JP2006124455A - Adhesive sheet, method for producing the same and laminate produced by using the sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive sheet useful as a transparent adhesive layer for a film-reinforced glass, a laminated safety glass, etc., and having good heat-ray shielding performance without deteriorating excellent adhesiveness and penetration resistance, a method for producing the adhesive sheet and a laminate obtained by using the sheet. <P>SOLUTION: The adhesive sheet is composed of a transparent adhesive layer containing a synthetic resin and a heat-ray shielding layer formed on the adhesive layer and containing fine particles of a metal oxide in a state dispersed in a synthetic resin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a sheet-like adhesive useful as a transparent adhesive layer for film tempered glass and laminated glass, which is excellent in impact resistance, penetration resistance, crime prevention, etc. used in automobiles, railway vehicles, buildings, showcases, etc. The present invention relates to an agent, a production method thereof, and laminates such as these film-reinforced glass and 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.

  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 1 and 2, for example.

  The 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 is required to have excellent adhesion and penetration resistance as described above. .

  The laminated glass generally has excellent adhesion and penetration resistance and is excellent in safety, but does not take into account heat ray blocking properties. As glass having a heat ray blocking function, for example, heat ray cut glass is commercially available. This heat ray cut glass is obtained by applying a metal / metal oxide multi-layer coating on the surface of a glass plate by vapor deposition of metal or the like and sputtering processing for the purpose of directly blocking sunlight. This multilayer coating is vulnerable to external scratches and has poor chemical resistance. Such glass is generally made of laminated glass by laminating an intermediate film made of EVA or the like.

  Moreover, since the said heat ray cut glass uses a metal, there exists a problem that transparency falls, obstructs permeation | transmission of electromagnetic waves, and exerts a bad influence on communication functions, such as a mobile telephone and a car navigation system. Furthermore, since the above-mentioned heat ray cut glass uses a multilayer coating, there is a problem that it becomes expensive.

  Patent Document 3 proposes to use a plasticized polyvinyl butyral film containing a metal oxide as an intermediate film of laminated glass.

JP 2002-046217 A JP 2002-068785 A JP 2001-302288 A

  However, in the intermediate film described in Patent Document 3, according to the study of the present inventor, since the metal oxide is contained, the original characteristics of the intermediate film, excellent adhesion, and penetration resistance may be impaired. It became clear that there was.

  Accordingly, the present invention provides a sheet-like adhesive useful as a transparent adhesive layer for film-reinforced glass and laminated glass having good heat ray cutting performance without impairing excellent adhesiveness and penetration resistance. Is the purpose.

  Another object of the present invention is to provide a sheet-like adhesive that has good heat ray cutting performance and is easy to manufacture without impairing excellent adhesion and penetration resistance.

Furthermore, the present invention aims to provide a method for producing the above sheet-like adhesive. Furthermore, the present invention provides excellent heat ray cutting performance without impairing excellent adhesiveness and penetration resistance. It is an object of the present invention to provide a laminate that can be used as a film tempered glass and a laminated glass.

  The above object is achieved by a sheet-like adhesive comprising a transparent adhesive layer containing a synthetic resin and a heat ray cut layer in which fine particles of metal oxide provided thereon are dispersed in the synthetic resin. can do.

  In the present invention, the heat ray generally means infrared rays.

The metal oxide is preferably at least one oxide selected from ZnO, SnO ₂ , tin-doped indium oxide (ITO), antimony-doped tin oxide, and aluminum-doped zinc oxide. The heat ray can be cut efficiently with a small amount of addition. The average particle diameter of the metal oxide is generally 10 to 90 nm, preferably 20 to 80 nm. The content of the metal oxide is generally 5 to 40% by mass, preferably 10 to 30% by mass with respect to the synthetic resin. Thereby, good heat ray cutting performance can be imparted to the sheet-like adhesive without impairing the excellent adhesiveness and penetration resistance of the sheet-like adhesive.

  The thickness of the transparent adhesive layer is generally in the range of 0.2 to 3 mm, and preferably 0.3 to 1.0 mm. The thickness of the heat ray cut layer is generally 2 to 80 μm, and preferably 5 to 50 μm. The ratio of the thickness of the transparent adhesive layer to the thickness of the heat ray cut layer is generally in the range of 2: 1 to 100: 1, and preferably in the range of 5: 1 to 50: 1. By setting the layer thickness in this way, it is possible to impart good heat ray cutting performance to the sheet adhesive without impairing the excellent adhesiveness and penetration resistance of the sheet adhesive.

  The synthetic resin for the transparent adhesive layer is generally an ethylene / vinyl acetate copolymer and / or polyvinyl butyral, with an ethylene / vinyl acetate copolymer being preferred. The synthetic resin for the heat ray cut layer is generally an ethylene / vinyl acetate copolymer and / or polyvinyl butyral, with an ethylene / vinyl acetate copolymer being preferred. Thereby, the outstanding adhesiveness of a sheet-like adhesive and penetration resistance are ensured. The synthetic resin of the transparent adhesive layer and the synthetic resin of the heat ray cut layer are preferably the same type. It is preferable that the synthetic resin of the transparent adhesive layer and the heat ray cut layer are both ethylene / vinyl acetate copolymers, and it is particularly preferable that the vinyl acetate contents are substantially equal. By setting in this way, excellent adhesiveness between the transparent adhesive layer and the heat ray cut layer can be ensured.

  When an ethylene / vinyl acetate copolymer is used for the transparent adhesive layer and / or the heat ray cut layer, an organic peroxide is preferably further contained. In addition to this, it is particularly preferred to contain triallyl (iso) cyanurate. This makes it easy to obtain a high crosslinking rate, excellent adhesion, and improved penetration resistance. By setting both the transparent adhesive layer and the heat ray cut layer to the same composition, curing can be performed under the same conditions, and mutual adhesiveness is also improved.

  It is preferable that the organic peroxide is generally contained in an amount of 0.5 to 5.0 parts by mass, particularly 1.0 to 3.0 parts by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer.

The sheet-like adhesive described above is
A production method comprising a step of bonding a sheet of a transparent adhesive layer containing a synthetic resin and a sheet of a heat ray cut layer in which metal oxide fine particles are dispersed in the synthetic resin; or a transparent adhesive containing a synthetic resin It can be advantageously obtained by a production method including a step of applying a coating solution for forming a heat ray cut layer in which fine particles of metal oxide are dispersed in a synthetic resin on a sheet of the agent layer and then drying.

  The present invention also resides in a laminate in which the above sheet-like adhesive 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 sheet-like adhesive that can be advantageously used for the production of the film tempered glass and the laminated glass of the present invention comprises a transparent adhesive layer containing a synthetic resin and metal oxide fine particles dispersed in the synthetic resin. It consists of two layers with a heat ray cut layer. That is, the transparent adhesive layer has excellent adhesion to glass and the like, and penetration resistance, and the heat ray cut layer has a function of giving good heat ray cut performance to the sheet adhesive in particular. Since each layer shares roles, each function is performed without impairing each other. In addition, when metal oxide fine particles are uniformly dispersed in a thick transparent adhesive layer as in the past, the productivity is low because high energy and long time are required for the dispersion, but by adopting the configuration of the present invention Dispersion is easy and productivity is remarkably improved.

  Therefore, the sheet-like adhesive of the present invention (generally subjected to a crosslinking treatment) can be easily manufactured, exhibits excellent adhesion and penetration resistance, and exhibits good heat ray-cutting performance, particularly film strengthening. It is advantageous for use in glass and laminated glass.

  The sheet-like adhesive of the present invention is composed of two layers of a transparent adhesive layer containing a synthetic resin and a heat ray cut layer in which fine particles of metal oxide are dispersed in the synthetic resin. It is particularly excellent as a transparent adhesive layer for laminates such as glass.

  In FIG. 1, it is sectional drawing which shows an example of embodiment in the sheet-like adhesive agent of this invention. A heat ray cut layer 12 is formed on the transparent adhesive layer 11 to constitute the sheet-like adhesive of the present invention. The transparent adhesive layer 11 is a layer mainly containing a synthetic resin, and the heat ray cut layer 12 is a layer mainly containing a mixture in which fine particles of metal oxide are dispersed in a synthetic resin. Thus, in addition to excellent adhesiveness with glass and the like, the transparent adhesive layer having the performance of maintaining penetration resistance, and excellent adhesiveness with glass and the like and good heat ray cutting performance for sheet adhesives When used as an adhesive layer of laminates such as film tempered glass and laminated glass by laminating with a heat ray cut layer having a function to impart, these laminates have excellent adhesion and penetration resistance, Furthermore, it becomes possible to have favorable heat ray cut property. In this case, it is possible to cure under the same conditions by using the same composition in both the transparent adhesive layer and the heat ray cut layer (preferably using ethylene / vinyl acetate copolymer for both), and mutual curing is possible. Adhesiveness is also improved, which is preferable.

  The laminated body of the present invention (generally a transparent laminated body) generally has a laminated glass in which a single glass plate, a transparent adhesive layer composed of the above-mentioned sheet-like adhesive, and a single glass plate or plastic film are sequentially laminated. Film tempered glass.

  In FIG. 2, an example of embodiment in the laminated body of this invention is shown. The laminate is configured by sandwiching a sheet-like adhesive composed of the transparent adhesive layer 21 and the heat ray cut layer 22 similar to those described above between the glass plate 23A and the glass plate 23B, and integrating them with each other. . The glass plate 23B may be a plastic sheet. The former is generally called laminated glass, and the latter is generally called film-reinforced glass. Both the glass plates 23A and 23B may be plastic sheets.

  Since the laminated body uses the sheet-like adhesive of the present invention as a transparent adhesive layer, the glass plate and the glass plate, or the glass plate and the plastic film are firmly bonded to each other. Not only does it hardly penetrate even when a large impact is applied, it shows improved penetration resistance, but it also has excellent heat ray cutting properties. That is, a conventional adhesive layer is used for bonding between a glass plate and a glass plate, and a relatively thin heat ray cut layer dispersed in a synthetic resin of metal oxide is provided on the transparent adhesive layer. Since this heat ray cut layer itself has a performance close to that of a conventional transparent adhesive layer and is a thin layer, when the laminate is produced using the sheet-like adhesive of the present invention, almost no penetration resistance is obtained. Heat ray cutting performance can be obtained without deteriorating. By using a laminated body having such a heat ray-cutting performance, for example, on a glass such as a window glass provided in a vehicle body, a building, etc., the car and the building are hardly affected by outside air, and the electricity charge of the air conditioning equipment Can be reduced.

  When one side is a plastic film, the laminate of the present invention can also be designed to have moderate performance in impact resistance, penetration resistance, and the like. For this reason, for example, windows installed in various vehicle bodies, buildings, etc. It can be used for glass such as glass or glass such as showcase and show window. 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 used for a side glass and a fitted glass of an automobile, it is not necessary to make it thick like a windshield, and 1.0 to 10 mm is common, and 2 to 5 mm is preferable. 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 1.0 to 10 mm, and preferably 2 to 3 mm.

  On the other hand, in the case of laminated glass of plastic film, for example, in the case of automobile side glass and embedded glass, the thickness of the transparent adhesive layer is in the range of 0.1 to 1.0 mm because the thickness of the front glass is not required. The range is generally 0.2 to 0.6 mm. Similarly, the thickness of the plastic film 3 is generally in the range of 0.02 to 2 mm, and preferably in the range of 0.02 to 1.2 mm. The thickness of the transparent adhesive layer and the plastic film can be changed depending on the place where the glass is used.

  As the synthetic resin used in the transparent adhesive layer containing the synthetic resin in the present invention, an ethylene / vinyl acetate copolymer (EVA), a polyvinyl acetal resin (for example, polyvinyl formal, polyvinyl butyral (PVB resin), modified PVB). Vinyl chloride resin or the like can also be used. Ethylene / vinyl acetate copolymer (EVA) and polyvinyl butyral (PVB resin) are preferable, and ethylene / vinyl acetate copolymer is particularly preferable.

  EVA used for the transparent adhesive layer 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.

  The composition forming the transparent adhesive layer of the present invention contains various additives such as an organic peroxide, a crosslinking aid, an adhesion improver, and a plasticizer as necessary, in the synthetic resin such as EVA. Can be made.

  Hereinafter, various additives such as an organic peroxide, a crosslinking aid, an adhesion improver, and a plasticizer that are preferably used when EVA is used as a synthetic resin will be described. These can be appropriately selected and used for other synthetic resins (other than PVB).

  In the present invention, any organic peroxide that can be decomposed at a temperature of 100 ° C. or higher to generate radicals can be used. 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, the one having a decomposition temperature of 70 ° C. or more with a half-life of 10 hours is preferable.

  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 monocarbonate.

  The transparent adhesive layer is used to improve or adjust various physical properties of the film (optical properties such as mechanical strength, adhesion, and transparency, heat resistance, light resistance, crosslinking speed, etc.), especially to improve mechanical strength. , An acryloxy group-containing compound, a methacryloxy group-containing compound and / or an epoxy group-containing compound are preferably 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 the polyfunctional compound (crosslinking aid) include esters obtained by esterifying a plurality of acrylic acids or methacrylic acids with glycerin, trimethylolpropane, pentaerythritol, and the like, and further, triallyl cyanurate and triallyl isocyanurate.

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, 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 transparent adhesive 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.

  In this invention, it is preferable that 1-3 mass parts of triaryl (iso) cyanurate is contained with respect to 100 mass parts of EVA. The adhesiveness can be further improved. 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 55:45 to 50:50. Improved adhesion is likely to be obtained.

  When a PVB resin is used as the synthetic resin, the PVB resin has a polyvinyl acetal unit of 70 to 95% by mass, a polyvinyl acetate unit of 1 to 15% by mass, and an average degree of polymerization of 200 to 3000, preferably 300 to 2500. Some are preferred and the PVB resin is used as a resin composition containing a plasticizer.

  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, Esters obtained by reaction with ethylene glycol are preferred, more preferably triethylene-di-2-ethylbutyrate, triethylene glycol-di-2-ethylhexoate, triethylene glycol-di-capronate, triethylene Glycol-di-n-octate and the like. 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, and dibutyl seba is more preferable. Kate, dioctyl azelate, dibutyl carbitol adipate and the like can be mentioned.

  Examples of the phosphoric acid plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.

  In the PVB resin composition, if the amount of the plasticizer is small, the film-forming property is deteriorated, and if it is large, the durability at the time of heat resistance is impaired. Therefore, the plasticizer is 5 to 50 parts by weight with respect to 100 parts by weight of the polyvinyl butyral resin. The amount is preferably 10 to 40 parts by weight.

  The layer thickness of the transparent adhesive layer is generally 0.2 to 3 mm, preferably 0.7 to 1.0 mm.

  The heat ray cut layer of the present invention is basically a layer in which metal oxide fine particles are dispersed in a synthetic resin. When the heat ray cut layer contains metal oxide fine particles, the obtained sheet-like adhesive has excellent heat ray shielding properties, optical properties such as transmittance, and excellent electromagnetic wave permeability. It will have.

  The metal oxide fine particles preferably have an average particle diameter of 10 to 90 nm, particularly 20 to 80 nm. When these ranges are exceeded, the heat ray cutting performance may be deteriorated, and when they are less than these ranges, the transparency may be significantly reduced.

Examples of the material for the metal oxide fine particles include ZnO, SnO ₂ , tin-doped indium oxide (ITO), antimony-doped tin oxide, and aluminum-doped zinc oxide. These can be used alone or in combination of two or more. ITO is preferred.

  In the heat ray cut layer of the present invention, the content of the metal oxide fine particles is 10 to 40% by mass, preferably 10 to 30% by mass with respect to the synthetic resin. If the content is less than 10 parts by mass, the heat ray cutting effect may not be sufficient. If it exceeds 40 parts by weight, the transmittance of visible light may decrease. In addition, this makes it possible to impart good heat ray cutting performance to the sheet-like adhesive without impairing the excellent adhesiveness and penetration resistance of the sheet-like adhesive.

  As the synthetic resin for the heat ray cut layer, a transparent adhesive layer can be used. It is preferable to use the same type of synthetic resin for the transparent adhesive layer. It is particularly preferable to use EVA. Furthermore, even for EVA, it is particularly preferable to use those having the same or substantially the same composition, such as the same or almost the same vinyl acetate content.

  The layer thickness of the heat ray cut layer is generally 2 to 80 μm, preferably 5 to 50 μm. By setting to this range, it is possible to impart good heat ray cutting performance to the sheet-like adhesive without impairing the excellent adhesiveness and penetration resistance of the obtained sheet-like adhesive.

  In order to ensure the penetration resistance of the transparent adhesive layer and the like, it is preferable that the heat ray cut layer is thin. Therefore, the ratio of the layer thickness of the transparent adhesive layer to the layer thickness of the heat ray cut layer is 2: 1 to 100. : 1 range is common, 5: 1 to 50: 1 range is preferred, and 10: 1 to 30: 1 range is particularly preferred. By setting the layer thickness in this way, it is possible to impart good heat ray cutting performance to the sheet adhesive without impairing the excellent adhesiveness and penetration resistance of the sheet adhesive.

  For example, the transparent adhesive layer of the sheet-like adhesive of the present invention is formed from a composition containing the above EVA, organic peroxide, etc. by ordinary extrusion molding, calendar molding (calendering) or the like. It can be manufactured by the method to obtain. 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 transparent adhesive layer of the present invention by calendar molding is shown in FIG. A composition (raw material) containing the EVA, organic peroxide and the like is put into a kneader 31, and after kneading, the kneaded material 30 is conveyed by a conveyor 32 and supplied to a kneading roll 33. The kneaded material formed into a sheet shape by the kneading roll 33 is conveyed by the conveyor 34, smoothed by the calender roll 35 (first roll 35A, second roll 35B, third roll 35C, fourth roll 35D) and smoothed. The sheet is taken out by the take-off roll 36. Thereafter, the surface is embossed with an embossing roll 37, cooled with five cooling rolls 38, and the obtained sheet 20 is wound up by a winder 39. The embossing process is appropriately performed.

  The heat ray cut layer of the present invention can be produced in the same manner as the transparent adhesive layer by the above extrusion molding and calendar molding. Moreover, what is necessary is just to apply | coat directly to the obtained transparent adhesive layer, when producing the heat ray cut layer of this invention by application | coating.

  That is, the sheet-like adhesive of the present invention can be obtained, for example, by laminating a sheet of a transparent adhesive layer and a sheet of a heat ray cut layer obtained by the above-described calendar molding or the like. An example of this bonding method will be described with reference to FIG. The transparent adhesive layer sheet 41 is fed from the feed roll 45 and sent to the squeeze rolls 48 a and 48 b via the roll 46. At the same time, the sheet 42 of the heat ray cut layer is fed from the feed roll 47, and is superposed on the sheet 41 of the transparent adhesive layer by the squeeze rolls 48a and 48b and pressure-bonded. In this way, the sheet-like adhesive 40 is obtained and taken up by the take-up roll 49. If necessary, the sheet in front of the squeeze rolls 48a and 48b can be heated, heated after passing through the squeeze rolls, or many squeeze rolls can be used.

  When producing the heat ray cut layer of the present invention by coating, for example, a coating solution containing an organic solvent and a metal oxide dispersed in a synthetic resin may be directly coated on the transparent adhesive layer and dried. preferable. An example of this coating method will be described with reference to FIG. The sheet 51 of the transparent adhesive layer is fed from the feed roll 55, and the coating liquid 57 is supplied to the sheet 51 leveled by the roll 56 and scraped off by the doctor blade 58, thereby providing a coating layer of a heat ray cut layer. The solvent is removed by the dryer 61, and thus the sheet-like adhesive 50 is obtained and taken up by the take-up roll 59.

  The sheet-like adhesive (transparent adhesive layer) of the present invention, that is, the sheet obtained as described above, is generally 100 to 150 ° C. (especially around 130 ° C.) for 10 minutes when used as a laminate. Crosslink for ~ 1 hour. Such cross-linking is performed in the state of being sandwiched between transparent substrates when producing a laminate, and then pre-pressed at a temperature of, for example, 80 to 120 ° C., and 100 to 150 ° C. (especially around 130 ° C.). ) And pressurizing for 10 minutes to 1 hour.

  Examples of the plastic film used for the transparent substrate of 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. This ultraviolet curable resin is, for example, an oligomer such as a urethane oligomer having a plurality of ethylenic double bonds, a polyester oligomer or an epoxy oligomer, pentaerythritol tetraacrylate (PETA), pentaerythritol tetramethacrylate, 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.

  The laminate of the present invention is made by laminating one glass plate, a sheet-like transparent adhesive layer and one glass plate or plastic film, degassing the sandwich structure, and then pressing 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 laminate (particularly 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 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 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 following examples further illustrate the present invention.

[Example 1]
(Production of sheet adhesive)
An EVA sheet having a thickness of 0.4 mm was obtained as a transparent adhesive layer by the calendar molding method shown in FIG. 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 EVA sheet formation (parts by mass))
EVA (vinyl acetate content 25% by mass,
Product name: Ultrasen 635, manufactured by Tosoh Corporation): 100
Cross-linking agent (perbutyl E; t-butyl peroxy-2-ethylhexyl monocarbonate manufactured by NOF Corporation): 2.2
Silane coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.): 1.0
Ultraviolet absorber (Ubinal 3049; manufactured by BASF Japan Ltd.): 0.1

  On the surface of the obtained EVA sheet (transparent adhesive layer) having a thickness of 0.4 mm, a coating solution for forming a heat ray cut layer having the following composition was applied, dried at 40 ° C. for 15 minutes, and a heat ray having a thickness of 20 μm. A cut layer was formed. This application was performed using the apparatus shown in FIG.

(Coating liquid formulation for heat ray cut layer formation (parts by mass))
EVA (vinyl acetate content 26% by mass,
Product name: Ultrasen 634, manufactured by Tosoh Corporation): 100
Cross-linking agent (perbutyl E; t-butyl peroxy-2-ethylhexyl monocarbonate manufactured by NOF Corporation): 2.2
Silane coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.): 1.0
Ultraviolet absorber (Ubinal 3049; manufactured by BASF Japan Ltd.): 0.1
ITO dispersion (15% by weight ITO in toluene solution, average particle size 30 nm,
Product Name: Nanotech Slurry ITR Toll 15WT% -G30;
CAI Kasei Co., Ltd.): 120
Toluene: 400

[Example 2]
Instead of the EVA sheet used in Example 1, a PVB sheet (S-LEC film (RZ, manufactured by Sekisui Chemical Co., Ltd.)) having a thickness of 0.4 mm was used in the same manner to obtain a sheet adhesive. Produced.

[Comparative Example 1]
(Production of sheet adhesive)
An EVA sheet having a thickness of 0.4 mm was obtained as a transparent adhesive layer by the calendar molding method shown in FIG. 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.

(Composition for forming EVA sheet with heat ray cut material (parts by mass))
EVA (vinyl acetate content 25% by mass,
Product name: Ultrasen 635, manufactured by Tosoh Corporation): 100
Cross-linking agent (perbutyl E; t-butyl peroxy-2-ethylhexyl monocarbonate manufactured by NOF Corporation): 2.2
Silane coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.): 1.0
Ultraviolet absorber (Ubinal 3049; manufactured by BASF Japan Ltd.): 0.1
ITO (average particle size 30 nm,
Product name: Nanotech ITO-R; manufactured by CI Kasei Co., Ltd.): 0.5

[Comparative Example 2]
Only the EVA sheet used in Example 1 was used as it was as a transparent sheet adhesive.
"Production of laminated glass"
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 transparent sheet adhesive obtained above, put into a rubber bag, vacuum degassed, and pre-pressed at a temperature of 110 ° C. Next, this pre-press-bonded glass was put in an oven and subjected to a pressure treatment for 30 minutes at a temperature of 130 ° C. to produce a laminate (laminated glass).

<Evaluation of the laminate and sheet adhesive>
(1) Infrared transmittance (transmittance of 1200 nm) and visible light transmittance (transmittance of 650 nm)
Using a spectrophotometer (UV3100 manufactured by Shimadzu Corporation), the transmittance of the laminated glass obtained using the sheet-like adhesives of Example 1 and Comparative Examples 1 and 2 was measured for transmittance in the wavelength region of 350 to 1250 nm. did. The measurement was performed according to JIS-R-3212. The light transmittance of 1200 nm and 650 nm is shown.

(2) Shotback test (penetration resistance)
A falling ball test in accordance with JIS-R-3205 of the transparent laminated plate obtained in Example 1 and Comparative Examples 1 and 2 (a laminate in which two sheets of glass are sandwiched between sheet adhesives (transparent adhesive layers)). And the penetration resistance was evaluated.

  The measurement results are shown below.

  As is clear from the above results, the laminates using the sheet adhesives of Examples 1 and 2 according to the present invention have a low infrared transmittance and a good level of penetration resistance. Although the laminated body using the sheet-like adhesive of Comparative Example 1 has good infrared transmittance, the penetration resistance was not satisfactory.

FIG. 1 shows an example of an embodiment of the sheet adhesive of the present invention. FIG. 2 shows an example of an embodiment of the laminate of the present invention. FIG. 3 shows an example of a method for producing the transparent adhesive layer constituting the sheet-like adhesive of the present invention by calendar molding. FIG. 4 shows an example of a method for producing the sheet-like adhesive of the present invention by the bonding method. FIG. 5 shows an example of a production method by a coating method of the sheet-like adhesive of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11, 21 Transparent adhesive layer 12, 22 Heat ray cut layer 23A, 23B Glass plate 20 Sheet 30 Kneaded material 31 Kneading machine 32 Conveyor 33 Kneading roll 34 Conveyor 35 Calendar roll 36 Take-off roll 37 Embossing roll 38 Cooling roll 39 Winding machine 40 , 50 Sheet adhesive 41, 51 Sheet 42 Sheet of heat ray cut layer 45, 47, 55 Delivery roll 46, 56 Roll 48a, 48b Squeeze roll 49, 59 Take-up roll 57 Coating liquid 58 Doctor blade

Claims (15)

  A sheet-like adhesive comprising: a transparent adhesive layer containing a synthetic resin; and a heat ray cut layer in which fine particles of metal oxide provided thereon are dispersed in the synthetic resin. Metal oxides, ZnO, SnO _2, tin-doped indium oxide, a sheet-like adhesive according to claim 1 which is an oxide of at least one selected from antimony-doped tin oxide and aluminum-doped zinc oxide.   The sheet-like adhesive according to claim 1 or 2, wherein the metal oxide has an average particle size of 10 to 90 nm.   Item 4. The sheet-like adhesive according to any one of Items 1 to 3, wherein the content of the metal oxide is 5 to 40% by mass with respect to the synthetic resin.   The sheet-like adhesive according to any one of claims 1 to 4, wherein the transparent adhesive layer has a thickness of 0.2 to 3 mm.   The layer thickness of a heat ray cut layer is 2-80 micrometers, The sheet-like adhesive agent in any one of Claims 1-5.   The sheet-like adhesive according to any one of claims 1 to 6, wherein the ratio of the thickness of the transparent adhesive layer to the thickness of the heat ray cut layer is in the range of 2: 1 to 100: 1.   The sheet-like adhesive according to any one of claims 1 to 7, wherein the synthetic resin of the transparent adhesive layer is an ethylene / vinyl acetate copolymer and / or polyvinyl butyral.   The sheet-like adhesive according to any one of claims 1 to 8, wherein the synthetic resin of the heat ray cut layer is an ethylene / vinyl acetate copolymer and / or polyvinyl butyral.   The sheet-like adhesive according to any one of claims 1 to 9, wherein the synthetic resin of the transparent adhesive layer and the synthetic resin of the heat ray cut layer are of the same type.   The sheet | seat of the transparent adhesive layer containing a synthetic resin and the process of mutually bonding the sheet | seat of the heat ray cut layer by which the fine particle of a metal oxide is disperse | distributed in a synthetic resin are included in any one of Claims 1-10. A method for producing a sheet-like adhesive.   The method according to claim 1, further comprising a step of applying a coating solution for forming a heat ray cut layer in which fine particles of metal oxide are dispersed in a synthetic resin on a sheet of a transparent adhesive layer containing the synthetic resin, and then drying. A method for producing the sheet-like adhesive according to any one of the above.   A laminate having the sheet-like adhesive according to any one of claims 1 to 9 sandwiched between two transparent substrates and integrated by crosslinking.   The laminate according to claim 13, wherein one of the two transparent substrates is a glass plate and the other is a plastic film. The laminate according to claim 13, wherein the two transparent substrates are both glass plates.

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