts of ultraviolet curable resin, and 0.5-5 mass parts is preferable. The content of the photopolymerization initiator is preferably 5 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable resin.

  As the thermosetting resin, a reactive acrylic resin, a melamine resin, an epoxy resin, or the like can be used. The ultraviolet curable resin can also be used.

  When a hard coat layer is formed using an ultraviolet curable resin, the ultraviolet curable resin is diluted as it is or with an organic solvent to an appropriate concentration, and the resulting solution is applied to an appropriate film with an appropriate coating machine (coater). After coating on top and drying as necessary, a hard coat layer can be formed by irradiating with UV light for several seconds to several minutes directly or through a release sheet (after vacuum degassing) with a UV lamp. As the UV lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, or the like can be used.

  When a hard coat layer is formed using a thermosetting resin, an organic solvent solution of the thermosetting resin is applied onto an appropriate film with an appropriate coating machine (coater), and a release sheet is provided if necessary, a laminator, etc. After degassing, heat curing and thermocompression bonding are performed. In the case where the release sheet is not used, it is preferable to dry for 60 seconds before heating and pressure bonding to evaporate the solvent of the coating layer and to prevent the surface from sticking. Even when a release sheet is used, it is preferable that the release sheet is provided after slightly drying.

  You may provide the transparent conductive layer which consists of a metal and / or a metal oxide in the surface of the glass plate of the laminated body obtained by this invention.

  A barrier layer may be formed on the side surface of the laminate obtained as described above. In general, the thickness of the barrier layer is preferably 0.1 to 20 μm and 1 to 10 μm.

  The laminate thus obtained can be used for the following applications. In other words, glass fitted in automobiles, side glass and rear glass, railway vehicles such as ordinary vehicles, express vehicles, express vehicles and sleeper vehicles, door windows for passenger doors, window glasses and indoor door glasses, windows in buildings, etc. Glass and indoor door glass, indoor display showcases and show windows. Preferably, it is useful for automobile side or rear glass, railcar window glass, especially automobile door glass.

  The following examples further illustrate the present invention.

[Comparative Examples 1-6 and Examples 1-3]
PVB and EVA sheets (thicknesses shown in Table 1) were obtained by a calendar molding method using the following blend as a raw material. The kneading of the blend was carried out at 80 ° C. for 15 minutes, the calender roll temperature was 80 ° C., and the processing speed was 5 m / min.

(Formulation for PVB sheet formation (parts by mass))
PVB resin (degree of acetalization 66 mol%): 100
Plasticizer (triethylene glycol-di (2-ethylbutyrate)): 33
UV adsorbent (2,2′-dihydroxy-4,4′-dimethoxybenzophenone): 0.15
(Formulation for EVA sheet formation (parts by mass))
EVA resin (vinyl acetate content 26% by weight): 100
Cross-linking agent (1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane): 2.0
Silane coupling agent (γ-methacryloxypropyltrimethoxysilane): 0.5
Crosslinking aid (triallyl isocyanurate): 2.0
UV adsorbent (2,2′-dihydroxy-4,4′-dimethoxybenzophenone): 0.15
As the glass plate, two silicate glass plates having a thickness of 5 mm that had been washed and dried in advance were prepared.

  Two glass plates were laminated via the laminate of the EVA sheet / PVB sheet / EVA sheet obtained above, and pre-pressed at a temperature of 110 ° C. using a nip roll. Next, this pre-pressed glass is put in an oven, heat-treated for 30 minutes at a temperature of 130 ° C., and then cooled so that the ambient temperature decreases at 20 ° C./minute, and a laminated glass (see FIG. 2) is obtained. Manufactured.

[Comparative Example 7]
In Example 1, a laminated glass was produced in the same manner except that only a PVB sheet having a thickness of 0.8 mm was used.

[Evaluation of laminated glass]
(Penetration resistance)
According to the method described in JIS-R-3211 (1998), an impact was applied from one glass surface, and the penetration resistance property was investigated. The case of penetrating due to impact was marked with ◯, and the case of not penetrating was marked with ×.

  The above test was performed at 25 ° C. (room temperature) and −5 ° C. (low temperature).

(Sound insulation)
The sound transmission loss was investigated according to the method described in JIS-A-1416 (2000), and the sound transmission loss of sound of 3000 to 5000 Hz was examined.

  The measurement results are shown below.

As is clear from the above results, it can be seen that the laminated glasses obtained in Examples 1 to 3 according to the present invention are excellent in penetration resistance at both room temperature and low temperature and excellent in sound insulation.
It can be said that the laminated glass has excellent transparency, high transparency, and excellent durability.

An example of embodiment of the laminated body of this invention is shown. An example of preferable embodiment of the laminated body of this invention is shown. An example of preferable embodiment of the laminated body of this invention is shown. The graph of tan-delta of the PVB layer and the EVA layer with respect to temperature is shown.

Explanation of symbols

10, 20, 30 Laminate 11A, 11B, 21A, 21B, 31A, 31B Glass plate 12, 22, 32 Intermediate layer EVA layer 13, 23A, 23B, 33
PVB layer 14, 24, 34A, 34B

Claims (13)

An intermediate film is sandwiched between two transparent substrates and bonded and integrated,
The interlayer film includes a laminated film of a layer of a composition containing polyvinyl butyral (PVB layer) and a crosslinked layer (EVA layer) of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide, and,
A laminate having a PVB layer thickness of 0.1 mm or more and an EVA layer thickness of 0.1 mm or more. An intermediate film is sandwiched between two transparent substrates and bonded and integrated,
The intermediate layer is a crosslinked layer (EVA layer) of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide, a layer of a composition containing polyvinyl butyral (PVB layer), and an EVA layer in this order. Including a laminated three-layer laminated film, and
A laminate having a PVB layer thickness of 0.1 mm or more and a total EVA layer thickness of 0.1 mm or more. An intermediate film is sandwiched between two transparent substrates and bonded and integrated,
The interlayer is a layer of a composition containing polyvinyl butyral (PVB layer), a crosslinked layer of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide (EVA layer), and a PVB layer in this order. Including a laminated three-layer laminated film, and
A laminate having a total PVB layer thickness of 0.1 mm or more and an EVA layer thickness of 0.1 mm or more.   The laminate according to any one of claims 1 to 3, wherein the total thickness of all PVB layers is in the range of 0.1 to 2.0 mm.   The laminate according to any one of claims 1 to 4, wherein the total thickness of all EVA layers is in the range of 0.1 to 1.0 mm.   The ratio of the total thickness of all EVA layers to the total thickness of all PVB layers (total EVA layer / total PVB layer) is in the range of 1-6, according to any one of claims 1-5. Laminated body.   The laminate according to any one of claims 1 to 6, wherein the total thickness of all PVB layers and all EVA layers is in the range of 0.3 to 3.0 mm.   The laminate according to any one of claims 1 to 7, wherein the total thickness of all PVB layers and all EVA layers is in the range of 0.7 to 1.0 mm.   The laminate according to any one of claims 1 to 8, wherein the vinyl acetate unit of the ethylene / vinyl acetate copolymer is in the range of 23 to 38% by mass with respect to 100 parts by mass of the ethylene vinyl acetate copolymer.   The ethylene / vinyl acetate copolymer contains 0.05 to 4.0 parts by mass of an organic peroxide with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer. The laminate according to item.   The laminated body according to any one of claims 1 to 10, wherein the two transparent substrates are both glass plates.   The laminated body according to any one of claims 1 to 10, wherein one of the two transparent substrates is a glass plate and the other is a plastic film. The two transparent substrates are both plastic films, The laminate according to any one of claims 1 to 10.

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