JP2007331952A - Interlayer for laminated glass and laminated glass using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide film-reinforced glass without a fear of environmental pollution, excellent in adhesiveness and in durability and with high transparency, and to provide an interlayer for laminated glass that is useful as a transparent adhesive layer for laminated glass or the like, and laminated glass. <P>SOLUTION: The interlayer for laminated glass is one that is obtained by allowing an organic peroxide to be included in an ethylene-vinyl acetate copolymer, wherein the organic peroxide is represented by formula I, and is a peroxy ketal having a 10-hr half-life temperature of 100°C or lower. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is an intermediate film useful as a transparent adhesive layer of laminated glass including film-reinforced glass excellent in impact resistance, penetration resistance, crime prevention, and the like used for automobiles, railway vehicles, buildings, showcases, etc. And a laminated glass.

  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. For example, Patent Documents 2 and 3 describe film-reinforced glass in which a glass plate and a plastic film are bonded via a transparent adhesive layer (intermediate film) as glass suitable for such applications. In the present invention, a laminated body (film reinforced glass) in which a glass plate and a plastic film are bonded through an intermediate film and a laminated body in which two glass plates are bonded through an intermediate film are both referred to as laminated glass. .

  As described above, the two glass plates of laminated glass or the transparent adhesive layer (that is, the interlayer film for laminated glass) that bonds the glass plate and the plastic film has excellent adhesiveness and penetration resistance. In addition, there is a demand for characteristics such as almost no reduction in transparency or strength of the film over time, that is, excellent durability.

  Recently, environmental pollution of chemical substances has become a problem, and it is necessary to avoid the use of substances that pollute the environment in the transparent adhesive layer. For example, in Examples of Patent Documents 2 and 3, 1,1-bis (t-butylperoxy) 3 is used as a crosslinking agent (organic peroxide) for crosslinking an ethylene / vinyl acetate copolymer (EVA). 3,5-trimethylcyclohexane is used. By using this organic peroxide, EVA can be crosslinked in a relatively short time to obtain excellent adhesion and penetration resistance. However, the above-mentioned organic peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, is classified as Class 1 Monitoring Chemical by the Law on Chemical Substance Examination and Production (Chemical Examination Law). It is designated as a substance, and its manufacture, import and other specified matters are obliged to be reported, and its use may be prohibited.

JP 2002-187746 A JP 2002-046217 A JP 2002-068785 A

  Therefore, in the laminated glass, it is desired to further improve the adhesiveness and durability in consideration of the environmental pollution problem and from the viewpoint of the performance of the laminated glass and the safety at the time of collision.

  For this reason, it is necessary to search for organic peroxides that are not subject to the Chemical Substances Control Law and that have EVA cross-linked and have improved adhesion and durability as compared with the prior art.

  An object of the present invention is to provide an interlayer film for laminated glass that is useful as a transparent adhesive layer such as film tempered glass and laminated glass that does not cause environmental pollution.

  Another object of the present invention is to provide a laminated glass that can be used as a film tempered glass and a laminated glass that do not cause environmental pollution.

  Furthermore, the present invention provides an interlayer film for laminated glass that is useful as a transparent adhesive layer such as film-reinforced glass and laminated glass, which has no fear of environmental pollution, has excellent adhesion and durability, and has high transparency. That is the purpose.

  Still another object of the present invention is to provide a laminated glass that can be used as a film-reinforced glass, laminated glass, or the like that has no risk of environmental pollution, has excellent adhesion and durability, and has high transparency. .

  The above object is an interlayer film for laminated glass comprising an organic peroxide in an ethylene / vinyl acetate copolymer, wherein the organic peroxide has the following formula I:

[Wherein R ¹ represents a linear or branched hydrocarbon group having 5 to 10 carbon atoms, R ² represents a linear or branched hydrocarbon group having 2 to 10 carbon atoms, and R ³ and R ⁴ each independently represents a linear or branched hydrocarbon group having 2 to 6 carbon atoms, or R ³ and R ⁴ are substituted with each other together with adjacent carbon atoms. A cyclic group having 3 to 8 carbon atoms which may have a group (preferably an alkyl group) is formed. ]
And an interlayer film for laminated glass characterized by being a peroxyketal having a 10-hour half-life temperature of 100 ° C. or lower.

  Preferred embodiments of the interlayer film for laminated glass of the present invention are listed below.

(1) In the above formula I, R ¹ and R ² each independently represent a branched hydrocarbon group having 5 to 8 carbon atoms (preferably an alkyl group), and R ³ and R ⁴ are adjacent to each other. And an alicyclic group having 3 to 8 carbon atoms which may have a substituent by bonding to each other. Excellent adhesion and improved durability (for example, transparency or strength decrease is small with time) are easily obtained.

  (2) The organic peroxide is represented by the following formula II:

[However, R ¹ represents a linear or branched hydrocarbon group (preferably an alkyl group) having 5 to 10 carbon atoms, and R ² represents a linear or branched carbon group having 2 to 10 carbon atoms. Represents a hydrogen group (preferably an alkyl group), and R ^{5 to} R ⁹ and R ^{5 ′ to} R ^{9 ′} each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms. (Preferably an alkyl group). ]
It is a peroxyketal represented by Excellent adhesion and improved durability are easily obtained.

In the above formula II, R ¹ and R ² each independently represents a branched hydrocarbon group (preferably an alkyl group) having 5 to 8 carbon atoms (particularly 6). It is particularly preferred that R ¹ and R ² are the same.

  (3) The organic peroxide is contained in an amount of 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer. Excellent adhesion and improved durability are easily obtained.

  (4) Furthermore, 0.1-3.0 mass parts of triallyl (iso) cyanurate is contained with respect to 100 mass parts of ethylene / vinyl acetate copolymer. In particular, excellent adhesion and improved durability are easily obtained.

  (5) The ratio of the organic peroxide to triallyl (iso) cyanurate is 60:40 to 40:60 (organic peroxide: triallyl (iso) cyanurate). In particular, excellent adhesion and improved durability are easily obtained.

  (6) The vinyl acetate unit of the ethylene / vinyl acetate copolymer is in the range of 20 to 35% by mass with respect to 100 parts by mass of the ethylene vinyl acetate copolymer.

  (7) It is obtained by calendering an ethylene / vinyl acetate copolymer containing an organic peroxide.

  (8) It is obtained by applying a liquid containing an ethylene / vinyl acetate copolymer containing an organic peroxide.

  The present invention also resides in a laminate in which the interlayer film for laminated glass is sandwiched between two transparent substrates and is integrated by crosslinking.

  In the laminate, it is preferable that one of the two transparent substrates is a glass plate, the other is a plastic film, and the two transparent substrates are both glass plates. It is useful as film tempered glass and laminated glass.

  The cross-linking agent used in the interlayer film for laminated glass of the present invention has no fear of environmental pollution among known organic peroxides, and interlayer films such as film-reinforced glass and laminated glass (transparent adhesive layer) ) Is selected so as to improve adhesion and durability while maintaining high reactivity during crosslinking. In particular, in the interlayer film for laminated glass of the present invention, when the organic peroxide of the present invention is used and a specific ethylene vinyl acetate copolymer and a specific crosslinking aid are used in a specific ratio, the adhesiveness As a result, it is possible to remarkably suppress an increase in haze and a decrease in film strength that occur with time, and it is possible to obtain a particularly excellent durability.

  Therefore, the interlayer film for laminated glass after cross-linking has no fear of environmental pollution, and particularly has improved adhesiveness and durability. Laminated glass including film-reinforced glass obtained by using this is also environmentally polluted. The adhesion and transparency are particularly improved.

  The interlayer film for laminated glass of the present invention is an interlayer film for laminated glass in which a specific organic peroxide is contained in a material mainly composed of an ethylene / vinyl acetate copolymer, and is transparent for laminated glass including film-reinforced glass. Used as an adhesive layer.

  The specific organic peroxide is represented by the following formula I:

[However, R ¹ represents a linear or branched hydrocarbon group having 5 to 10 carbon atoms, and R ² represents a linear or branched hydrocarbon group having 2 to 10 carbon atoms (eg, alkyl Group, alkenyl group, alkynyl group), and R ³ and R ⁴ each independently represents a straight or branched hydrocarbon group having 2 to 6 carbon atoms, or R ³ and R ⁴ are , A cyclic group having 3 to 8 carbon atoms (eg, an alicyclic group (cycloalkyl group)) which may have a substituent (eg, an alkyl group) bonded to each other with adjacent carbon atoms, A cycloalkenyl group, an aryl group). ]
And a 10-hour half-life temperature of 100 ° C. or lower. The 10-hour half-life temperature is preferably 90 ° C. or less (particularly 80 to 90 ° C.). Thereby, it is easy to obtain dense three-dimensional crosslinking of the ethylene / vinyl acetate copolymer with good reactivity.

In the peroxyketal of the above formula I, it is preferable that R ¹ and R ² each independently represent a branched hydrocarbon group having 5 to 8 carbon atoms (further, an alkyl group, particularly a branched alkyl group). R ¹ and R ² are preferably the same group. Furthermore, it is preferable that at least one of R ¹ and R ² is t-hexyl (that is, 1,1-dimethylbutyl group), and particularly that both are t-hexyl (1,1-dimethylbutyl group).

R ³ and R ⁴ may be bonded to each other together with adjacent carbon atoms to form an alicyclic group having 3 to 8 carbon atoms (especially 5) which may have a substituent. preferable. The substituent is generally a linear or branched hydrocarbon group having 1 to 4 carbon atoms (preferably an alkyl group, particularly a methyl group).

  Accordingly, the peroxyketal of the above formula I is represented by the following formula II:

[However, R ¹ represents a linear or branched hydrocarbon group (preferably an alkyl group) having 5 to 10 carbon atoms, and R ² represents a linear or branched carbon group having 2 to 10 carbon atoms. Represents a hydrogen group (preferably an alkyl group), and R ^{5 to} R ⁹ and R ^{5 ′ to} R ^{9 ′} each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms. (Preferably an alkyl group). ]
It is preferable that it is peroxyketal represented by these. In the above formula II, it is preferable that R ¹ and R ² each independently represent 5 to 8 branched hydrocarbon groups (further, an alkyl group, particularly a branched alkyl group). Further, at least one of R ¹ and R ² is preferably t-hexyl (1,1-dimethylbutyl group), and particularly preferably both are t-hexyl (1,1-dimethylbutyl group). R ^{5 to} R ⁹ and R ^{5 ′ to} R ^{9 ′} are preferably each independently a hydrogen atom or a methyl group. In particular, all of R ^{5 to} R ⁹ and R ^{5 ′ to} R ^{9 ′} are hydrogen, or 3 to 6 of R ^{5 to} R ⁹ and R ^{5 ′ to} R ^{9 ′} , especially 3 (especially R ⁶ , R ^{6 ′} , R ⁸ ) is preferably a methyl group, and the others are preferably hydrogen atoms.

  As the peroxyketal of the present invention, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and 1,1-bis (t-hexylperoxy) cyclohexane are particularly preferable.

  By using such a specific organic peroxide, a high crosslinking rate, excellent adhesion, improved durability, and high transparency are easily obtained. Particularly preferred is the compound of the above formula II. Unlike 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, which has heretofore been used for obtaining good characteristics, the compound of the above formula I of the present invention can be used for the ketal oxygen. Since the alkoxy group to be bonded has a large number of carbon atoms, accumulation in the body or the like is unlikely to occur.

  The intermediate film of the present invention is preferably an ethylene / vinyl acetate copolymer crosslinked with an organic peroxide together with triallyl (iso) cyanurate. Thereby, it is easy to obtain a high crosslinking rate, excellent adhesion, improved durability, and high transparency (low haze). In that case, it is preferable to use an ethylene / vinyl acetate copolymer having a specific vinyl acetate content, which will be described later, and a specific amount of an organic peroxide and triallyl (iso) cyanurate.

  The laminated glass of the present invention is generally a laminated glass (film tempered glass) in which one glass plate, the interlayer film for laminated glass, and one glass plate or plastic film are laminated in order.

  In FIG. 1, an example of embodiment of the laminated glass of this invention is shown. In the laminated body, an interlayer film 12 for laminated glass in which the specific organic peroxide of the above formula I is contained in an ethylene vinyl acetate copolymer is sandwiched between the glass plate 11A and the glass plate 11B, and crosslinked integration is performed. Has been configured. The glass plate 11B may be a plastic sheet. In the present invention, both the former laminate and the latter laminate (film tempered glass) are referred to as laminated glass. Both glass plates 11A and 11B may be plastic sheets.

  The laminated glass uses the interlayer film for laminated glass of the present invention as a transparent adhesive layer, and thus firmly bonds the glass plate and the glass plate, or the glass plate and the plastic film, and It has excellent durability that can remarkably suppress an increase in haze and a decrease in film strength. In addition, the organic peroxide of the present invention exhibits a high crosslinking rate, which is not inferior to conventional ones, and the laminate can be easily produced. Furthermore, the specific organic peroxide used in the present invention has almost no risk of environmental pollution as described above, and the laminated glass obtained using the same has no risk of environmental pollution. The laminated glass of the present invention has high transparency, excellent adhesiveness and durability. In particular, the use of a specific ethylene vinyl acetate copolymer and the organic peroxide in the amount range described below In particular, by using the organic peroxide and TAIC in the above ratio, particularly improved adhesion and durability can be obtained.

  When one side is a plastic film, the laminated glass of the present invention can also be designed to have moderate performance in impact resistance, penetration resistance, transparency, etc. It can be used for glass such as window glass or glass for 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.

  On the other hand, in the case of laminated glass of plastic film, for example, side glass and embedded glass of an automobile, the thickness of the plastic film 3 is generally in the range of 0.02 to 2 mm because the thickness is not as large as that of the windshield. A range of 0.02 to 1.2 mm is preferable. The thicknesses of the intermediate film and the plastic film can be changed according to the place where the glass is used.

  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.

  As the organic resin used for the intermediate film (transparent adhesive layer) of the present invention, an ethylene / vinyl acetate copolymer (EVA) is used. Furthermore, polyvinyl acetal resins (for example, polyvinyl formal, polyvinyl butyral (PVB resin), modified PVB), and vinyl chloride resins can be used as secondary agents. In that case, PVB is particularly preferable.

  EVA used for the interlayer film generally has a vinyl acetate content of 15 to 40% by mass, 20 to 35% by mass, more preferably 22 to 30% by mass, and particularly preferably 24 to 28% by mass. If the vinyl acetate content is less than 15% by mass, the transparency of the resin obtained when crosslinked and cured at a high temperature is not sufficient. Conversely, if the vinyl acetate content exceeds 40% by mass, the impact resistance when a crime prevention glass is obtained. The penetration resistance tends to be insufficient. In particular, the adhesiveness and durability can be improved while maintaining high transparency by setting the content in the range of 20 to 35% by mass, further 22 to 30% by mass, and particularly 24 to 28% by mass.

  In the composition for forming the interlayer for laminated glass of the present invention, the above-mentioned EVA, the organic peroxide (crosslinking agent) represented by the above specific formula I or II, a crosslinking aid if necessary, and adhesion improvement Various additives such as an agent and a plasticizer can be contained.

  The organic peroxide of formula I is generally contained in an amount of 0.5 to 5.0 parts by weight, preferably 1.0 to 3.0 parts by weight, especially 1.5 to 2.5 parts by weight, based on 100 parts by weight of EVA. It is preferable. Thereby, excellent adhesiveness and durability can be obtained without worrying about environmental pollution. Further, triallyl (iso) cyanurate is generally contained in an amount of 0.5 to 5 parts by mass, preferably 1.0 to 3.0 parts by mass, particularly 1.5 to 2.5 parts by mass with respect to 100 parts by mass of EVA. It is preferable. Adhesiveness and durability can be improved while maintaining high transparency. Triallyl (iso) cyanurate represents both triallyl isocyanurate and triallyl cyanurate, with triallyl isocyanurate being particularly preferred. The ratio of the organic peroxide to triallyl (iso) cyanurate is preferably 60:40 to 40:60 (organic peroxide: triallyl (iso) cyanurate), particularly preferably 60:40 to 52:48. Improved penetration resistance is easily obtained. The layer thickness of the intermediate film is generally in the range of 10 to 2000 μm, preferably 10 to 1000 μm, especially 20 to 500 μm.

  The laminated glass of the present invention is also excellent in transparency. In particular, the organic peroxide is 2.2 to 3.0 parts by mass, and the ratio of the organic peroxide to triallyl (iso) cyanurate is 60: By setting it to 40-52: 48, a low haze is easily obtained. By blending in this way, the organic peroxide and triallyl (iso) cyanurate can be added to EVA in a liquid state, and it is easy to obtain good dispersion, and the crosslinking point is greatly increased. It is considered that the haze can be remarkably reduced.

  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.

  In the present invention, the organic peroxide represented by the above specific formula I or II is used as the organic peroxide. In addition to this peroxide, the organic peroxide decomposes at a temperature of 100 ° C. or higher. Any substance that generates radicals can be used in combination. 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 , T-butylperoxy-2-ethylhexyl carbonate.

  The interlayer film according to the present invention improves or adjusts various physical properties of the film (optical properties such as mechanical strength, adhesiveness and transparency, heat resistance, light resistance, cross-linking speed, etc.), especially improvement of mechanical strength. For this reason, it is preferable that a crosslinking aid, an acryloxy group-containing compound, a methacryloxy group-containing compound and / or an epoxy group-containing compound are included.

  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.

  The crosslinking aid, acryloxy group-containing compound, methacryloxy group-containing compound or epoxy group-containing compound is generally 0.5 to 5.0 parts by weight, particularly 1.0 to 4.0 parts by weight, respectively, per 100 parts by weight of EVA. It is preferably included.

  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 intermediate film 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 intermediate film (transparent adhesive layer) for laminated glass of the present invention, for example, the composition containing EVA, organic peroxide, etc. is formed into a sheet by molding by ordinary extrusion molding, calendar molding (calendering) or the like. It can manufacture by the method of obtaining a thing. The composition containing EVA, organic peroxide, etc. is dissolved in a solvent, and this solution is coated on a suitable support with a suitable coating machine (coater) and dried to form a coating film. A product can also be obtained.

  An example of a method for producing the interlayer film for laminated glass of the present invention by calendar molding is shown in FIG. The composition (raw material) containing the EVA, organic peroxide, etc. is charged into the kneader 11, and after kneading, the kneaded material 10 is conveyed by the conveyor 12 and supplied to the kneading roll 13. The kneaded material formed into a sheet shape by the kneading roll 13 was conveyed by the conveyor 14, and smoothed by the calender roll 15 (first roll 15A, second roll 15B, third roll 15C, fourth roll 15D) and smoothed. The sheet is taken out by the take-off roll 16. Thereafter, the surface is embossed with an embossing roll 17, cooled with five cooling rolls 18, and the obtained sheet 20 is wound up by a winder 19. The embossing process is appropriately performed.

  When used for laminated glass, the interlayer film for laminated glass of the present invention, that is, the sheet obtained as described above, is generally 100 to 150 ° C. (especially around 130 ° C.) and 10 minutes to 1 hour (especially 10). ~ 40 minutes) Crosslink. Such cross-linking is performed by depressurization in a state of being sandwiched between transparent substrates (generally glass plates) when manufacturing laminated glass, and then, for example, pre-pressed at a temperature of 80 to 120 ° C, and 100 to 150 ° C. (Especially around 130 ° C.) for 10 minutes to 1 hour. The heat treatment is preferably, for example, at 130 ° C. for 10 to 40 minutes (atmospheric temperature). The layered product after crosslinking is generally performed at room temperature, and in particular, the faster the cooling, the better.

  Examples of the plastic film used in the present invention include a polyethylene terephthalate (PET) film, a polyethylene aphthalate (PEN) film, and a polyethylene butyrate film, and a 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 glass obtained by this invention.

  The laminated glass of the present invention is formed by laminating one glass plate, an interlayer film for laminated glass and one glass plate or a plastic film, and after degassing the laminated glass having a sandwich structure, it is pressed under heating. Thereafter, if desired, it can be obtained by performing a hard coat treatment on a plastic film. Alternatively, after the lamination, the hard coat may be applied, UV cured, and then pressed under heating. Thereafter, the crosslinking treatment is performed.

  A barrier layer may be formed on the side surface of the laminated glass 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 laminated glass 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 opening and closing doors for passengers, window glasses and indoor door glasses, windows in buildings such as buildings 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 intermediate film for cross-linked (cured) laminated glass of the present invention has improved adhesion and durability as described above. Further, the reactivity of the interlayer film for laminated glass can be evaluated as a cure torque indicating the toughness of the film after curing for a predetermined time. The cure torque is set to 130 ° C. with a 0.4 mm thick sheet for forming an interlayer film for laminated glass, and the value after 15 minutes is measured with a cure torque meter (type IV; manufactured by JSR Corporation). Measured by reading. The curing torque of the interlayer film for laminated glass of the present invention can provide a high curing torque in a short time of 15 minutes and exhibits excellent reactivity. In general, it is 80 to 100 N · cm, particularly 85 to 95 N · cm, and shows excellent performance comparable to the conventional one. The interlayer film for laminated glass of the present invention has improved durability, with a high cure torque hardly decreasing over time (for example, after a long period of time after a moist heat resistance test).

  Moreover, the interlayer film for laminated glass of the present invention has high adhesive strength while maintaining the good reactivity (penetration resistance). That is, the adhesive force is preferably 15 to 25 N / cm, particularly 17 to 23 N / cm (the test method will be described later).

  The following examples further illustrate the present invention.

[Comparative Example 1]
An interlayer film for laminated glass (thickness: 400 μm) was obtained by the calendar molding method shown in FIG. The calender roll temperature was 80 ° C. and the processing speed was 5 m / min.

(Formulation for forming an interlayer film for transparent laminated glass (parts by mass))
EVA (vinyl acetate content 28% by mass): 100
Crosslinker 1 (t-butylperoxy-2-ethylhexyl carbonate;
10 hour half-life temperature: 90 ° C.): 2.0
Triallyl isocyanurate: 2.0
Silane coupling agent (3-methacryloxypropyltrimethoxysilane): 0.5
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 through the interlayer film for transparent laminated glass obtained above, put in a rubber bag, vacuum degassed, and pre-pressed at a temperature of 110 ° C. Next, this pre-pressed glass was put in an oven, heat-treated for 30 minutes at a temperature of 130 ° C., and then cooled so that the ambient temperature was lowered at 20 ° C./minute to produce a laminated glass.

[Example 1]
In Comparative Example 1, instead of cross-linking agent 1 (t-butylperoxy-2-ethylhexyl carbonate; 10 hour half-life temperature: 90 ° C.), cross-linking agent 2 (1,1-bis (t-hexylper Laminated glass was produced in the same manner except that the same amount of (oxy) 3,3,5-trimethylcyclohexane; 10 hour half-life temperature: 86.7 ° C.) was used.

[Example 2]
In Comparative Example 1, instead of the crosslinking agent 1 (t-butylperoxy-2-ethylhexyl carbonate; 10 hour half-life temperature: 90 ° C.), the crosslinking agent 3 (1,1-bis (t-hexylper Laminated glass was produced in the same manner except that the same amount of oxy) cyclohexane; 10 hour half-life temperature: 87.1 ° C.) was used.

[Example 3]
In Comparative Example 1, instead of 2.0 parts by mass of crosslinking agent 1 (t-butylperoxy-2-ethylhexyl carbonate; 10 hour half-life temperature: 90 ° C.), crosslinking agent 2 (1,1-bis 1.7 parts by mass of (t-hexylperoxy) 3,3,5-trimethylcyclohexane; 10 hour half-life temperature: 86.7 ° C.) and the amount of triallyl isocyanurate used from 2.0 parts by mass A laminated glass was produced in the same manner except that the amount was changed to 1.7 parts by mass.

[Example 4]
In Comparative Example 1, instead of 2.0 parts by mass of the crosslinking agent 1 (t-butylperoxy-2-ethylhexyl carbonate; 10 hour half-life temperature: 90 ° C.), the crosslinking agent 3 (1,1-bis 1.7 parts by mass of (t-hexylperoxy) cyclohexane; 10 hour half-life temperature: 87.1 ° C.) and the amount of triallyl isocyanurate used was changed from 2.0 parts by mass to 1.7 parts by mass A laminated glass was produced in the same manner as described above.

<Evaluation of the laminated glass and interlayer film for laminated glass>
(1) Adhesive strength In the same manner as in Comparative Example 1 and Examples 1 to 4, a laminated glass (laminated body) was produced in the same manner using a PET (polyethylene terephthalate) film having a thickness of 50 mm instead of one glass. Then, this was cut into a size of 2.5 cm wide and 10 cm long, and the 180 ° peel strength from the glass plate / intermediate film was measured with a tensile tester at a tensile rate of 100 mm / min. Three samples were measured, and the average value was taken as the adhesive strength. Adhesive strength (N / cm) = average peel strength (N) /2.5 (cm). The measurement was performed in an environment of 22 ± 5 ° C.

(2) Cure torque In the same manner as in Comparative Example 1 and Examples 1 to 4, a sheet of the composition for forming an interlayer film for laminated glass having a thickness of 400 μm was formed on a glass plate having a release layer, and the sheet was peeled off. The sheet was set at 130 ° C., and the torque was measured by reading the value after 15 minutes with a cure torque meter (type IV; manufactured by JSR Corporation).

(3) Moisture and heat resistance (durability 1)
The laminated glasses obtained in Comparative Example 1 and Examples 1 to 4 were left in an environment of 60 ° C. and 90% RH for 2000 hours, and the difference between the haze value before being left and the haze value after being left (Δhaze) was determined. Asked. The smaller the difference, the better the heat and moisture resistance.

  The haze value was measured by using a color computer SM-5 (manufactured by Suga Test Instruments Co., Ltd.) for each of the three laminated glasses obtained. Each haze value is an average value of three sheets.

(4) Storage stability (durability 2)
The sheet obtained in (2) was allowed to stand at room temperature for 160 hours, and the cure torque of the sheet after the standing was measured using a cure torque meter (type IV; manufactured by JSR Corporation). Cure torque maintenance rate (%)
Cure torque after standing for 160 hours / Cure torque before standing obtained by (2) × 100 The higher the value, the better the storage stability.

  The measurement results are shown below.

  As is clear from the above results, the interlayer films for laminated glass (laminated glass) of Examples 1 to 4 according to the present invention are interlayer films for laminated glass (Comparative Example 1) using a crosslinking agent generally used conventionally. ) And a curing torque (excellent reactivity) comparable to those of the conventional steel. Furthermore, it has an improved adhesive strength as compared with the prior art, and also has improved heat and humidity resistance.

FIG. 1 shows an example of an embodiment of a laminated glass of the present invention. FIG. 2 shows an example of a method for producing the interlayer film for laminated glass of the present invention by calendar molding.

Explanation of symbols

11A, 11B Glass plate 12 Intermediate film for laminated glass

Claims (14)

An interlayer film for laminated glass comprising an organic peroxide in an ethylene / vinyl acetate copolymer, wherein the organic peroxide has the following formula I:

[Wherein R ¹ represents a linear or branched hydrocarbon group having 5 to 10 carbon atoms, R ² represents a linear or branched hydrocarbon group having 2 to 10 carbon atoms, and R ³ and R ⁴ each independently represents a linear or branched hydrocarbon group having 2 to 6 carbon atoms, or R ³ and R ⁴ are substituted with each other together with adjacent carbon atoms. A cyclic group having 3 to 8 carbon atoms which may have a group is formed. ]
An interlayer film for laminated glass, wherein the interlayer film is a peroxyketal having a 10-hour half-life temperature of 100 ° C. or lower. In the above formula I, R ¹ and R ² each independently represents a branched hydrocarbon group having 5 to 8 carbon atoms, and R ³ and R ⁴ are bonded to each other together with adjacent carbon atoms. The interlayer film according to claim 1, wherein an alicyclic group having 3 to 8 carbon atoms which may have a substituent is formed. The organic peroxide is represented by the following formula II:

[Wherein R ¹ represents a linear or branched hydrocarbon group having 5 to 10 carbon atoms, R ² represents a linear or branched hydrocarbon group having 2 to 10 carbon atoms, and R ^{5 to} R ⁹ and R ^{5 ′ to} R ^{9 ′} each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms. ]
The interlayer film according to claim 1, which is a peroxyketal represented by the formula: The intermediate film according to claim 3, wherein in the formula II, R ¹ and R ² each independently represents a branched hydrocarbon group having 5 to 8 carbon atoms.   The intermediate film according to any one of claims 1 to 4, wherein in the formulas I and II, the hydrocarbon group is an alkyl group.   The intermediate film according to any one of claims 1 to 5, wherein the organic peroxide is contained in an amount of 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer.   Furthermore, 0.1-3.0 mass parts of triallyl (iso) cyanurate is contained with respect to 100 mass parts of ethylene / vinyl acetate copolymers, The intermediate film of any one of Claims 1-6 .   The intermediate film according to claim 7, wherein the ratio of the organic peroxide to triallyl (iso) cyanurate is 60:40 to 40:60 (organic peroxide: triallyl (iso) cyanurate).   The interlayer film according to any one of claims 1 to 8, wherein a vinyl acetate unit of the ethylene / vinyl acetate copolymer is in a range of 20 to 35% by mass with respect to 100 parts by mass of the ethylene vinyl acetate copolymer.   The interlayer film according to any one of claims 1 to 9, which is obtained by calendering an ethylene / vinyl acetate copolymer containing an organic peroxide.   The interlayer film according to any one of claims 1 to 9, which is obtained by coating a liquid containing an ethylene / vinyl acetate copolymer containing an organic peroxide.   A laminated glass, wherein the interlayer film for laminated glass according to any one of claims 1 to 1 is sandwiched between two transparent substrates and integrated by crosslinking.   The laminated glass according to claim 12, wherein one of the two transparent substrates is a glass plate and the other is a plastic film. The laminated glass according to claim 12, wherein the two transparent substrates are both glass plates.

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