JP3112125B2 - Glass plate with molding or holder and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic or organic glass plate, for example, a raw or reinforced single plate having a flat or bent plate shape, a laminated or double-glazed window member and a door member, and the like. The glass before forming a molding or a holder integrally with the periphery of the glass plate-like body, which can be used for construction, for vehicles, etc., and is particularly useful for vehicles requiring moving up and down and for movable window glass for automobiles, etc. A film or a film-like layer of the specified adhesive composition is coated on the surface in advance, and the coated surface is integrated with a molding or a synthetic resin for a holder, particularly a molding or a holder made of the specified multi-phase thermoplastic resin composition. An object of the present invention is to provide a molding or a glass plate with a holder and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a method of imparting adhesiveness to a substrate such as glass, for example, Japanese Patent Publication No. 37-18392 or Japanese Patent Publication No. 52-32654 discloses a polyolefin represented by polyethylene or polypropylene. Into which a polar group is introduced by graft modification with, for example, an unsaturated carboxylic acid such as acrylic acid or maleic anhydride or an anhydride thereof, and, for example, JP-B-46-27527 or JP-A-48-11388. Has an α represented by ethylene
A copolymer obtained by copolymerization of an olefin and a polar monomer such as glycidyl (meth) acrylate; for example, JP-A-47-15486 discloses a laminate of a copolymer of ethylene and maleic anhydride and a polyamide; It is also known that the addition of an elastomer such as polyisobutylene to a copolymer of ethylene and maleic anhydride improves the adhesion to a polyamide resin.

On the other hand, as a method of integrally forming a molding or a holder after forming an adhesive layer at a predetermined portion of a peripheral portion of a glass plate, for example, JP-A-59-199228 discloses a method.
After surrounding the outer edge of the glass plate from both sides, after attaching a cushioning member made of elastic rubber or soft synthetic resin and also serving as a sealing material molded in a substantially U-shaped cross section to the entire outer edge of the glass plate, It is sandwiched by an injection mold composed of a core mold and a cavity mold via the cushioning member, and into a space formed by both molds, a molten synthetic resin is injected to form a frame portion, and a frame portion is formed. It is disclosed that an attempt is made to prevent the occurrence of burrs by making a cut in the seal / buffer member along the inner peripheral edge and removing the buffer member.

For example, Japanese Patent Application Laid-Open No. 62-25024 discloses that a thermally activated adhesive layer is formed on the periphery of a plate-shaped window glass, and the periphery of the window glass on which the adhesive layer is formed is injection-molded. Insert into a mold and perform injection molding of synthetic resin to form a frame material on the periphery of the window glass, and activate the adhesive by the heat of the injected resin to integrally fix the window glass and the frame material. A method for manufacturing a vehicle window is disclosed.

Further, for example, Japanese Patent Application Laid-Open No. 1-209116 filed by the present applicant discloses that a molding or a holder is integrally formed and fixed at a required portion of a peripheral portion of a plate-like body.
The corresponding end faces from the peripheral edges of both front and back surfaces are arranged so as to surround at least one resin film having a fusing property at a temperature of 60 to 150 ° C. and a thickness of 5 to 250 μ in advance at a required portion of the peripheral portion of the plate-like body. With a molding or holder that removes the plate from the mold after placing the plate in the mold, injecting the resin into the cavity space consisting of the resin film surface and the mold inner surface, and solidifying the resin. A method for manufacturing a plate is proposed.

Further, for example, West German Patent No. 911,781 describes a method of attaching a rubber sealing member to the periphery of a window glass. The edge surface of a glass plate is metallized with aluminum, for example, to 0.05 to 0.15 mm. To form a thin metal coating, apply an adhesive, such as a solution-based rubber adhesive, to the surface in some cases, then set the glass plate in a mold, mold the rubber, and heat and vulcanize it. The disclosure is known.

[0007]

As described above, for example, JP-B-37-18392, JP-B-52-32654, JP-B-46-27527, JP-A-48-11388 and In the method of imparting adhesiveness described in Japanese Patent Laid-Open No. 47-15486, etc., for example, in the case of a laminate used for building parts or automobile parts, especially in the case of a glass plate as such parts, Is required to have heat-resistant adhesiveness, and also needs adhesive strength at low-temperature bonding, and the improvement by the above-mentioned conventional methods is not sufficient, and it is difficult to use, and rather it cannot be used. .

On the other hand, in the manufacturing method described in Japanese Patent Application Laid-Open No. 62-25024, the outer peripheral edge of the glass plate is surrounded from both sides.
Even if a molding is integrally formed by simply mounting a cushioning member which also serves as a sealing material formed in a substantially U-shaped cross section made of elastic rubber or soft synthetic resin, it does not necessarily enhance the adhesive force strongly. It is. Further, the method described in West German Patent No. 911,781 only describes that a solution adhesive is applied to form an adhesive layer, and does not describe the thickness and melting temperature of the adhesive layer. In order to avoid the adverse effect on the interlayer, the vulcanization temperature of the rubber molded as the sealing member is preferably about 100 to 110 ° C., and it can be said that the rubber is hardly melted at this temperature. It is not an exaggeration to say that it does not necessarily exhibit sufficient adhesive strength, especially heat resistant adhesiveness, and does not exhibit adhesive strength at low temperature bonding. Further, in the method described in JP-A-1-209116,
Although a considerable improvement is recognized from the above various methods and the like, for example, in an ascending and descending window glass for an automobile window glass, when used in various severe environments on temperature, although the heat-resistant adhesiveness is improved, It is not always possible to say that it is stable for a sufficiently long period.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and has been made in consideration of the fact that a molding or a holder is integrally molded and fixed to a peripheral portion of a glass plate-like body. a predetermined position of the plate periphery, Gala particular with at film or film-like layer of a specific adhesive composition comprising an alkoxysilane compound and a polyamide resin
The glass plate-like body is formed by being interposed in a state of being attached so as to surround the peripheral part of the plate-like body , and further by using a multi-phase thermoplastic resin composition in which the molding or the holder is a matrix-phase polyamide resin. By improving the adhesiveness between the resin film or resin film-like layer and the resin molding or holder components, high-strength bonding, improved accuracy in mounting, etc., of course, heat resistance is significantly better, Provided is a glass plate with a molding or a holder, which is an integrally molded product which significantly improves the adhesive strength by low-temperature bonding and the peeling strength at high temperatures, and also has good water resistance and the like, and a method for producing the same. It is.

[0010] That is, the present invention is to provide a resin film or at least one resin film-like layer at a predetermined portion of the periphery of the glass plate-like body from the periphery of the front and back surfaces so as to surround the end of the glass. A resin molding or holder is attached to the corresponding end face by injection molding , and the resin film or the resin film-like layer is provided.
The resin film or the resin film-like layer is formed of an ethylene-α, β-unsaturated carboxylic acid ester-maleic anhydride in a molding or a glass plate with a holder , which is integrally molded with the glass plate at the periphery of the lath plate. 55 to 90% by weight of the acid terpolymer and R'nSi (OR) <SUB> 4-n <
/ SUB> (R ′ is an amino group, an epoxy group, a mercapto group,
A methacryloxy group, a polar group having an acryloxy group, a vinyl group, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group; R represents an alkyl group having 1 to 8 carbon atoms;
Or 2. A) A molding or a glass plate with a holder, comprising 0.5 to 10% by weight of an alkoxysilane compound represented by the formula and 40 to 5% by weight of a polyamide resin.

[0011] Further, the alkoxysilane compound may be vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,
The above-mentioned molding or glass plate with holder, characterized in that it is at least one kind of alkoxysilane compound selected from γ-aminopropyltriethoxysilane.

The ethylene-α, β-unsaturated carboxylic acid ester-maleic anhydride terpolymer comprises 40 to 90% by weight of ethylene units and 55 to 5% by weight of α, β-unsaturated carboxylic acid alkyl ester units. , Maleic anhydride unit 0.
The molding or the glass plate with holder described above, which is a copolymer comprising 1 to 10% by weight.

Further, the above-mentioned molding or glass plate with holder is characterized in that the resin molding or holder is made of a polyamide resin or a multi-phase thermoplastic resin whose matrix phase is a polyamide resin. Furthermore, the multi-phase thermoplastic resin in which the matrix phase is a polyamide resin is a resin composition obtained from a polyamide resin and polyphenylene ether or polypropylene or ABS. body. Further, the polyamide resin is a multi-phase thermoplastic resin, a polyamide resin,
The above-mentioned glass plate with a molding or a holder, which is a resin composition obtained from polyphenylene ether, polypropylene or ABS, and glass fiber.

The above-mentioned polyamide resin is polyamide-6 or polyamide-66. And the resin composition obtained from the polyamide resin and polyphenylene ether is a resin composition comprising a polyamide resin, polyphenylene ether and a compatibility improver, wherein the molding or the glass plate-like body with a holder described above. .

Further, when a resin molding or a holder is integrally molded and fixed to a required portion of the peripheral portion of the glass plate-like body, ethylene-α, β-unsaturated carboxylic acid ester-maleic anhydride is added to the required portion. Original copolymer 55
~ 90% by weight and R'n Si (OR) _4-n (R 'is an amino group,
An epoxy group, a mercapto group, a methacryloxy group, a polar group having an acryloxy group, a vinyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, R represents an alkyl group having 1 to 8 carbon atoms, and n is 1 or 2. )) At least one sheet containing a resin film composed of 0.5 to 10% by weight of the alkoxysilane compound represented by the formula and 40 to 5% by weight of a polyamide resin is coated on both sides of the glass plate in advance so as to surround the periphery of the glass plate . The glass plate is placed in the mold from the peripheral edge to the corresponding end face, the glass plate is placed in the mold, and the mold is clamped.The polyamide resin or matrix phase is filled in the cavity space formed by the surface of the resin film and the mold inner surface. A resin composition comprising a multi-phase thermoplastic resin which is a polyamide resin is injected and injected, and after the resin composition is solidified, the glass plate is removed from the mold, or a molding or a glass plate with a holder. How to make the body.

Further, the present invention provides a method for producing a glass plate with a molding or a holder as described above, wherein the multiphase thermoplastic resin whose matrix phase is a polyamide resin contains glass fibers. Is what you do.

Here, the ethylene-α, β-unsaturated carboxylic ester-maleic anhydride terpolymer is a copolymer produced by high-pressure radical copolymerization. The α, β-unsaturated carboxylic acid ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, an alkyl ester such as acrylic acid and methacrylic acid. Specific examples thereof include methyl acrylate and acrylic acid. Ethyl, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-methacrylate -Butyl, isobutyl methacrylate, and the like.
Particularly, methyl acrylate, ethyl acrylate, n-butyl acrylate and methyl methacrylate are preferred, and these comonomers can be used alone or in combination of two or more.

Further, the content of the α, β-unsaturated carboxylic acid ester is about 5 to 55% by weight.
If the content exceeds 55% by weight, the adhesive strength is sufficient, but the production cost is increased and the odor is deteriorated.

Further, the content of the maleic anhydride is about 0.1 to 10% by weight. When the content is less than 0.1% by weight, the effect of improving the adhesiveness is small, which is not preferable. When it exceeds 10% by weight, the adhesive strength is not sufficient. However, this is not preferable because the manufacturing cost increases.

Next, the alkoxysilane compound is represented by R
^' nSi (OR) _4-n formula (R ^' represents an amino group, an epoxy group, a mercapto group, a methacryloxy group, a polar group having an acryloxy group, a vinyl group, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group. , R represents an alkyl group having 1 to 8 carbon atoms, and n is 1 or 2.). Examples of suitable alkoxysilane compounds include those containing an amino group, such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (βaminoethyl) -aminopropyltrimethoxysilane, and N-aminopropyltrimethoxysilane. (Β-aminoethyl) -aminopropyltriethoxysilane and the like. Examples of those containing an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Further, those containing a mercapto group include γ-mercaptopropyltrimethoxysilane, γ-mercaptomethyldiethoxysilane and the like. Further, those containing a methacryloxy group include γ- (methacryloxypropyl) trimethoxysilane. Further, those containing a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (β-methoxyethoxy) silane. Furthermore, those containing an alkyl group include methyltriethoxysilane, methyltriisopropoxysilane and the like.

Next, as the above-mentioned polyamide resin, for example, various polyamides obtained by polycondensation of a lactam having three or more rings, a polymerizable ω-amino acid, a dibasic acid and a diamine or the like can be used. Specifically, for example, polymers such as ε-caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, or butanediamine, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine , Diamines such as meta-xylene diamine, and terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid,
A polymer obtained by polycondensing a dicarboxylic acid such as glutaric acid or the like, or a copolymer thereof is exemplified. Specific examples thereof include aliphatic polyamides such as polyamide 6, polyamide 66, polyamide 6,10, polyamide 11, polyamide 12, and polyamide 6.12, polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, and xylene group. Aromatic polyamides such as contained polyamides and the like can be mentioned, and these can be used as a mixture or a copolymer of two or more kinds.

Furthermore, the reason that the content of the ethylene-α, β-unsaturated carboxylic acid ester-maleic anhydride terpolymer is set to 55 to 90% by weight is that when the content is less than 55% by weight, moldability deteriorates. If the content exceeds 90% by weight, the adhesiveness to the glass plate is reduced. The content of the alkoxysilane compound is 0.5 to 10% by weight, preferably 1 to 10% by weight.
If it is less than 0.5% by weight, the adhesiveness to the glass plate decreases, and if it exceeds 10% by weight, the effect of increasing the amount is not recognized. Further, the content of the polyamide resin is 40 to 5% by weight, and outside of this range, the adhesiveness to the glass plate is reduced.

The multiphase thermoplastic resin in which the matrix phase is a polyamide resin is a composition comprising a polyamide resin and a resin such as polyphenylene ether, polypropylene and ABS resin. , Polyamide
It is 66 mag.

Further, since the resin composition comprising the polyamide resin and polyphenylene ether has poor affinity and exhibits only extremely low mechanical properties, a compatibility improver is added. Examples of the compatibility improver include maleic acid, maleic anhydride, fumaric acid, unsaturated amine, glycidyl methacrylate and the like, and ester compounds of saturated aliphatic polycarboxylic acids such as citric acid, malic acid and agaric acid, amides Compounds, anhydrides, hydrates and salts and the like, for example, chloroformyl succinic anhydride, chloroethanoyl succinic anhydride, trimellitic anhydride chloride, trimellitic anhydride acetic anhydride, terephthalic acid chloride, etc. And, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (βaminoethyl) -aminopropyltrimethoxysilane , N- (βaminoethyl)- It is at least one compound selected from the group consisting of aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptomethylethoxysilane and the like. When the compatibility improver is blended, a radical initiator may be used in combination.

Further, these resin compositions are as follows:
For example, polyphenylene ether is useful in improving the difficulty in processing and low solvent resistance and the low heat resistance and high water absorption of a polyamide resin, and uses a polyamide resin as a matrix to ensure processability.

Further, the resin composition comprising the above polyamide resin and polypropylene improves the heat resistance and coating properties of polypropylene and the water resistance, chemical resistance and impact resistance of the polyamide resin, and ensures heat resistance. Therefore, a polyamide resin is used as a matrix.

Further, the polyamide resin and ABS
The resin composition comprising a polyamide resin has heat resistance and oil resistance possessed by the polyamide resin, and has the disadvantages of impact resistance and moisture absorption of A.
It is improved by BS and further reduces the molding shrinkage.

As the reinforcing material for the synthetic resin composition, general reinforcing materials such as inorganic fibers such as glass fibers and organic fibers such as aramid fibers are used.
On the other hand, as a method for forming the resin film, for example, a method using a 30 mmφ twin-screw extruder with a vent device and a 20 mmφT die film forming machine and the like, which shows a fusion property at a temperature of about 50 to 200 ° C., Resin temperature during molding of the molding or holder, for example, a temperature at least lower than about 60 to 250 ° C.,
Preferably, a temperature as low as about 10 to 150 ° C. exerts a strong fusion force. The temperature is determined by the combination of the molding resin and the resin film, the thickness of the film, and the mold temperature (usually 50 ° C.).
-100 ° C), and the thickness of the resin film is about 5 to 250 µm. If the thickness exceeds 250 µm, the adhesion of the integrally molded holder or molding to the glass plate is improved. It is difficult to obtain, for example, about 100 to 200 μ
When the thickness is less than 5 μm, the effect of improving the adhesion is likely to be reduced, and it is difficult to stabilize the film at the time of molding.
It is preferable that the total thickness be 250 μm or less, such as using about 1 to 3 sheets having a thickness of μ.

Further, as the sealing material and the cushioning member, for example, fluororesin, silicone resin, silicone rubber or the like can be adopted. It goes without saying that the sealing material may be fixed using a spring or the like.

Further, as the injection molding method, for example, RIM (reaction injection molding) method, R-RIM (reinforced reaction injection molding)
Method, LIM (Liquid Injection Molding) method or R-LIM (Reinforced Liquid Injection Molding) method can be adopted for integral molding. R-RIM method or R-LIM method is used for the holder, and RIM is used for the molding. The method or the LIM method is preferred. Further, when the composition is applied to a glass plate or the like, application by brushing or impregnated cloth may be used, and depending on the case, an ordinary application method such as a dipping method or a spray method may be appropriately employed.

Further, as the glass plate-like body,
It may be an inorganic or organic transparent glass plate,
It is not particularly limited to colorless or colored, and its type, color tone, shape, etc. Further, as well as bent sheet glass, various functional glass such as various strengthened glass, strengthened glass, heat ray reflective glass, flat plate and single plate And multi-layer glass or laminated glass, and an acrylic plate, a polycarbonate plate and the like which have been subjected to a hard coat treatment as required, and are used for construction, furniture, vehicles, automobiles and the like.

Further, the required portion of the peripheral portion of the glass plate in which the holder is integrally molded is preferably on the lower edge side of the glass plate, but depending on the method of elevating the glass plate, opening and closing the glass plate, and the like, it is preferable. One or both side edges or the upper edge side of the shape body may be provided, and the number of integrally molded holders may be one in a wide portion or may be provided by dividing into two or more. The selection depends on the lifting, opening and closing method and the balance, weight, shape, and the like of the size of the glass plate, and a glass plate formed integrally with a molding (including a gasket). The required portion of the peripheral portion means the entire periphery from at least one side of the glass plate.

[0033]

As described above, according to the present invention, a specific adhesive resin film or a specific adhesive resin film containing an alkoxysilane compound and a polyamide resin having a specific hot-melt property can be obtained by the method of the present invention. In a state in which the conductive resin film-like layer is set in advance so as to be adhered to at least a predetermined portion of the peripheral portion of the glass plate-like body, a molding made of a multi-phase thermoplastic resin composition in which the polyamide layer or the matrix phase is a polyamide resin or Since the holder is to be integrally molded, the resin film or the resin film-like layer itself will be in a kind of molten state or a state close to it, and the fusion part between the glass plate and the molding or holder will be stronger. Ensures ideal integration, as well as water, weather, heat and chemical resistance Sex like durability increases, especially shear peel strength of the heat resistance, for example, after exposure to about about 5 hours in an atmosphere of about 80 ° C., remarkably improved about 5.0 ~5.5kg / cm ² less than approximately And cannot be obtained by bonding a conventional glass plate and a molding or a holder,
For example, by blending an alkoxysilane compound and a polyamide as one component in the adhesive resin film or film-like layer, the adhesive strength by thermocompression bonding at a temperature much lower than the melting point of the polyamide resin will be significantly improved, Adhesion and molding can be performed simultaneously and instantly, resulting in high work efficiency and reduced man-hours, which can save labor, further improve the work environment, and improve the curvature of the glass plate. It is possible to improve the dimensional accuracy without developing it, and to avoid those that are likely to reduce the strength of the glass plate, and to achieve high quality, and furthermore, lighter, smaller, thinner, etc. The present invention can provide a molding or a glass plate-like body with a holder and a method for producing the same, which exhibit a number of remarkable effects such as enabling In particular automotive window glass, in particular lifting window glass, architectural window glass, is intended in particular to be a widely adopted possible to the door glass, various Furniture Hinto a variety of applications.

[0034]

Embodiments of the present invention will be described below with reference to the drawings. However, the present invention is not limited to such an embodiment.

As shown in the schematic front view of FIG.
Peripheral edge 3 of a required portion of a door glass for elevation, which is a side window for an automobile, of a clear float glass plate 2 having a required shape of about 1000 mm x 800 mm and a thickness of about 4 mm.
As shown in an enlarged partial side sectional view of FIG. 4, a molding or a holder according to the present invention, which is integrally molded with the resin film 5 in a set state immediately before injection of the liquid synthetic resin for the holder 4 in the mold 6 . As shown in FIG. 2 and FIG. 3, which are taken along the line II in FIG.
An intended holder 4 having a side cross section is attached integrally,
To obtain a mall or holder with a glass plate-like body 1 which is an embodiment of a glass plate body with the holder of the present invention shown in FIG.

First, a ternary copolymer of ethylene-α, β-unsaturated carboxylic acid ester-maleic anhydride was prepared using Pondyne TX8030 [ethylene / ethyl Acrylate / maleic anhydride = 85 / 11.5 / 3.5% by weight, MRF = 3.0g
/ 10 min (190 ° C, 2160g)] (manufactured by Sumika Atochem), KBE1003 (vinyltriethoxysilane), KBM1003 (vinyltrimethoxysilane), KBM4 as alkoxysilane compounds
03 (γ-glycidoxypropyltrimethoxysilane) and A1022S (polyamide 6, relative viscosity = 2.17 dl / g, manufactured by Unitika Ltd.) as a polyamide resin in a weight ratio of 7 to
An adhesive composition melt-kneaded in a ratio of 8 to 3 to 1 to 30 to 20 is dried, then filmed at a set temperature of about 260 ° C. using a 20 mm φT die film molding machine, and a resin having a thickness of about 50 μm and about 150 μm is formed. Film 5 was obtained and prepared in advance.

Next, as shown in FIG. 4, the mold 6 includes a core mold member 7 at a lower portion and a mold mold member 8 at an upper portion. ,
First, the both parts are opened, and a required portion of the peripheral part 3 of the glass plate body 2 is put on the sealing material 10 which is also a cushioning material of the holding part 9 of the core type member 7. The peripheral portion of the glass plate 2 which has been coated with the primer treatment layer 12 with a silane coupling agent such as aminopropyltriethoxysilane or the like so as to surround the above-mentioned resin film 5 of about 150 μm in advance in the treated portion. 3 is placed in contact with a predetermined portion, and then the mold member 8 is placed on the glass plate 2 at about 70 ° C. via a sealing material 10 which is also a cushioning material.
A glass space 2 is formed by clamping and sealing the glass plate 2 at the clamping portions 9 of the mold members 7 and 8 by clamping with a pressure of about 120 to 150 kg / cm ^2. Complete the set.

A polyamide resin, for example, polyamide-6 or polyamide-66 (PA-6, PA-66), polyphenylene ether (PPE) and maleic anhydride (MAH) sent from an injection molding apparatus main body (not shown) Furthermore, a composition obtained by melt-kneading glass fiber (GF) (PPE /
PA-6 or PA-66 / MAH / GF = 35/35 / 0.5 / 30 parts by weight), a liquid synthetic resin composition for holder 4 which is a multiphase structure in which polyphenylene ether is finely dispersed in a polyamide resin matrix. About 240-280 ° C, mold temperature about 70-80 ° C
About 110 to 130 kg / cm ² from the inlet through an after-mixer etc. in the cavity space 13 under the condition of about
After the injection and injection for about 60 seconds, the molding is performed and the synthetic resin composition is solidified. Then, the glass plate 2 is taken out from the mold 6 to remove the peripheral edge of the glass plate 2 as shown in FIGS. The holder 4 is molded at a required portion of the part 3.

When the above-mentioned resin film is adhered to a peripheral portion of a required portion of the glass plate, the resin film may be pinched and fixed, for example, by pressing the peripheral portion of the resin film with the sealing material. Depending on the shape, the injection port of the liquid synthetic resin composition may be provided at two upper and lower locations or simply at several locations around the mold depending on the shape. It is intended to maintain a suitable temperature so that it can be controlled in consideration of heat shock or foaming of the synthetic resin composition or formation of a skin layer, and in any case, at any time, temperature, injection location, It is natural that injection injection can be performed while adjusting the injection amount and the like.

As shown in FIG. 1, the obtained glass plate-like body 1 with a holder is a glass plate-like body 2 cut into a substantially trapezoidal shape, in particular, a flat plate-like shape on the peripheral edge 3 on the lower side of the glass plate-like body 2. (It is not always necessary to have such a shape or may be omitted in some cases.), And the projections 14 correspond to the peripheral portions 3 on the front and back surfaces surrounding the flat dish-shaped projection 14. Over the end face 11, and integrally molded with the resin composition,
Made by fixing the holder 4 is a plan T shape, the holder 4 are those provided with a tongue 16 having a threaded portion 15 for fixing the guide channel or the like for coupling to the lifting device (not shown) 2 and FIG. 3, which is a partially enlarged view of FIG. 2, the glass plate 2 and the coupling treatment layer 12, the coupling treatment layer 12 and the resin film 5, and the resin film 5 By using the holder 4 made of the synthetic resin composition, not only the adhesive strength between the respective members but also the overall adhesive strength is remarkably improved.

That is, with the obtained holder of the present invention
A glass plate-like body and a single unit without the conventional resin film
The shear peel strength was compared between
For example, about 1.2 to 1.5 kg without conventional resin film
/cm^TwoOr less than that of the present invention.
About 13kg / cm for glass plate with rudder^TwoAbnormalities still occur
Not heat-resistant, especially about 50-80
Even after being exposed to the atmosphere for about 4 to 5 hours at about
For example, under the condition of a peeling rate of about 10 mm / min at a predetermined temperature
The shear peel strength is improved in, for example, about 5.
0 to 5.5 kg / cm ^TwoOr more.

The strength of the glass plate with holder of the present invention is extremely high, which is markedly different from the conventional bonding method using, for example, silicon, which is not integrally formed. As the resin film, for example, a polyvinyl butyral resin or a polyacetal copolymer resin having a thickness of about 300 to 350 μm, or an ethylene copolymer resin having a thickness of about 150 μm is used. Similar prototypes had little or no improvement in the strength, or were not what was expected. Further, the strength of the glass plate with holder of the present invention is higher than the strength of the glass plate with holder of the present invention already proposed in Japanese Patent Application Laid-Open No. 1-209116, particularly in terms of heat resistance. there were. In addition, the glass plate-shaped body with a holder of the present invention has moisture resistance (for example, about 40 to 50 ° C., about 95 to 98%
RH, about 160-170H peel strength measurement) and water resistance and weather resistance (immersion in water at room temperature of about 20 ° C, about 70
剥離 170H under the condition of peel strength).

[0043]

As described above, according to the present invention,
It is fused to the glass plate and fused with the synthetic resin composition for moldings or holders to function as a gradient composition, achieving more effective integral molding. To provide an unprecedented overall strength, and in particular, to significantly improve the heat resistance, especially when the thermocompression bonding at a temperature much lower than the melting point of the polyamide resin. In addition to providing various functions and effects such as improved water resistance, it can also respond to high-grade appearance, high function or multi-functional orientation, and can save labor and efficiency of work and high environment, An object of the present invention is to provide a useful molding or glass plate with a holder, which has a wide range of effects such as improved dimensional accuracy and high quality and high productivity, and a method for producing the same.

[Brief description of the drawings]

FIG. 1 is a schematic front view of a glass plate with a holder according to an embodiment of the present invention.

FIG. 2 is an enlarged partial side sectional view of the holder integrated molding portion, as viewed from II in FIG.

FIG. 3 is a side cross-sectional view in which the holder integrally molded portion shown in FIG. 2 is further partially enlarged.

FIG. 4 is a partial side sectional view showing, in an enlarged scale, an in-mold set state before integral molding in an explanatory view when the manufacturing method according to the present invention is performed.

[Description of Signs] 1 Glass plate with holder 2 Glass plate 3 Peripheral part 4 Holder 6 Resin film 6 type 7 Core type member 8 Cabi type member 13 Cavity space

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI E06B 3/54 E06B 3/54 // B29K 105: 20 B29L 31:30 (58) Investigation field (Int.Cl. ⁷ , DB Name) B29C 45/14 B32B 27/28 B60J 1/00 C03C 27/06 C03C 27/12 E06B 3/54 B60J 1/17

Claims (10)

(57) [Claims]

1. A resin film or a resin film-like layer is preliminarily provided at a required portion of a peripheral portion of a glass plate from at least one sheet or one layer so as to surround the peripheral portion of the glass plate. Apply the resin over the corresponding end face , and insert a resin molding or holder by the injection molding method.
Glass plate with film or resin film layer
The resin film or the resin film-like layer is formed of an ethylene-α, β-unsaturated carboxylic acid ester-maleic anhydride ternary mold in a molding or a glass plate with a holder , which is integrally molded with a glass plate at the peripheral portion of the glass plate. Polymer 55 ~
90% by weight and R'nSi (OR) _4-n (R 'is an amino group, an epoxy group, a mercapto group, a methacryloxy group, a polar group having an acryloxy group, a vinyl group, an alkyl group having 1 to 20 carbon atoms. R is an alkyl group having 1 to 8 carbon atoms, and n is 1 or 2.) 0.5 to 10% by weight of an alkoxysilane compound represented by the formula and 40 to 5% by weight of a polyamide resin. %, And a glass plate with a molding or a holder.

2. The method according to claim 1, wherein the alkoxysilane compound is at least one selected from vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltriethoxysilane.
The glass plate with a molding or a holder according to claim 1, which is a kind of alkoxysilane compound.

3. The ethylene-α, β-unsaturated carboxylic acid ester-maleic anhydride terpolymer comprises 40 to 90% by weight of ethylene units and 55 to 5% by weight of α, β-unsaturated carboxylic acid alkyl ester units. , Maleic anhydride unit 0.1 ~
3. The glass plate with a molding or a holder according to claim 1, which is a copolymer comprising 10% by weight.

4. The resin molding or holder,
2. A molding or a glass plate with a holder according to claim 1, wherein said glass plate is made of a polyamide resin or a multi-phase thermoplastic resin whose matrix phase is a polyamide resin.

5. The multi-phase thermoplastic resin in which the matrix phase is a polyamide resin is a resin composition obtained from a polyamide resin and polyphenylene ether, polypropylene, or ABS.
The glass plate-like body with the molding or holder described in the above.

6. A multi-phase thermoplastic resin in which the matrix phase is a polyamide resin, wherein the polyamide resin comprises a polyamide resin and polyphenylene ether or polypropylene or ABS;
5. A molding or a glass plate with a holder according to claim 4, which is a resin composition obtained from glass fibers.

7. The method according to claim 7, wherein the polyamide resin is polyamide-6.
7. The molding or the glass plate with a holder according to claim 5, wherein the glass plate is a polyamide 66.

8. A resin composition obtained from the polyamide resin and polyphenylene ether, comprising: a polyamide resin;
The glass plate with a molding or a holder according to claim 5, which is a resin composition comprising polyphenylene ether and a compatibility improver.

9. A resin molding or a holder is integrally molded and fixed to a required portion of a peripheral portion of the glass plate-like body, and ethylene-α, β-unsaturated carboxylic acid ester-maleic anhydride ternary component is fixed to the required portion. 55 to 90% by weight of a copolymer and R'nSi (OR) _4-n (R 'is a polar group having an amino group, an epoxy group, a mercapto group, a methacryloxy group, an acryloxy group, a vinyl group, and a carbon number of 1 to 1)
Represents 20 alkyl groups or alkenyl groups, and R represents 1 carbon atom
Represents up to 8 alkyl groups, and n is 1 or 2. )
0.5 to 10% by weight of an alkoxysilane compound represented by the formula
At least one sheet containing a resin film composed of 40 to 5% by weight of a polyamide resin is applied so as to surround beforehand from the peripheral edges of both front and back surfaces to the corresponding end surfaces, and the glass plate is placed in a mold. A resin composition comprising a polyamide resin or a multi-phase thermoplastic resin whose matrix phase is a polyamide resin is injected and injected into a cavity space defined by the surface of the resin film and the inner surface of the mold. A method for producing a molding or a glass plate with a holder, wherein the glass plate is removed from the mold after the product is solidified.

10. The method according to claim 9, wherein the multi-phase thermoplastic resin in which the matrix phase is a polyamide resin contains glass fibers.