WO2006046726A1

WO2006046726A1 - Sheet adhesive, method for producing same and multilayer body using same

Info

Publication number: WO2006046726A1
Application number: PCT/JP2005/019945
Authority: WO
Inventors: Masao Hashimoto
Original assignee: Bridgestone Corporation
Priority date: 2004-10-27
Filing date: 2005-10-25
Publication date: 2006-05-04
Also published as: JP2006124455A

Abstract

Disclosed is a sheet adhesive which is characterized by consisting of a transparent adhesive layer containing a synthetic resin and a heat ray-cutting layer arranged on the transparent adhesive layer wherein fine particles of a metal oxide is dispersed in a synthetic resin. Since such a sheet adhesive has good heat ray-cutting performance without deteriorating excellent adhesiveness and penetration resistance, it is suitable as a transparent adhesive layer for film-reinforced glasses or laminated glasses.

Description

Specification

Sheet adhesive, method for producing the same, and laminate using the same

1. Technical field

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 of these film-reinforced glass and laminated glass. 2. Background art

Generally, laminated glass having a structure in which a transparent adhesive layer (intermediate film) is sandwiched between glass plates is used for glass used in automobiles, particularly windshields. This transparent adhesive layer is formed of, for example, a P V B film, an E V A film or the like, and the presence of the transparent adhesive layer improves the penetration resistance of the laminated glass. In addition, in response to external impacts, broken glass fragments remain adhered to the transparent adhesive layer, preventing scattering. For this reason, for example, a laminated glass of an automobile cannot be opened freely even if it is broken for the purpose of theft or intrusion, so it is also useful as a security glass.

-On the other hand, for example, automobile door glass and fitted glass are generally not easily destroyed by accidents, and therefore do not require the penetration resistance of the above windshield, etc. Glass plates are used. However, when only one such glass plate is used, there are, of course, the following drawbacks. (1) Inferior to laminated glass in terms of impact resistance, penetration resistance, etc. (2) If broken for the purpose of theft or intrusion, etc., it breaks into many pieces and opens the window freely Can, and so on. For this reason, the use of glass with characteristics similar to laminated glass is also being considered for door glass and fitted glass. As glass suitable for such applications, glass plates and plastic films Film tempered glass bonded through a transparent adhesive layer is described in, for example, Patent Document 1 (Japanese Patent Laid-Open No. 2002-046217) and Patent Document 2 (Japanese Patent Laid-Open No. 2002-068785).

And, as described above, 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 adhesiveness and penetration resistance. ing.

The above 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-cut glass has a metal / metal oxide multi-layer coating on the surface of the glass plate by vapor deposition of metals and sputtering for the purpose of directly blocking sunlight. This multi-layer coating is vulnerable to external scratches and has poor chemical resistance. Such glass is generally made of laminated glass made of, for example, EVA and laminated glass.

In addition, since the heat ray cut glass uses a metal, there is a problem that the transparency is deteriorated or the transmission of electromagnetic waves is hindered to adversely affect communication functions such as a mobile phone and a car navigation system. Furthermore, the heat ray cut glass has a problem that it is expensive because it uses a multilayer coating.

Patent Document 3 (Japanese Patent Laid-Open No. 2001-302288) proposes the use of a plasticized polybutylpropylar film containing a metal oxide as an intermediate film of laminated glass.

3. Disclosure of the invention

However, according to the study of the present inventors, the intermediate film described in Patent Document 3 contains a metal oxide, which may impair the original characteristics of the intermediate film, excellent adhesion, and penetration resistance. It became clear that there was.

Therefore, the present invention provides excellent heat radiation without impairing excellent adhesion and penetration resistance. It is an object of the present invention to provide a sheet-like adhesive useful as a transparent adhesive layer for film-reinforced glass and laminated glass having cut performance.

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

Furthermore, the object of the present invention is to provide a method for producing the sheet-like adhesive.

Still another object of the present invention is to provide a laminate that can be used as a film tempered glass, laminated glass, etc. having excellent heat ray cutting performance without impairing excellent adhesion and penetration resistance. .

An object of the present invention is to provide 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 be achieved.

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

The metal oxide is, Z n O, S N_〇 _2, tin-doped indium oxide (ITO), is preferably also less selected from § Nchimondopu tin oxide and aluminum-doped zinc oxide is an oxide of one kind. The heat ray can be cut efficiently with a small addition amount. 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, based on the synthetic resin. As a result, the sheet adhesive can be imparted with good hot wire performance without impairing the excellent adhesion and penetration resistance of the sheet adhesive.

The layer thickness of the transparent adhesive layer is generally in the range of 0.2 to 3 mm, preferably 0.3 to 1.0 mm. The layer thickness of the heat ray cut layer is generally 2 to 80 um, preferably 5 to 50 m. 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, 5 :! ~ 50: The range of 1 is preferred. By setting the layer thickness in this way, the excellent adhesiveness of the sheet adhesive, Without impairing the penetration resistance, the sheet-like adhesive can be imparted with a good heat ray performance.

The synthetic resin for the transparent adhesive layer is generally an ethylene vinyl acetate copolymer and z or polybutyral, with ethylenenoacetate copolymer being preferred. The synthetic resin of the heat ray cut layer is generally an ethylene / butyl acetate copolymer and / or polyvinyl butyral, with an ethylene / vinyl acetate copolymer being preferred. This ensures the excellent adhesion and sheet penetration resistance of the sheet adhesive. 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 layer can be ensured.

When the ethylene vinyl acetate copolymer is used for the transparent adhesive layer and / or the heat ray cut layer, it is preferable that an organic peroxide is further included. 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 using the same formulation for both the transparent adhesive layer and the heat ray coating layer, it becomes possible to cure under the same conditions, and also improve the mutual adhesion.

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 manufacturing method comprising a step of mutually bonding a sheet of a transparent adhesive layer containing a synthetic resin and a sheet of a heat ray coating layer in which metal oxide fine particles are dispersed in the synthetic resin; or

Advantageous by a manufacturing 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 a transparent adhesive layer containing the synthetic resin, and then drying. Obtainable. The present invention also resides in a laminate in which the above-mentioned sheet-like adhesive is sandwiched between two transparent substrates and is crosslinked and integrated.

In the laminate, one of the two transparent substrates is preferably 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 invention's effect]

The sheet-like adhesive that can be advantageously used in the production of the film-reinforced glass and the laminated glass of the present invention is a heat ray in which a transparent adhesive layer containing a synthetic resin and metal oxide fine particles are dispersed in the synthetic resin. It consists of two layers with a cut layer. That is, the transparent adhesive layer retains excellent adhesion to glass and the like and penetration resistance, and the heat ray cutting layer has a function of imparting good heat ray cutting performance particularly to the sheet-like adhesive. Each layer shares roles, so that each function is performed without any loss. 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 the configuration of the present invention is adopted. This facilitates dispersal and significantly improves productivity.

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

4. Brief description of the drawings

FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of the sheet-like adhesive of the present invention. FIG. 2 is a schematic sectional view showing an example of the embodiment of the laminate of the present invention.

FIG. 3 is a schematic view showing an example of a method for producing the transparent adhesive layer constituting the sheet-like adhesive of the present invention by calendering.

FIG. 4 shows an example of a method for producing the sheet adhesive of the present invention by the bonding method. FIG.

FIG. 5 is a schematic view showing an example of a production method by a sheet-like adhesive coating method of the present invention. 5. BEST MODE FOR CARRYING OUT THE INVENTION

The sheet-like adhesive of the present invention is basically composed of two layers of a transparent adhesive layer containing a synthetic resin and a heat ray layer formed by dispersing metal oxide fine particles in the synthetic resin. It is particularly excellent as a transparent adhesive layer for laminates such as film tempered glass and laminated glass.

FIG. 1 is a cross-sectional view showing an example of an embodiment of the sheet adhesive of the present invention. A heat ray coating layer 12 is formed on the transparent adhesive layer 11 and constitutes 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 adhesion to glass and the like, a transparent adhesive layer having the performance of maintaining penetration resistance, excellent adhesion to glass and the like, and good heat ray cutting for sheet-like adhesives When used as an adhesive layer for laminates such as film tempered glass and laminated glass by laminating a heat ray cutting layer having a function of imparting performance, these laminates have excellent adhesion and penetration resistance. In addition, it is possible to have a better heat ray cutting property. In this case, it is possible to cure under the same conditions by using the same formulation in both the transparent adhesive layer and the heat ray cut layer (preferably using ethylene / vinyl acetate copolymer for both) and mutual curing. It is also preferable because it improves the adhesion.

The laminate of the present invention (generally a transparent laminate) is generally a laminate in which one glass plate, a transparent adhesive layer composed of the above sheet-like adhesive, and one glass plate or plastic film are laminated in order. Glass or film tempered glass.

FIG. 2 shows an example of an embodiment of the laminate of the present invention. The laminated body has a transparent adhesive layer 21 similar to the above and a thermal plate between the glass plate 23 A and the glass plate 23 B. A sheet-like adhesive composed of the wire-cut layer 22 is sandwiched and integrated by crosslinking. The glass plate 2 3 B may be a plastic sheet. The former is generally called laminated glass, and the latter is generally called film-reinforced glass. Both glass plates 2 3 A and 2 3 B may be plastic sheets.

The laminate uses the sheet-like adhesive of the present invention as a transparent adhesive layer, and thus strongly bonds the glass plate and the glass plate or the glass plate and the plastic film. In addition to exhibiting almost no improved penetration resistance even when a large impact is applied to it, it has excellent heat resistance. In other words, 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 metal oxide synthetic resin is provided on the transparent adhesive layer. Since the heat ray cut layer itself has a performance close to that of the conventional transparent adhesive layer and is a thin layer, when the laminate is produced using the sheet adhesive of the present invention, the penetration resistance is reduced. Heat ray cutting performance can be obtained with almost no deterioration. By using a laminate with such heat ray-cutting performance, for example, for glass such as window glass mounted on the car body and buildings, etc., the car and the building are less affected by the outside air. 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, etc. For this reason, for example, windows installed in various vehicle bodies, buildings, etc. It can be used for glass such as 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 in 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 thickness varies depending on the location where it is installed. For example, 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 1 O mm, especially 2 to 5 mm. 2 to 3 mm is preferred. The one glass plate 1 is chemically or thermally strengthened. It is.

On the other hand, in the case of laminated glass of plastic film, for example, in the case of side glass and embedded glass for automobiles, the thickness of the transparent adhesive layer is 0.1 to 1.0 because the thickness of the windshield is not required. A range of mm is common, and a range of 0.2 to 0.6 mm is preferred. Similarly, the thickness of the plastic film 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 according to the place where the glass is used.

The synthetic resin used in the transparent adhesive layer containing the synthetic resin in the present invention includes ethylene / vinyl acetate copolymer (EVA), polyvinylacetal resin (for example, polyvinyl formal, polyvinyl butyral (PVB resin)). , Modified PVB), and salted bull resin can also be used. Preferred are ethylene vinyl acetate copolymer (EV A) and polyvinyl ptyral (PVB resin), and particularly preferred is ethylene / vinyl acetate copolymer.

EVA used for the transparent adhesive layer generally has a vinyl acetate content of 15 to 40% by mass, 20 to 35% by mass, further 22 to 30% by mass, especially 24 to 28% by mass. preferable. If the vinyl acetate content is less than 15% by mass, the transparency of the resin obtained when crosslinking and curing at high temperature is not sufficient, and conversely 40 mass. If it exceeds / ₀ , the impact resistance and penetration resistance of the crime prevention glass tend to be insufficient.

In the composition forming the transparent adhesive layer of the present invention, various additives such as an organic peroxide, a crosslinking aid, an adhesion improver, and a plasticizer are added to the synthetic resin such as EVA as necessary. Can be included.

The following describes various additives such as organic peroxides, lacquer auxiliaries, adhesion improvers, and plasticizers that are preferably used when EVA is used as the synthetic resin. These can be appropriately selected and used for other synthetic resins (other than PVB). In the present invention, the organic peroxide is generally decomposed at a temperature of 100 ° C. or higher. Anything that generates a zical can be used. In general, the organic peroxide is selected in consideration of the film forming temperature, the adjustment condition of the composition, the curing (bonding) temperature, the heat resistance of the adherend, and the storage stability. In particular, those having a half-life of 10 hours and a decomposition temperature of 70 ° C or higher are preferred.

Examples of such organic peroxides include 2,5-dimethylhexane-1,5-dihydroperoxide, 2,5-dimethyl-1,2,5-di (t-butyl baroxy) hexane 1-3 t-Butyl peroxide, t-Butylcumyl peroxide, 2,5-Dimethyl _ 2,5-Di (t-Butylperoxide) Hexane, Dicumyl peroxide, α, a 'Bis (t-Butyl (Peroxyisopropyl) benzene, n-butyl-1,4-bis (t_butylperoxy) valerate, 1,1-bis (t-butylperoxy) hexane, 1,1_bis (t-butyloxy) 1,3,3,5-trimethylcyclohexane, t-butyl peroxybenzoate, benzoyl peroxide, t-butyl peroxyacetate, methyl ketone ketone peroxide 2,5—Dimethylhexinole 2,5—Bisperoxybenzoate, Butylhydride Peroxide, p-Mentanehydride Peroxide, p _Chronobenzoyl Peroxide, Hydroxyheptinoreperoxy , Hexanone peroxide, Octanoyl peroxide, Decanoyl peroxide, Lauroyl peroxide, Cumyl peroxide agent, Succinic acid peroxide, Acetylper Cite oxoxide, m-toluoinole peroxide, t-butyl peroxyisobutylene, and 2,4-dichlorobenzoyl peroxide, t-butyl peroxy 2-ethyl ether monocarbonate Can do.

The transparent adhesive layer improves or adjusts various physical properties of the film (mechanical strength, adhesiveness, optical properties such as transparency, heat resistance, light resistance, cross-linking speed, etc.), especially mechanical strength improvement. Therefore, it is preferable to include an acryloxy group-containing compound, a methacryloxy group-containing compound, and a no- or epoxy-group-containing compound.

As the acryloxy group-containing compound and the methacryloxy group-containing compound to be used, Generally, it is a derivative of acrylic acid or methacrylic acid, 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_hydroxychetinore group, 3- Examples thereof include a hydroxypropynole group and a 3-chloro-2-hydroxypropyl group. In addition, polyhydric alcohols such as ethylene glycol, triethylene glycolone, polypropylene glycol, polyethylene glycol, trimethylolpropane, and pentaerythritol and esters of acrylic acid or methacrylic acid can be mentioned.

An example of an amide is diacetone acrylamide.

Examples of the polyfunctional compound (crosslinking aid) include esters obtained by esterifying a plurality of acrylic acid or methacrylic acid with glycerin, trimethylolpropane, pentaerythritol, and the like, and triarylcyanurate and triallyl isocyanurate. .

Epoxy-containing compounds include triglycidyl tris (2-hydroxyxetyl) isocyanurate, neopentylglycol diglycidyl ether, 1,6—hexane diau ^ / diglycidino reetenole, allylic glycidino reetenole, 2-ethino les Xinoleglycidyl ether, Phenyldaricidyl ether, Phenonor (ethylenoxy) ₅ Glycidyl ester, P-t-Butyl glycidyl ester, Adipic acid diglycidyl ester, Phthalic acid diglycidyl ester, Glycidyl methacrylate, Butyl Mention may be made of daricidyl ether.

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-chloropropyl propyl silane, vinyl ethoxy silane, vinylol tris (| 3-methoxy ethoxy) silane, γ-methacryloxyprovir trimethy silane, butyl triacetoxy silane, one Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, butyltrichlorosilane, γ-mercaptopropyl trimethoxysilane, γ—aminopropyl Mention may be made of triethoxysilane, 0-0- (aminoethyl) -1-γ-aminopropyl trimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Further, the content of the above compound is preferably 5 parts by mass or less with respect to 100 parts by mass of EVA.

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

In the present invention, triaryl (iso) cyanurate as a crosslinking aid is added to 100 parts by mass of EVA:! ~ 3 parts by weight, preferably contained. The adhesiveness can be further improved. Triarinore (iso) cyanurate represents both triarinoleiso cyanurate and triarylcyanurate, with trialinole isocyanurate being particularly preferred. The ratio of organic peroxide to triallyl (iso) cyanurate is 60:40 to 40:60 (organic peroxide: triarinole (iso) cyanurate), especially 5 5: 4 5 to 50:50 It is preferable that Improved adhesion is easy to obtain.

When using a PVB resin as a synthetic resin, the PVB resin, Poribyurua acetal units 70-9 5 wt ^_0/0, with polyvinyl acetate Bulle units 1-1 5 mass%, average degree of polymerization of 200 to 3 000, Those having 300 to 2500 are preferred, and 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 butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid), and decylic acid. Esters obtained by the reaction of an acid with triethylene glycol are preferred, more preferably triethylene di-di-2-ethylbutyrate, triethyleneglycolene di-2-ethylenohexoate, triethylene glycol Pronate, triethylene glycol-di- _n- octate, etc. 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 more preferably, Examples include dibutyl sebacate, dioctylazelate, and dibutyl carbitol adipate.

Phosphate-based plasticizers include tributoxetyl phosphate, isodecyl phosphate

-Rufophosphate, triisopropyl phosphate, etc.

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 during heat resistance is impaired. Therefore, the plasticizer with respect to 100 parts by weight of the polybutyral resin. 5 to 50 parts by weight, preferably 10 to 40 parts by weight.

The layer thickness of the transparent adhesive layer is generally in the range of 0.2 to 3 mm, preferably 0.7 to: I 0.0 mm.

The heat ray cutting 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 good 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. If these ranges are exceeded, the heat ray cutting performance will decrease, If it is less than these ranges, the decrease in transparency may be significant.

Examples of the metal oxide fine particles include ZnO, SnO ₂ , tin-doped indium oxide (ITO), antimony monotin 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 preferably 10 to 40% by mass, and 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 mass, 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 of the sheet-like adhesive and the penetration resistance.

As the synthetic resin for the heat ray cutting layer, a transparent adhesive layer can be used. It is preferable to use the same type of synthetic resin as 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 μΐη, preferably 5 to 50 um. By setting within this range, it is possible to give the sheet-like adhesive a good heat radiation performance 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, etc., it is preferable that the heat ray cut layer is thin. For this reason, the ratio of the layer thickness of the transparent adhesive layer to the layer thickness of the heat ray cut layer is 2: The range of! ~ 10: 0: 1 is general, the range of 5 ::! ~ 50: 1 is preferable, and the range of 10 ::! ~ 30: 1 is particularly preferable. By setting the layer thickness in this way, it is possible to give the sheet-like adhesive good thermal linear force performance without impairing the excellent adhesiveness and penetration resistance of the sheet-like adhesive. .

For example, the transparent adhesive layer of the sheet-like adhesive of the present invention can be prepared by using, for example, the above-mentioned EVA, an organic peroxide, and the like by ordinary extrusion molding, calendar molding (calendering), etc. It can be manufactured by a method of forming a sheet by molding. In addition, the above composition containing EVA, organic peroxide, etc. is dissolved in a solvent, and this solution is applied onto an appropriate support with an appropriate applicator (coater) and dried to form a coating film. Thus, a sheet can be obtained.

FIG. 3 shows a schematic diagram of an example of a method for producing the transparent adhesive layer of the present invention by force rendering. The composition (raw material) containing the above EVA, organic peroxide and the like is put into a kneading machine 31, and after kneading, the kneaded product 30 is conveyed by a conveyor 32 and supplied to a kneading roll 33. The kneaded material formed into a sheet by the kneading roll 3 3 is conveyed by the conveyor 3 4, and then the calender roll 3 5 (first roll 3 5 A, second roll 3 5 B, third roll roll 3 5 C, fourth roll 3 5 D) Smooth the sheet, and take out the smoothed sheet with 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 scraped off with a scraper 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. Further, when the heat ray cut layer of the present invention is produced by coating, it may be applied directly to the obtained transparent adhesive layer.

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 sheet 41 of the transparent adhesive layer is sent out from the feed roll 45, and sent to the squeeze rolls 48a and 48b through the roll 46. At the same time, the sheet 4 2 of the heat ray cut layer is fed out 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 pressed. In this way, the sheet-like adhesive 40 is obtained and scraped off by the scraping roll 49. If necessary, the sheet before the squeeze rolls 48a, 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, the above transparent adhesion It is preferable that a coating solution containing a metal oxide dispersed in an organic solvent and a synthetic resin is directly applied on the agent layer and dried. 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 feeding roll 55, and the coating liquid 57 is supplied to the sheet 51 that has been leveled by the roll 56, and is scraped off by the doctor blade 58. A coating layer is provided, and the solvent is removed by the dryer 61, and thus the sheet-like adhesive 50 is obtained and wound up by the winding 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 1300 ° C) when used as a laminate. Then, it is heated for 10 minutes to 1 hour to crosslink. Such cross-linking is carried out by depressurizing in the state of being sandwiched between transparent substrates when producing a laminate, and then pre-pressing at a temperature of, for example, 80 to 120 ° C, and 100 to 150 ° C ( In particular, it is performed by pressurizing at around 1 30 ° C for 10 minutes to 1 hour.

Examples of the plastic film used for the transparent substrate of the present invention include polyethylene terephthalate (PET) film, polyethylene phthalate (PEN) film / rem, and polyethylene butyrate film, and PET film is preferred.

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

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 UV-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 (ΡΕΤΑ), pentaerythritol tetrametaacrylate, dipentaerythritol hexax. Monofunctional or polyfunctional oligomers such as relate (DPEHA), reactive diluents, Generally composed of initiator. Furthermore, various additives can be contained. As the reactive diluent, an acrylic group-containing compound, a methacryloxy group-containing compound and / or an epoxy group-containing compound used in the transparent adhesive layer can be used. As a photopolymerization initiator, the transparent adhesive can be used. The compound used in the agent layer can be used.

Each of the oligomer, reactive diluent and initiator may be used alone or in combination of two or more. The content of the reactive diluent is generally from 0.1 to 10 parts by weight, preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the ultraviolet curable resin. 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, reactive acrylic resin, melamine resin, epoxy resin, etc. 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 obtained solution is applied to an appropriate film with an appropriate 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). As the UV lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, etc. can be used.

When forming a hard coat layer using a thermosetting resin, apply an organic solvent solution of the thermosetting resin on an appropriate film with an appropriate coating machine (coater), and provide a release sheet if necessary. After deaeration, etc., perform thermosetting and thermocompression bonding. When the release sheet is not used, it is preferable to dry it for 60 seconds before heating and pressure bonding to evaporate the solvent of the coating layer and 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 includes, for example, one glass plate, a sheet-like transparent adhesive layer, and 1 It can be obtained by laminating a sheet of glass or plastic film, degassing the sandwich structure, pressing it under heating, and then subjecting it to a hard coat treatment on the plastic film if desired. Alternatively, after the lamination, a hard coat can be applied, UV cured, and then heated and pressed. 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. The thickness of the layer is generally 0. l ~ 20 / xm ,! ~ Ι Ο μηι is preferred.

The laminate thus obtained can be used for the following applications. In other words, automotive glass, side glass and rear glass, railway vehicles such as ordinary vehicles, express vehicles, express vehicles, sleeper vehicles, etc., passenger door door glass, window glass and indoor door glass, buildings, etc. Window glass and indoor door glass, and so on. It is preferably used for automobile side or rear glass, railcar window glass, especially automobile door glass.

The following examples illustrate the present invention in further detail.

[Example]

[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 force-render molding method shown in FIG. The compound was kneaded at 80 ° C. for 15 minutes, the calender roll temperature was 80 ° C., and the processing speed was 5 minutes.

(Formulation for EVA sheet formation (parts by mass))

EVA (Butyl acetate content 25% by mass,

Product name: Ultrasen 635, manufactured by Tosoh Corporation): 1 00 Cross-linking agent (Perbutyl E; manufactured by NOF Corporation)

t-Butylperoxy 2-ethylhexyl monocarbonate): 2.2 Silane coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.): 1.0 UV absorber (Ubinal 3049; manufactured by BASF Japan): 0.1 EVA sheet with a thickness of 0.4 mm On the surface of the transparent adhesive layer), a coating solution for forming a heat ray cut layer having the following composition was applied and dried at 40 ° C. for 15 minutes to form a heat ray cut layer having a thickness of 20 μm. 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; manufactured by NOF Corporation)

t-Butylperoxy 2-ethylhexyl monocarbonate): 2.2 Silane coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.): 1.0 UV absorber (Ubinal 3049; manufactured by BAS F Japan Co., Ltd.) ): 0.1 ITO dispersion (15% by weight ITO solution in ITO, average particle size 30 nm,

Product Name: Nanotech Slurry I TR Toll 1 5WT% _G30;

CI Kasei Co., Ltd.): 1 20 Toluene: 400 [Example 2]

Instead of the EVA sheet used in Example 1, a 0.4 mm thick PVB sheet (S-LEC film (RZ, manufactured by Sekisui Chemical Co., Ltd.)) 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 force-render molding method shown in FIG. The compound was kneaded at 80 ° C for 15 minutes, the calender roll temperature was 80 ° C, and the processing speed was 5 m / "min. (Formation for forming EVA sheet with heat ray cut material (parts by mass))

EVA (vinyl acetate content 25 mass ^_0/0,

Product name: Ultrasen 635, manufactured by Tosoh Corporation): 100 Cross-linking agent (Perbutyl E; manufactured by NOF Corporation)

t-Butylperoxy 2-ethyl ethyl monocarbonate): 2.2 Silane coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.): 1.0 UV absorber (Ubinal 3049; manufactured by BAS F Japan Co., Ltd.) ): 0.1 I TO (average particle size 30 nm,

Product name: Nanotech I TO-R; manufactured by Shi 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 glass plates, two silicate glass plates with a thickness of 5 mm, which had been washed and dried in advance, were prepared.

Two glass plates were laminated via the transparent sheet adhesive 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 and pressurized for 30 minutes under the condition of a temperature of 1300C to produce a laminate (laminated glass).

(1) Infrared transmittance (transmittance of 1200 nm) and visible light transmittance (transmittance of 650 nm)

The laminated glass obtained using the sheet-like adhesives of Example 1 and Comparative Examples 1 and 2 was transmitted through a wavelength range of 350 to 1250 nm using a spectrophotometer (UV3 100, manufactured by Shimadzu Corporation). The rate was measured. The measurement was performed according to JI S-R-3212. The light transmittance at 1200 nm and 650 nm is shown.

(2) Shotback test (penetration resistance) The transparent laminated plate obtained in Example 1 and Comparative Examples 1 and 2 (a laminated body in which two sheets of glass are held with a sheet-like adhesive (transparent adhesive layer)) is a ball falling in accordance with JIS-R-3205. A test was conducted to evaluate penetration resistance.

The measurement results are shown below.

As is clear from the above results, the laminates using the sheet-like 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 laminate using the sheet-like adhesive of Comparative Example 1 had good infrared transmittance, the penetration resistance was not satisfactory.

[Explanation of symbols]

1 1, 21 Transparent adhesive layer

12, 22 Heat cut layer

23 A, 23 B glass plate 30 Kneaded material

3 1 Kneading machine

32 conveyor

33 Kneading Mouth

34 Conveyor

35 Power Render

36 Take Ofronore

37 Embossing Nore

38 Cooling roll

39 Scraper

40, 50 Sheet adhesive

41, 51 sheets

42 Heat ray power layer sheet

45, 47, 55 Feeding roll

46, 56

48 a, 48 b Squeeze Ronore

49, 59 Scoop roll

57 Coating solution

58 Doctor blade

6. Industrial applicability

The sheet-like adhesive of the present invention can be easily produced, exhibits excellent adhesiveness and penetration resistance, and exhibits good heat ray cutting performance, particularly for use in film tempered glass and laminated glass. Is advantageous.

Claims

The scope of the claims

1. 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.

2. metal oxides, ZnO, Sn0 _2, Suzudoichipu indium oxide, sheet of claim 1 is at least one of oxides selected from anti Monde-loop tin oxide and aluminum-doped zinc oxide adhesive Agent.

3. The sheet-like adhesive according to claim 1 or 2, wherein the metal oxide has an average particle size of 10 to 90 nm.

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.

5. The sheet-like adhesive according to any one of claims 1 to 4, wherein the thickness of the transparent adhesive layer is 0.2 to 3 mm.

6. The sheet adhesive according to any one of claims 1 to 5, wherein the layer thickness of the heat ray cut layer is 2 to 80; um.

7. The ratio of the layer thickness of the transparent adhesive layer to the layer thickness of the heat ray power layer is 2::! The sheet-like adhesive according to any one of claims 1 to 6, which is in a range of ~ 100: 1.

8. 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 petitar.

9. 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 Z-butyl acetate copolymer and Z or polyvinyl butyral.

10. 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 the same type.

1 1. The method includes 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 fine particles of metal oxide are dispersed in a synthetic resin to each other. A method for producing the sheet-like adhesive according to any one of the above.

12. A process 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 1 to 10.

1 3. A laminate comprising the sheet-like adhesive according to any one of claims 1 to 9 sandwiched between two transparent substrates and integrated by crosslinking.

14. The laminate according to claim 13, wherein one of the two transparent substrates is a glass plate and the other is a plastic film.

15. The laminate according to claim 13, wherein the two transparent substrates are both glass plates.