KR101727906B1 - Glazing sheet using vehicle - Google Patents

Glazing sheet using vehicle Download PDF

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Publication number
KR101727906B1
KR101727906B1 KR1020150073009A KR20150073009A KR101727906B1 KR 101727906 B1 KR101727906 B1 KR 101727906B1 KR 1020150073009 A KR1020150073009 A KR 1020150073009A KR 20150073009 A KR20150073009 A KR 20150073009A KR 101727906 B1 KR101727906 B1 KR 101727906B1
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KR
South Korea
Prior art keywords
layer
glass
plastic
hard coating
polycarbonate
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KR1020150073009A
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Korean (ko)
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KR20160138752A (en
Inventor
김남일
오미혜
윤여성
김아영
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자동차부품연구원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B60J1/001—Double glazing for vehicles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10366—Reinforcements of the laminated safety glass or glazing against impact or intrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/24—Organic non-macromolecular coating

Abstract

The present invention relates to an automotive glazing sheet having an impact resistance and a light weight, comprising: a glass layer; A plastic layer formed on one surface of the glass layer; An adhesive layer formed between the glass layer and the plastic layer; And a hard coating layer comprising a mixture of at least two or more polyfunctional acrylic monomers formed on one surface of the plastic layer.

Description

[0001] Glazing sheet using vehicle [

The present invention relates to automotive glazing heterogeneous bonding sheets. Specifically, this invention relates to a heterogeneous bonded sheet of plastic such as glass and polycarbonate, an adhesive suitable for heterojunction bonding, and a hard coating layer having excellent scratch resistance.

Due to the increasing environmental regulations and high oil prices, development of low fuel consumption vehicles has become essential. It can be expected that the fuel efficiency can be improved by about 3.8% even if the weight of the passenger car is reduced by only 10%, and the acceleration performance, the steering performance and the durability life are also improved. In order to achieve the functionality and lighter weight of automobiles currently being marketed, researchers have been steadily developing research and development projects to replace heavy metal and ceramic materials with lightweight polymer resins. A replacement window is a typical example.

Glass glazing parts for automobiles are mainly used because they have excellent durability and excellent transparency. Automotive windshields are manufactured by joining two sheets of glass with polyvinyl butyral (PVB) film, and tempered glass is used for sunroof. However, glass is fundamentally heavy, and there is a problem in securing stability due to cracking at the time of collision, and development of alternative materials is progressing steadily. Polycarbonate (PC) has excellent inherent transparency and impact resistance, and it is expected that the demand for parts for automobile windows will increase greatly in the future. Its specific gravity is about 1.2 g / ㎤, which is more than 1/2 lighter than glass, and its refractive index is about 1.585. When transparent plastic is applied to windshield, side glass and sunroof for vehicle, the weight is reduced by 30% or more, which leads to improvement in fuel efficiency due to light weight. However, due to the ductility characteristics, the surface hardness is low, yellowing occurs when exposed to the outdoor for a long time, and the chemical resistance to the organic solvent is low, which limits the application field. Therefore, it is necessary to develop a material that can attain light weight while maintaining excellent surface hardness and transmittance of glass.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a glazing sheet for automobiles which is excellent in impact resistance and light in weight by bonding dissimilar sheets of glass and plastic.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. It can be understood.

To achieve the above object, the glazing sheet for automobile of the present invention comprises a glass layer; A plastic layer formed on one surface of the glass layer; An adhesive layer formed between the glass layer and the plastic layer; And a hard coating layer comprising a mixture of at least two or more polyfunctional acrylic monomers formed on one surface of the plastic layer.

In one embodiment, the material of the plastic may be polycarbonate.

In another embodiment, the polycarbonate may be a bio-polycarbonate of formula (1).

[Chemical Formula 1]

Figure 112015050248571-pat00001

In Formula 1, m and n are integers of 1 to 5.

In another embodiment, the material of the adhesive layer may be polyurethane.

In another embodiment, the material of the adhesive layer may be a polyolefin elastomer.

In yet another embodiment, the adhesive layer may be formed of OCA.

In yet another embodiment, the hard coating layer may further comprise a bifunctional acrylate having a molecular weight of 7,000 to 20,000.

In yet another embodiment, the bifunctional acrylate may comprise at least one hydroxyl group or ethylene oxide in the molecule.

In another embodiment, the multifunctional acrylic monomer mixture may include at least two acrylic monomers selected from the group consisting of a 15-functional acrylic monomer, a 10-functional acrylic monomer and a 6-functional acrylic monomer.

The present invention is a glazing sheet for automobiles that overcomes the limitations of conventional glass and plastic materials, and achieves excellent impact resistance and light weight by bonding glass and plastic sheets to each other.

Also, there is provided a glazing sheet for automobiles having excellent scratch resistance by applying a hard coating layer comprising two or more polyfunctional acrylic monomers.

1 is a sectional view showing a glazing sheet for an automobile according to the present invention.
Fig. 2 is a photograph showing the impact resistance of an automotive glazing sheet according to the present invention.
3 is a graph showing impact resistance of a glazing sheet for an automobile according to the present invention.
4 is a graph showing the weight reduction of a glazing sheet for an automobile according to the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms " comprising, "" including, "or" having ", when used in this application, specify features, numbers, steps, operations, elements, But do not preclude the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, the well-known functions or constructions are not described in order to simplify the gist of the present invention.

The automotive glazing sheet 100 of the present invention comprises a glass layer 200, an adhesive layer 300, a plastic layer 400, and a hard coat layer 500, as shown in FIG.

The plastic layer 400 may be polycarbonate (PC). Polycarbonate has excellent transparency, mechanical strength, and heat resistance, and is widely used in the manufacture of transparent sheets for construction. Polycarbonate is expected to have a great demand for automobile window parts. It has a specific gravity of about 1.2g / ㎤, which is more than 1/2 lighter than glass and has a refractive index of about 1.585. In addition, since it has an impact resistance of about 250 times or more than that of plate glass, it is effective for prevention of detachment of passengers in collision and overturning, which is excellent in safety and hard to break from outside. (Tm) of 220 to 250 ° C, a glass transition temperature (Tg) of 145 ° C, and a heat distortion temperature (HDT) of 120 to 140 ° C. Polycarbonate has attracted much attention as a substitute material for glass due to its advantages such as high visible light transmittance (85% or more), impact resistance, weatherability and self-extinguishing ability.

The polycarbonate may be a biopolycarbonate having a molecular structure represented by the following formula (1).

[Chemical Formula 1]

Figure 112015050248571-pat00002

M and n in Formula 1 may be an integer of 1 to 5.

The use of bio-polycarbonate solves the problem of bisphenol A (BPA), which affects environmental hormones, and its mechanical and thermal optical properties are equivalent to that of BPA-based polycarbonate.

The adhesive layer 300 may be a film type or a liquid type. As the film type, polyurethane (PU) or polyolefin elastomer (POE) can be used. Such a film-type adhesive layer 300 may be laminated between the glass layer 200 and the plastic layer 400 and then heated to 100 ° C or higher to be bonded. The bonding may be formed by a thermal compression method, an autoclave method, or the like.

The liquid type may be optically transparent and LOCA (lucid optically clear adhesive) having excellent adhesion to the glass layer (200) and the plastic layer (400). In the case of the LOCA bonding liquid, a double-faced tape is attached to both ends of the glass layer 200 to make a space between the plastic layer 400 and the glass layer 200. The LOCA bonding liquid flows through the gap, (Total light amount: 1,200 mJ / cm < 2 >). By the application of the LOCA, it is possible to prevent the occurrence of bubbles between the glass layer 200 and the space of the plastic layer 400, and also to prevent the view distortion due to the difference in refractive index.

In the present invention, the polycarbonate applied to one embodiment of the plastic layer (400) has low scratch resistance due to its ductility, and has poor adhesion to the coating layer, which may limit its application. Therefore, it is necessary to develop a coating system capable of improving adhesion to polycarbonate and improving scratch resistance. In order to solve such a problem, the present invention has developed a hard coating layer 500 comprising a mixture of two or more polyfunctional acrylic monomers.

The hard coating layer 500 is formed on one surface of the plastic layer 400, has excellent scratch resistance with a pencil hardness of H or higher, and can achieve a visible light transmittance of 85% or more.

The hard coat layer 500 may include at least two or more multifunctional acrylic monomer mixture, and may further include a bifunctional acrylate having a molecular weight of 7,000 to 20,000, an organic solvent, and an additive.

The multifunctional acrylic monomer mixture is a mixture of urethane-based acrylic monomers and may include a 15-functional acryl monomer, a 10-functional acrylic monomer, a 6-functional acrylic monomer or a mixture thereof. The hard coating composition comprising a urethane-based acrylic monomer mixture is advantageous in terms of control of final properties of the coating layer since the curing rate upon irradiation with ultraviolet rays is fast and the curing conditions such as light quantity, temperature and irradiation time can be easily controlled. The reason for mixing at least two kinds of the multi-functional acrylic monomer mixture is that the scratch characteristics of the coating layer can be controlled by controlling the density of the network. 15 functional group acrylic monomers may be 10% by weight to 40% by weight, 10-functional acrylic monomers may be 10% by weight to 30% by weight, and 6-functional acrylic monomers may be 5% by weight to 10% by weight.

The hard coat layer 500 may further comprise a bifunctional acrylate. The bifunctional acrylate having a high molecular weight can improve the flexibility and hardness of the hard coating layer 500. A bifunctional acrylate having a large molecular weight may be used, and preferably has a molecular weight of 7,000 to 20,000, more preferably 10,000 to 15,000. Bifunctional acrylates may be hydrophilic. And may contain a hydroxyl group or ethylene oxide to impart hydrophilicity. The bifunctional acrylate may be included in an amount of 5 to 15% by weight.

Ethyl acetate (EA) may be used as the organic solvent. The organic solvent may comprise from 30% to 85% by weight of the total composition forming the hard coat layer. Since ethyl acetate has a low boiling point (BP, ~ 77 ° C), it can be easily removed even in a general oven when the hard coating composition is dried. Also, if the contact time with the plastic layer to be coated is short, the interpolating layer can be formed by etching the surface without affecting transparency. The increase in the surface roughness of the plastic layer due to etching increases the contact area with the coating layer and consequently leads to an improvement in the adhesion.

As the additive, a photoinitiator may be used. The photoinitiator may comprise from 1 wt% to 5 wt% of the total composition forming the hard coat layer. The photoinitiator functions to decompose the photoinitiator and form radicals in the step of irradiating ultraviolet rays after coating the hard coat composition on the plastic layer. As the photoinitiator, generally known photoinitiators may be used. As the photoinitiator, commercially available Irgacure 184, Irgacure 754, Irgacure 1173, Irgacure 651 and the like can be used.

The hard coating layer 500 is prepared by preparing a hard coating composition comprising at least two polyfunctional acrylic monomer mixture, an organic solvent and an additive, coating the hard coating composition on one surface of the plastic layer 400, And drying the hard coating composition at a temperature of 60 ° C to 100 ° C for 1 minute to 10 minutes.

Also, the method of forming the hard coat layer 500 may include preparing a hard coat composition comprising at least two polyfunctional acrylic monomer mixtures, an acrylate having a molecular weight of 7,000 to 20,000, an organic solvent, and an additive; Coating the hard coating composition on one side of a plastic layer; Drying the hard coating composition at a temperature of from 60 DEG C to 100 DEG C for 1 minute to 10 minutes; And ultraviolet light having a total light amount of 500 mJ / cm 2 to 2000 mJ / cm 2 for 3 seconds to 30 seconds.

In preparing the hard coating composition, the hard coating composition is prepared according to the composition described above. The composition and composition of the hard coating composition are described above, and therefore, a description thereof will be omitted in order to avoid redundancy. First, 15-functional acrylic monomers, 10-functional acrylic monomers and 6-functional acrylic monomers are dissolved in an organic solvent. When the multifunctional acrylic monomer mixture is completely dissolved, the acrylate is added and mixed. The hard coating composition is then homogenized by stirring for at least 2 hours.

In the step of coating the hard coating composition on the plastic layer 400, the homogenized hard coating composition is coated on the plastic layer 400 using a bar coater or a spin coater. The coating method is not limited in this embodiment, and a coating method which is usually used in a similar process can be used. The thickness of the layer to be coated can be adjusted according to the required physical properties, so that the drying time, the total amount of light upon irradiation with ultraviolet rays and the irradiation time can be controlled in a subsequent process.

In the drying step, the plastic layer 400 coated with the hard coating composition is dried in an oven maintained at a temperature of 60 ° C to 100 ° C for 1 minute to 10 minutes. The drying time is adjustable according to the thickness of the coating, and it is preferable to leave in an oven for a time sufficient for the organic solvent to be completely removed. The hard coating composition thus removes the organic solvent and leaves only the mixture of monomers on the plastic layer 400. The apparatus used in the drying step may be one which is used in a general process such as a convection oven, and is not particularly limited. During the drying step, the surface of the plastic layer is etched to form irregularities while the organic solvent is completely removed. This unevenness increases the roughness of the surface of the plastic layer 400 and increases the contact area with the coating layer.

In the ultraviolet irradiation step, the hard coating layer is irradiated with ultraviolet light (UV) so that the monomer mixture can cause a photo-curing reaction. A mercury lamp or the like can be used for the ultraviolet ray irradiation, and the ultraviolet ray intensity is not particularly limited as long as the intensity of the ultraviolet ray is 200 mW / cm 2 to 300 mW / cm 2. In this embodiment, an ultraviolet curing conveyor system incorporating a mercury lamp is used. The UV curing conveyor system with the mercury lamp can control the curing speed and network density by controlling the speed of the continuously moving conveyor to control the total amount of exposure the specimen receives. When ultraviolet light (UV) is irradiated, the monomer mixture is polymerized to form a network. The polymer in which the network is formed enhances the hardness of the surface.

The hard coating layer thus formed may have a pencil hardness H or higher and a visible light transmittance of 85% or higher.

FIGS. 2 and 3 are photographs and graphs of a fallen impact strength test for the impact resistance effect of the automotive glazing sheet 100 of the present invention. Fig. 2 (a) is a glass / glass bonded specimen, Fig. 2 (b) is a polycarbonate / polycarbonate bonded specimen, and Fig. 2 (c) is a test result of a glass / polycarbonate bonded specimen. As can be seen in the photographs, (a) the glass / glass bonded specimen is broken and the fragments are separated after the impact, and (b) the polycarbonate / polycarbonate bonded specimen is only punctured (C) The glass / polycarbonate joint specimen has a hole in the impact surface and a slight crack along its periphery. Also, FIG. 3, which shows the drop impact strength as Joule, shows that the glass / polycarbonate bonded specimen shows a higher absorption energy than the glass / glass bonded specimen. Therefore, the heterogeneous bonded sheet of the present invention proved to have better impact resistance than the glass / glass bonded sheet.

The adhesive layer 300 used in the impact resistance test of FIGS. 2 and 3 used liquid OCA. Accordingly, it has been confirmed that OCA can have excellent impact resistance in the heterojunction of the present invention, and it is also confirmed that the film-type polyurethane and polyolefin elastomer of the present invention have excellent impact resistance.

4 is a graph showing the effect of lightening the glazing sheet 100 for an automobile according to the present invention. As shown in FIG. 4, the weight saving effect is about 30% as compared with the glass / glass bonded sheet.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It is obvious to those who have.

100: Glazing sheet
200: glass layer
300: plastic layer
400: adhesive layer
500: hard coat layer

Claims (9)

Glass layer;
A plastic layer formed on one surface of the glass layer;
An adhesive layer formed between the glass layer and the plastic layer; And
And a hard coating layer comprising a mixture of at least four or more polyfunctional acrylic monomers formed on one surface of the plastic layer,
The multifunctional acrylic monomer mixture may contain,
15 functional acrylic monomers, 10 functional acrylic monomers, 6 functional acrylic monomers and bifunctional acrylates,
Wherein the plastic material is polycarbonate and is a polycarbonate having the following formula (1):
[Chemical Formula 1]
Figure 112017019497901-pat00003

In Formula 1, m and n are integers of 1 to 5.
delete delete The method according to claim 1,
Characterized in that the material of the adhesive layer is polyurethane.
The method according to claim 1,
Characterized in that the adhesive layer is a polyolefin elastomer.
The method according to claim 1,
Characterized in that the adhesive layer is formed of OCA.
The method according to claim 1,
Wherein the hard coating layer comprises a bifunctional acrylate having a molecular weight of 7,000 to 20,000.
The method of claim 7,
Wherein the bifunctional acrylate comprises at least one hydroxyl group or ethylene oxide in the molecule,
delete
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KR102214121B1 (en) 2020-07-30 2021-02-10 주식회사 서연이화 Method for manufacturing plastic glazing
KR102335406B1 (en) 2020-07-30 2021-12-09 주식회사 서연이화 Method for manufacturing plastic glazing
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