JP4972534B2 - Colored laminated glass - Google Patents

Description

  The present invention relates to a laminated glass colored using an interlayer film containing a colorant, and in particular, has excellent appearance characteristics in which generation of flow marks is suppressed even in a shape where pressure unevenness is likely to occur during heating and pressurization. It relates to a colored laminated glass.

  Conventionally, a laminated glass having a structure in which a transparent adhesive layer is sandwiched between glass plates as an intermediate film is known. Laminated glass has improved penetration resistance and the like due to the presence of the intermediate film. Accordingly, the laminated glass is useful as a crime prevention glass because the window cannot be opened freely even if it is broken for the purpose of theft or intrusion. In addition, broken glass fragments remain attached to the intermediate film in response to an impact from the outside, thus preventing scattering.

  Such a laminated glass is used as a windshield or side glass of an aircraft or automobile, or a window glass of a building. Therefore, the laminated glass is required to have high transparency while ensuring safety such as penetration resistance and prevention of scattering of broken glass.

  As an intermediate film in a conventional laminated glass, a PVB resin film obtained by molding a composition containing a polyvinyl butyral resin (hereinafter also referred to as “PVB”) and a plasticizer into a sheet shape is used (Patent Document 1). While PVB is excellent in impact resistance, penetration resistance, etc., it is easily affected by moisture and has insufficient moisture resistance. Therefore, a resin film containing an ethylene vinyl acetate copolymer (hereinafter also referred to as “EVA”), which is excellent in moisture resistance and sound insulation, and inexpensive, instead of PVB has been proposed as an interlayer film for laminated glass (Patent Document). 2).

  In recent years, laminated glass has been used not only for exterior materials and interior walls and windows, but also for applications such as screens, lighting equipment, and modeling works. As the use diversifies in this way, the laminated glass is provided with various colors to improve the design value, thereby improving the utility value. For example, Patent Document 3 discloses a laminated glass colored by adding a colorant to an intermediate film.

  Such a colored interlayer film using conventional EVA is produced by film-forming a composition containing EVA, a crosslinking agent, a colorant and the like by, for example, heat rolling by extrusion molding or the like. By laminating two transparent substrates through the colored intermediate film thus obtained, and heating and pressurizing the obtained laminate, the EVA is crosslinked and cured, and the layers are joined and integrated. Glass is produced.

  In order to attach a laminated glass to a car or a building as a window glass, means for attaching the laminated glass directly to a window frame using an adhesive is known. In addition to this, there is used means for forming a through hole in the laminated glass and attaching the laminated glass to the window frame using an attachment member such as a bolt or a nut using the through hole (Patent Document 4).

JP 2006-160562 A JP-A-57-196747 JP 2005-127029 A JP 2005-127029 A

  In the laminated glass colored using the interlayer film containing the colorant described above, particularly when the pressure applied to the laminated glass during heating and pressurization is uneven, the EVA resin composition contained in the interlayer film flows. Marks may be generated, resulting in poor appearance. For example, in a laminated glass in which a through hole is formed for a mounting member or the like, pressure concentrates around the through hole and pressure unevenness may occur, and annual ring-shaped stripes may occur around the through hole. Therefore, it is necessary to improve the appearance characteristics by suppressing the flow marks generated in the colored laminated glass having through holes.

  Then, the objective of this invention is providing the colored laminated glass which has the through-hole in which generation | occurrence | production of the flow mark was suppressed.

  The present inventor has found that this EVA resin composition has a low melt viscosity and a high fluidity of the EVA resin composition contained in the intermediate film because the occurrence of flow marks in the colored laminated glass that is likely to cause pressure unevenness during heating and pressurization. The flow was not attached with a colorant, and the color density caused by the colorant was generated, resulting in the generation of a flow mark. As a result, it has been found that an intermediate film having a melt viscosity suitable for a colorant is required, and the present invention has been achieved. In other words, the use of a resin layer containing an ethylene vinyl acetate copolymer having a predetermined vinyl acetate content and a colorant so as to have a viscosity that is relatively difficult to flow in the intermediate film suppresses the generation of flow marks. I found out that I can do it.

That is, the present invention is a colored laminated glass having through-holes in which two transparent substrates are bonded and integrated through an intermediate film including a colored resin layer containing an ethylene vinyl acetate copolymer and a colorant. And
The above-mentioned problems are solved by the colored laminated glass, wherein the vinyl acetate content of the ethylene vinyl acetate copolymer is 20 to 23 parts by mass with respect to 100 parts by mass of the ethylene vinyl acetate copolymer. .

  The resin layer containing an ethylene vinyl acetate copolymer having a vinyl acetate content of 20 to 23 parts by mass has a moderately high melt viscosity and low fluidity during heating and pressurization, thereby suppressing the flow of the colorant. can do. Therefore, as a colored intermediate film, an attachment member using at least a colored resin layer containing an ethylene vinyl acetate copolymer having a vinyl acetate content of 20 to 23 parts by mass and a colorant for laminated glass is used. Even if the through-hole used for the purpose is formed, it is possible to suppress the generation of the flow mark due to the pressure unevenness during the heating and pressurization.

  FIG. 1 shows a cross-sectional view of a portion where the through hole of the colored laminated glass of the present invention is formed. As shown in FIG. 1, the colored laminated glass of the present invention has a configuration in which two transparent substrates 11 a and 11 b are bonded and integrated through an intermediate film 10. Further, the colored laminated glass has a through-hole 12 used for inserting a mounting member such as a bolt at an arbitrary place.

(Interlayer film)
The colored laminated glass includes a colored resin layer containing an ethylene vinyl acetate copolymer and a colorant, and the content of vinyl acetate in the ethylene vinyl acetate copolymer contained in the colored resin layer is equal to the ethylene vinyl acetate copolymer. An intermediate film containing a colored resin layer containing an ethylene-vinyl acetate copolymer and a colorant in an amount of 20 to 23 parts by mass, preferably 20 to 21.3 parts by mass is used with respect to 100 parts by mass of the coalescence. Thereby, generation | occurrence | production of the flow mark by the pressure nonuniformity at the time of heat pressurization is suppressed, and the colored laminated glass excellent in an external appearance characteristic is obtained. If the vinyl acetate content is less than 20 parts by mass, the melt viscosity is too low and the film forming property may be low. In addition, since ethylene vinyl acetate copolymer with vinyl acetate content within the above range has low fluidity during heating and pressurization, the intermediate film flows and protrudes into the edge of the laminated glass and through holes. Can also be suppressed.

  The melt flow rate (MFR) of the ethylene vinyl acetate copolymer contained in the colored resin layer is preferably 0.8 to 2.4 g / 10 minutes, particularly preferably 0.8 to 2.0 g / 10 minutes. Thereby, generation | occurrence | production of the flow mark by the pressure nonuniformity at the time of heat pressurization is suppressed, and the colored laminated glass excellent in an external appearance characteristic is obtained. In the present invention, the melt flow rate of the ethylene vinyl acetate copolymer is a value defined in JIS K 7210 (1976).

  The colored resin layer contains a colorant in addition to the ethylene vinyl acetate copolymer described above. As the colorant, conventionally known colorants such as pigments and dyes can be used.

  Specific examples of the pigment include barite powder, precipitated barium sulfate, barium carbonate, lime carbonate powder, calcium carbonate, precipitated calcium carbonate, gypsum, asbestos, clay, silica powder, finely divided silicic acid, diatomaceous earth, talc, and base. Magnesium carbonate, alumina white, gloss white, zinc white, lead white, basic lead sulfate, lead sulfate, lithopone, zinc sulfide, titanium oxide, antimony oxide, carbon black, acetylene black, lamp black, bone black, graphite, iron Black, mineral black, aniline black, cyanine black, zinc silicate, zinc cadmium sulfide, calcium sulfide, strontium sulfide, calcium tungstate, aluminum powder, bronze powder, copper powder, tin powder, lead powder, zinc powder, anthraquinone red, iso Indolinon Red, This Zo Red, Dianisidine Red, RK Antanthrone Red, Pyranthrone Orange, GR Perinone Orange, Isoindolinone Yellow, Flavanthrone Yellow, Anthrapyrimidine Yellow, Phthalocyanine Blue, Phthalocyanine Green, Cadmium Sulfoselenide, Cadmium Mercury , Iron oxide, ultramarine red, chrome tin, ultramarine pink, ultramarine violet, manganese violet, cadmium sulfide, chrome yellow, molybdate orange, titanium pigment, ceramic yellow, cobalt aluminate, chrome cobalt aluminum, ultra Marine blue, ultramarine green, chrome green, chromium oxide, ceramic bra Mention may be made of a click.

  In addition, as a dye, acridine dye, azo dye, alizarin dye, anthraquinone dye, indigoid dye, carbonium dye, xanthene dye, quinoline dye, quinoneimine dye, diphenylmethane dye, stilbene dye, thiazole dye, triphenylmethane dye, nitro dye, Examples thereof include nitroso dyes, pyrazolone dyes, methine dyes, and sulfur dyes. As the colorant, the pigments and dyes described above may be used alone or in combination of two or more.

  Among these, pigments such as calcium carbonate and titanium oxide are preferable because a colored resin layer having an appropriate melt viscosity can be obtained.

  The average particle size of the colorant is preferably 0.01 to 10 μm, particularly preferably 0.1 to 5 μm. When the average particle diameter of the colorant exceeds 10 μm, it becomes difficult for the colorant to follow the flow of the intermediate film during heating and pressurization, and a flow mark may be easily generated. Further, if the average particle size of the colorant is less than 0.01 μm, the colorant is likely to aggregate, and similarly, a flow mark may be easily generated.

  In the present invention, the average particle diameter of the colorant is the number average value obtained by observing the cross section of the intermediate film with a transmission electron microscope at a magnification of about 1,000,000 and determining the equivalent circle diameter of at least 100 colorants. And

  The content of the colorant is preferably 0.1 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the ethylene vinyl acetate copolymer contained in the colored resin layer. Thereby, generation | occurrence | production of a flow mark can be suppressed highly.

  The colored resin layer preferably contains an organic peroxide as a crosslinking agent in addition to the above-described ethylene vinyl acetate copolymer and colorant. Thereby, the crosslinking density of an ethylene vinyl acetate copolymer can be improved and the intermediate film which has the outstanding adhesive force is obtained.

  As the organic oxide, an organic peroxide that decomposes 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 temperature, the flame heat resistance of the adherend, and the storage stability. In particular, those having a decomposition temperature of 70 hours or more with a half-life of 10 hours are preferred.

  Examples of the organic peroxide include, from the viewpoint of resin processing temperature and storage stability, for example, benzoyl peroxide curing agent, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 3, 5, 5- Trimethylhexanoyl peroxide, di-n-octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, succinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, tert-hexylperoxy-2-ethylhexa Noate, 4-methylbenzoyl peroxide tert-butylperoxy-2-ethylhexanoate, m-toluoyl + benzoyl peroxide, benzoyl peroxide, 1,1-bis (tert-butylperoxy) -2-methylcyclohexanate, 1,1-bis (Tert-hexylperoxy) -3,3,5-trimethylcyclohexanate, 1,1-bis (tert-hexylperoxy) cyclohexanate, 1,1-bis (tert-butylperoxy) cyclohexanate 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane, 1,1-bis (tert-butylperoxy) cyclododecane, 1,1-bis (tert-hexylperoxy)- 3,3,5-trimethylcyclohexane tert-hexylperoxyisopropyl Rumonocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,3,5-trimethylhexanoate, tert-butylperoxylaurate, 2,5-dimethyl-2,5-di (methyl) Benzoylperoxy) hexane, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-hexylperoxybenzoate, 2,5-di-methyl-2,5-di (benzoylper) Oxy) hexane and the like.

  Examples of the benzoyl peroxide curing agent include benzoyl peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, p-chlorobenzoyl peroxide, m-toluoyl peroxide, 2, Examples include 4-dichlorobenzoyl peroxide and t-butyl peroxybenzoate. Moreover, you may use a crosslinking agent 1 type or in combination of 2 or more types.

  The content of the organic peroxide in the colored resin layer is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the ethylene vinyl acetate copolymer. Part.

  Furthermore, the colored resin layer may contain a crosslinking aid as required. The cross-linking aid can improve the gel fraction of the ethylene vinyl acetate copolymer and improve the mechanical strength of the intermediate film. As a crosslinking aid (compound having a radical polymerizable group as a functional group) used for this purpose, as well-known trifunctional crosslinking aids such as triallyl cyanurate and triallyl isocyanurate, ) Monofunctional or bifunctional crosslinking aids of acrylic esters (eg, NK esters, etc.) can also be mentioned. Of these, triallyl cyanurate and triallyl isocyanurate are preferable, and triallyl isocyanurate is particularly preferable. These crosslinking assistants are generally used in an amount of 10 parts by mass or less, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the ethylene vinyl acetate copolymer.

  Further, the colored resin layer improves or adjusts various physical properties of the film (optical properties such as mechanical strength, adhesion, transparency, flame heat resistance, light resistance, cross-linking speed, etc.), especially improvement of mechanical strength. Therefore, it may further contain various additives such as a plasticizer and an adhesion improver as necessary.

  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 the ethylene vinyl acetate copolymer.

  As the adhesion improver, a silane coupling agent can be used. Examples of the 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 adhesive improvement agent is 5 mass parts or less with respect to 100 mass parts of EVA.

  Furthermore, the colored resin layer may contain an ultraviolet absorber, a light stabilizer and an anti-aging agent.

  The ultraviolet absorber is not particularly limited, but 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4- Preferred examples include benzophenone ultraviolet absorbers such as methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and 2-hydroxy-4-n-octoxybenzophenone. In addition, it is preferable that the compounding quantity of the said benzophenone series ultraviolet absorber is 0.01-5 mass parts with respect to 100 mass parts of ethylene vinyl acetate copolymers.

  As the light stabilizer, a light stabilizer called a hindered amine type is preferably used. For example, LA-52, LA-57, LA-62, LA-63LA-63p, LA-67, LA-68 (all of which are stocks) ADEKA), Tinuvin 744, Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622LD, CHIMASORB 944LD (all manufactured by Ciba Specialty Chemicals Co., Ltd.), UV-3034 (manufactured by BF Goodrich) Can do. In addition, the said light stabilizer may be used individually or may be used in combination of 2 or more types, and the compounding quantity is 0.01-5 mass parts with respect to 100 mass parts of ethylene vinyl acetate copolymers. Preferably there is.

  Examples of the antioxidant include hindered phenol antioxidants such as N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]. , Phosphorus heat stabilizers, lactone heat stabilizers, vitamin E heat stabilizers, sulfur heat stabilizers, and the like.

  The thickness of the colored resin layer is preferably 2 μm to 2 mm, particularly preferably 0.1 to 2 mm. Thereby, sufficient adhesiveness can be exhibited.

  In the colored laminated glass of the present invention, the intermediate film may be composed of only the above-described colored resin layer, but it includes at least one layer containing the colored resin layer, an ethylene vinyl acetate copolymer, and no colorant. It is preferably a laminate comprising a colored resin layer. The intermediate film is required to have excellent adhesiveness. For this purpose, the intermediate film needs to have a predetermined thickness. If it is an intermediate film composed of a laminate having the above-described structure, even a small amount of colorant can be sufficiently colored, thereby suppressing the generation of flow marks to a higher level and further having a predetermined thickness as a whole. A laminated glass having excellent adhesiveness can be obtained. Furthermore, since the usage-amount of a coloring agent can be reduced, the manufacturing cost of laminated glass can also be reduced.

  The ethylene vinyl acetate copolymer contained in the uncolored resin layer preferably has a vinyl acetate content higher than the vinyl acetate content of the ethylene vinyl acetate copolymer contained in the colored resin layer. Thereby, the difference in melt viscosity between the colored resin layer and the uncolored resin layer can be reduced, and the occurrence of flow marks can be suppressed to a high level.

  Specifically, the vinyl acetate content of the ethylene vinyl acetate copolymer contained in the uncolored resin layer is 24 to 28 parts by mass, particularly 24 to 26 parts per 100 parts by mass of the ethylene vinyl acetate copolymer. It is preferable to set it as a mass part.

  The uncolored resin layer contains an ethylene vinyl acetate copolymer, but in addition, an organic peroxide, a crosslinking aid, a plasticizer, an adhesion improver, an ultraviolet absorber, a light stabilizer, and You may contain at least 1 sort (s) of anti-aging agent as needed. Since the specific description about these is the same as that described above for the colored resin layer, detailed description thereof is omitted.

  When using the laminated body of the said colored resin layer and the said non-colored resin layer as an intermediate film, the thickness of the colored resin layer contained in the said laminated body is 0.1-1 mm, especially 0.1-0.5 mm. It is preferable to do this. Further, the thickness of the uncolored resin layer is preferably 0.5 to 2 mm, particularly preferably 1 to 2 mm. Thereby, content of a coloring agent can be decreased, generation | occurrence | production of a flow mark is suppressed highly, and the laminated glass fully colored can be obtained. Furthermore, since the uncolored resin layer has a predetermined thickness, excellent adhesiveness can be ensured.

  In the laminate, if the thickness of the uncolored resin layer is within a range of 0.5 to 2 mm, particularly 1 to 2 mm, the uncolored resin layer is formed by laminating a plurality of thin uncolored resin layers. May be. For example, 2 to 5 thin uncolored resin layers having a thickness of 0.1 to 0.5 mm may be laminated on the colored resin layer.

  In order to produce the above-described colored resin layer and uncolored resin layer, in addition to EVA, each of the above-mentioned main components is kneaded with a roll mill while heating as necessary, and the resulting mixture is extruded, A method of forming a sheet by a film forming method such as calendar molding or T-die molding is used. Alternatively, the mixture is dissolved in a suitable solvent to form a solution, and this solution is coated on a suitable support using a coater such as a roll coater, knife coater or doctor blade, and dried to form a sheet. Can be used. In addition, it is preferable that the heating temperature at the time of film formation shall be 40-90 degreeC, especially 50-80 degreeC.

(Transparent substrate)
The two transparent substrates used in the laminated glass of the present invention may be the same transparent substrate or a combination of different transparent substrates. The combination of the transparent substrates is preferably determined in consideration of the strength of the transparent substrate and the use of the laminated glass.

  In the present invention, the “glass” in the laminated glass means the whole transparent substrate, and therefore the “laminated glass” means one obtained by sandwiching at least an intermediate film on the transparent substrate.

  Although it does not specifically limit as said transparent substrate, For example, you may use a plastic film other than glass plates, such as a silicate glass, an inorganic glass plate, a non-colored transparent glass plate. Examples of the plastic film include a polyethylene terephthalate (PET) film, a polyethylene aphthalate (PEN) film, and a polyethylene butyrate film, and a PET film is preferred. The thickness of the transparent substrate is generally about 1 to 20 mm.

  The colored laminated glass of the present invention has a through hole. Examples of the through hole include a through hole for a mounting member. For example, a method of attaching a colored laminated glass to the chassis by inserting an attachment member such as a bolt and a nut into the through hole, fastening a chassis such as a window frame of a vehicle or a building, and the colored laminated glass. Moreover, a laminated glass can also be joined by inserting an attachment member in the through-hole for attachment members. In addition to bolts and nuts, conventionally known members can be used as the mounting member, and examples thereof include flat bolts, cables, and rods.

  The said through-hole should just be provided in the arbitrary site | parts of the colored laminated glass according to the target object which attaches an attachment member or colored laminated glass. For example, through holes may be provided at the four corners of a rectangular colored laminated glass.

  The diameters of the through holes in the two transparent substrates are preferably the same. Further, as shown in FIG. 1, in one of the two transparent substrates, a through hole 12 is formed so that the diameter gradually increases from the inside toward the outside in accordance with the shape of the mounting member. May be.

  The colored laminated glass of the present invention has a configuration in which an intermediate film is sandwiched between two transparent substrates and bonded and integrated. In order to produce such a laminated glass, after laminating the transparent substrate, the intermediate film, and the transparent substrate described above in this order, the laminated body is degassed and pressed under heating to be included in the intermediate film. It is obtained by crosslinking and curing EVA and bonding and integrating the layers.

  The order in which the through holes are formed is not particularly limited. For example, a laminated body having through holes may be produced by forming through holes in each member before forming the laminated body, and laminating each member by aligning these positions. Moreover, after laminating each member and obtaining a laminated body, you may form a through-hole in this laminated body. In order to form the through hole, a drilling tool such as a drill may be used.

  Bonding and integration of the laminate is performed by heat-treating the laminate generally at 100 to 150 ° C., particularly around 140 ° C., for 10 minutes to 120 minutes, preferably 10 minutes to 60 minutes. The cross-linking may be performed after pre-bonding at a temperature of, for example, 80 to 120 ° C. The heat treatment is particularly preferably, for example, at 140 ° C. for 10 to 30 minutes (atmospheric temperature). Moreover, it is preferable to perform the said heat processing, applying the press pressure of 0-800 KPa to a laminated body. The layered product after crosslinking is generally performed at room temperature, and in particular, the faster the cooling, the better.

  The first laminated glass of the present invention described above has excellent appearance characteristics by suppressing the generation of flow marks and has a through hole, and therefore can be suitably 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 and sleeper vehicles, door windows for passenger doors, window glasses and indoor door glasses, windows in buildings, etc. Glass and indoor door glass, indoor display showcases and show windows, and water tanks. However, the application is not limited to these.

  As described above, the interlayer film used in the colored laminated glass of the present invention exhibits the effect of suppressing the generation of flow marks by being used in laminated glass that tends to cause unevenness in the pressure applied to the laminated glass during heating and pressing. can do. Therefore, as the use of the intermediate film, besides the colored laminated glass in which through holes are formed, it can be suitably used for colored laminated glass having a shape in which pressure unevenness is likely to occur during heating and pressing.

  Specifically as such a colored laminated glass, similarly to the first colored laminated glass described above, two transparent substrates are provided through an intermediate film including a colored resin layer containing an ethylene vinyl acetate copolymer and a colorant. The outer peripheral contour of colored laminated glass is triangular or pentagonal polygonal shape (for example, triangle, pentagon, hexagon, heptagon, octagon), circular, elliptical, semicircular, fan Shape, number shape, character shape (eg, hiragana, katakana, alphabet, kanji), flower shape, star shape, crescent shape, cloud shape, plant shape (eg, vegetable, fruit), animal shape (eg, dog, cat, Dolphin, insect), human shape, building shape (eg castle), vehicle shape (eg car, train, airplane, ship, motorcycle), heart shape, spade shape, or clover shape And it has a.

  Hereinafter, the present invention will be described with reference to examples. The present invention is not limited by the following examples.

Example 1A
1. Preparation of intermediate film (colored resin layer only) Ethylene-vinyl acetate copolymer (vinyl acetate content 20 parts by mass with respect to EVA 100 parts by mass, melt flow rate 2.0 g / 10 min) and colorant (CaCO ₃ , average particle) Was put into a Henschel mixer at a mass ratio of 85: 5 and stirred and mixed for 3 minutes. The obtained mixture was kneaded and extruded at 85 ° C. using a twin screw extruder to obtain resin pellets.

  Each material is supplied to a roll mill with the composition shown below and kneaded at 80 ° C., and the resulting composition is calendered at a calender roll temperature of 80 ° C. and a processing speed of 5 m / min, and allowed to cool to give a colored resin. An intermediate film composed of layers (thickness 0.4 mm) was produced.

Formulation;
100 parts by mass of resin pellets,
2.2 parts by mass of a crosslinking agent (benzoyl peroxide),
2 parts by mass of a crosslinking aid (triallyl isocyanurate),
1 part by mass of a silane coupling agent (γ-methacryloxypropyltrimethoxysilane),
0.1 part by mass of an ultraviolet absorber (2,2′-dihydroxy-4-methoxybenzophenone).

2. Production of laminated glass The intermediate film produced above is sandwiched between two glass plates (thickness: 3 mm) in which a through hole (diameter: 36 mm) has been previously opened, and an insert is inserted into the through hole of the glass plate. Thus, through holes were also formed in the intermediate film in accordance with the through holes of the glass plate. The resulting laminate was placed in an autoclave and pre-bonded (90 ° C., 60 minutes at a vacuum degree of 760 mmHg), then temporarily bonded (110 ° C., 30 minutes at a degree of vacuum of 760 mmHg) and main pressure bonding (135 ° C., normal) Laminated glass was obtained by performing the pressure for 30 minutes.

(Examples 2A, 3A, and Comparative Examples 1A-3A)
A laminated glass is produced in the same manner as in Example 1A, except that the EVA used for the interlayer film (colored resin layer) has the vinyl acetate content shown in Table 1 (vinyl acetate content relative to 100 parts by mass of EVA). did.

(Example 1B)
1. Preparation of intermediate film (laminated product of colored resin layer and uncolored resin layer) Each material was supplied to a roll mill with the following composition and kneaded at 80 ° C. The resulting composition was calendered at a roll temperature of 80 ° C and processing speed. An uncolored resin layer (thickness 0.4 mm) was produced by calendering at 5 m / min and allowing to cool.

Formulation;
EVA (vinyl acetate content 25 parts by mass with respect to EVA 100 parts by mass, melt flow rate 2.4 g / 10 min) 100 parts by mass,
2.5 parts by mass of a crosslinking agent (benzoyl peroxide)
2 parts by mass of a crosslinking aid (triallyl isocyanurate),
0.5 part by mass of a silane coupling agent (γ-methacryloxypropyltrimethoxysilane),
0.15 mass parts of ultraviolet absorbers (2,2′-dihydroxy-4-methoxybenzophenone).

  Next, an intermediate film was prepared by laminating three layers of the uncolored resin layer prepared above on the colored resin layer prepared in the same manner as in Example 1A.

2. Production of laminated glass The intermediate film produced above is sandwiched between two glass plates (thickness: 3 mm) in which a through hole (diameter: 36 mm) has been previously opened, and an insert is inserted into the through hole of the glass plate. Thus, through holes were also formed in the intermediate film in accordance with the through holes of the glass plate. The resulting laminate was placed in an autoclave and pre-bonded (90 ° C., 60 minutes at a vacuum degree of 760 mmHg), then temporarily bonded (110 ° C., 30 minutes at a degree of vacuum of 760 mmHg) and main pressure bonding (135 ° C., normal) Laminated glass was obtained by performing the pressure for 30 minutes.

(Examples 2B and 3B, and Comparative Examples 1B to 3B)
A laminated glass was produced in the same manner as in Example 1B, except that the EVA used for the colored resin layer in the intermediate film had the vinyl acetate content shown in Table 2 (vinyl acetate content relative to 100 parts by mass of EVA). .

(Evaluation)
1. Presence or absence of generation of flow rate The presence or absence of generation of flow rate was visually evaluated for each of the laminated glasses produced above. Table 1 shows whether or not a flow rate composed of annual ring-shaped stripes is generated around the mounting member through hole.

2. Presence or absence of protrusion of intermediate film About each laminated glass produced above, the presence or absence of protrusion of the intermediate film was visually evaluated. Table 1 shows the results. In Table 1, a case where the protruding portion of the intermediate film was 5 mm or more was determined as “present”, and a case where the protruding portion of the intermediate film was less than 5 mm was determined as “not present”.

3. Film Formability of the Intermediate Film The film formability of the intermediate film in each laminated glass produced above was evaluated visually. The interlayer film in the laminated glass was judged to be poor at least in terms of appearance and productivity, and the film forming property was “×”, and both the appearance and productivity were good, and the film forming property was “◯”. Table 1 shows the results.

The fragmentary sectional view of the colored laminated glass of this invention is shown.

Explanation of symbols

10 interlayer film,
11a, 11b transparent substrate,
12 Through hole.

Claims (9)

Two transparent substrates are bonded and integrated through an intermediate film including a colored resin layer containing an ethylene vinyl acetate copolymer and a colorant, and is a colored laminated glass having a through hole,
Colored laminated glass, wherein the ethylene vinyl acetate copolymer has a vinyl acetate content of 20 to 23 parts by mass with respect to 100 parts by mass of the ethylene vinyl acetate copolymer.   2. The colored laminated glass according to claim 1, wherein the ethylene vinyl acetate copolymer has a melt flow rate of 0.8 to 2.4 g / 10 minutes.   The colored laminated glass according to claim 1 or 2, wherein the colorant is calcium carbonate and / or titanium oxide.   The colored laminated glass according to any one of claims 1 to 3, wherein an average particle diameter of the colorant is 0.01 to 10 µm.   5. The coloring according to claim 1, wherein the content of the colorant is 0.1 to 10 parts by mass with respect to 100 parts by mass of the ethylene vinyl acetate copolymer. Laminated glass.   6. The intermediate film is a laminate comprising the colored resin layer and at least one uncolored resin layer containing an ethylene vinyl acetate copolymer and no colorant. The colored laminated glass according to any one of the above.   The vinyl acetate content of the ethylene vinyl acetate copolymer contained in the uncolored resin layer is higher than the vinyl acetate content of the ethylene vinyl acetate copolymer contained in the colored resin layer. Item 7. The colored laminated glass according to item 6.   The vinyl acetate content of the ethylene vinyl acetate copolymer contained in the uncolored resin layer is 24 to 28 parts by mass with respect to 100 parts by mass of the vinyl acetate content of the ethylene vinyl acetate copolymer. The laminated glass according to claim 6 or 7.   The laminated glass according to any one of claims 1 to 8, wherein the through hole is a through hole for an attachment member.

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