WO2017143987A1

WO2017143987A1 - Exterior trim, glass window including the exterior trim and injection molding method for forming glass window

Info

Publication number: WO2017143987A1
Application number: PCT/CN2017/074407
Authority: WO
Inventors: Tao He; Yunxin GU; Ce Shi
Original assignee: Saint Gobain Glass France SAS; Compagnie de Saint Gobain SA
Current assignee: Saint Gobain Glass France SAS; Compagnie de Saint Gobain SA
Priority date: 2016-02-23
Filing date: 2017-02-22
Publication date: 2017-08-31
Anticipated expiration: 2018-08-23

Abstract

The present disclosure provides an exterior trim, a glass window including the exterior trim and an injection molding method for forming a glass window. The exterior trim includes: a substrate and a modified polyurethane coating disposed on a surface of the substrate. The glass window includes: a glass plate, the above recited exterior trim, and an edge encapsulation around an edge of the glass plate, wherein the exterior trim is fixed to the glass window via the edge encapsulation. The injection molding method for forming the glass window includes: placing a glass plate and a exterior trim having a modified polyurethane coating on a surface thereof, which are placed together, in a mold; injecting a molding material into a mold cavity; and cooling the molding material which is injection molded to form an edge encapsulation around the edge of the glass plate.

Description

EXTERIOR TRIM, GLASS WINDOW INCLUDING THE EXTERIOR TRIM AND INJECTION MOLDING METHOD FOR FORMING GLASS WINDOW

This application claims the benefit of priorities to Chinese Patent Application No. CN201610099169.6 titled “GLASS WINDOW AND INJECTION MOLDING METHOD FOR FORMING THE SAME” , filed with the Chinese State Intellectual Property Office on February 23, 2016； Chinese Patent Application No. CN201620838573.6 titled “PLASTIC EXTERIOR TRIM” , filed with the Chinese State Intellectual Property Office on August 4, 2016； and Chinese Patent Application No. CN201620838593.3 titled “METAL EXTERIOR TRIM AND GLASS WINDOW INCLUDING THE SAME” , filed with the Chinese State Intellectual Property Office on August 4, 2016, the entire disclosures of which are incorporated herein by references.

FIELD

The present disclosure relates to the vehicle glass window field, in particular to a vehicle glass window including an exterior trim, and more particularly to a vehicle glass window including an exterior trim whose surface is covered with a modified polyurethane coating and a method for forming the glass window.

BACKGROUND

Plastic or metal are widely used as a material of bright bars of a vehicle glass window such as a vehicle windshield or an awning. However, in the course of using a vehicle, the bright bars may inevitably crack over time due to a variety of external conditions such as sun and rain, as well as its own aging. Thus, over time, appearance of the bright bars may become unsightly, and more severely, the bright bars may even crack and can not be used any more.

To date, no method has been developed in the art to effectively prevent the bright bars from cracking.

SUMMARY

Embodiments of the present disclosure provide a novel exterior trim, and a glass window including the exterior trim and an injection molding method for forming the same, so as to solve the deficiencies and problems of the existing technology.

Polyurethane (PU) is a generic term of polymer compounds whose main chain includes a carbamate (-NH-COO-) unit. The polyurethane is a multi-block polymer stepwise polymerized by polyols, small molecule chain extenders and polyisocyanates, where the polyols constitute soft segments, and the small molecule chain extenders and the polyisocyanates constitute hard segments. Thus, by adjusting compositions and proportions of the soft segments and the hard segments, a molecular structure, a physical property and a chemical property of the polyurethane can be effectively controlled. Moreover, the hard segments have a strong polarity and are easy to gather； and a micro-phase separation structure can be formed given a thermodynamic incompatibility between the hard segments and the soft segments. The micro-phase separation structure of the polyurethane makes the polyurethane have a better biocompatibility in comparison with other polymers, which makes the polyurethane capable of being used as a surface coating of medical devices or articles. In addition, the polyurethane has excellent and adjustable physical and mechanical properties, which makes the polyurethane capable of being widely used in surface coating. However, the polyurethane, especially the polyurethane coating, may inevitably be subjected to various external conditions in the course of use, which will directly affect the safety and service life of the polyurethane.

The inventors of the present disclosure found that, a modified polyurethane coating formed by modifying a polyurethane with specific materials can effectively prevent cracking. Thus, when the modified polyurethane is coated onto a functional layer, the functional layer can be effectively prevented from cracking. Based on the above finding, the present disclosure has been accomplished.

In an aspect, an exterior trim is provided according to an embodiment of the present disclosure. The exterior trim includes: a substrate (100) and a modified polyurethane coating (110) disposed on a surface of the substrate (100) , wherein raw materials of the modified polyurethane coating include:

(A) isocyanate, wherein each molecule of the isocyanate has three or more isocyanate groups；

(B) long chain alkyl alcohol, wherein a number of carbon atoms included in the long chain alkyl alcohol ranges from 10 to 25； and

(C) polycaprolactone-modified (meth) hydroxy ethyl acrylate having a formula as follow:

where, R’denotes –CH₃ or –H； and n＝1-25, and

by mole, hydroxyl in the long chain alkyl alcohol (B) : the isocyanate groups in the isocyanate (A) : hydroxy in the polycaprolactone-modified (meth) hydroxy ethyl acrylate (C) ＝ 1 : (3-50) : (2-60) .

In a preferred embodiment, the raw materials of the modified polyurethane coating further include: 0.01 to 5％by weight of an anti-scratch agent, 0.01 to 1％by weight of a catalyst, 0.01 to 1％by weight of an antistatic agent, 0.01 to 1％by weight of a polymerization inhibitor, and a solvent serving as a balance, wherein the raw materials of the modified polyurethane coating are 100％by weight.

In another preferred embodiment, the anti-scratch agent includes organic beads and inorganic beads.

In another preferred embodiment, the organic beads include: polymethyl methacrylate, polyurethane, nylon, and rubber.

In another preferred embodiment, the catalyst is 0.1 to 0.5 ％by weight； and the catalyst includes dibutyltin dilaurate and dibutyl tin diethyl n-hexanoate.

In another preferred embodiment, the antistatic agent includes: an antistatic agent containing lithium, sodium or potassium salt, a cationic antistatic agent containing amine salt or quaternary ammonium salt, and a nonpolar antistatic agent containing C8 to C12 alkyl or alkaryl.

In another preferred embodiment, the polymerization inhibitor includes hydroquinone monomethyl ether.

In another preferred embodiment, the solvent includes: xylene, ketone and ester.

In another preferred embodiment, the ketone includes: acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone； and the ester includes: ethyl acetate, propyl acetate, isobutyl acetate and butyl acetate.

In another preferred embodiment, the substrate is made of metal or non-metal.

In another preferred embodiment, the substrate is made of plastic.

In another preferred embodiment, the plastic includes polyacrylic acid.

In another preferred embodiment, the plastic includes polymethyl methacrylate.

In another preferred embodiment, the substrate is made of aluminum or steel.

In another preferred embodiment, when the substrate is made of metal, a metal oxide layer or an epoxy resin coating layer is further disposed between the substrate and the modified polyurethane coating.

In another preferred embodiment, the modified polyurethane coating has a thickness ranging from 10 microns to 200 microns.

In another preferred embodiment, the isocyanate includes:

where, R denotes

In another preferred embodiment, the long chain alkyl alcohol includes: tridecanol, tetradecanol, hexadecyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene monostearate, polyoxyethylene hexadecyl ether, polyoxyethylene stearyl ether and glycerol monostearate.

In another preferred embodiment, n ＝ 2-5.

In another aspect, a glass window is provided according to an embodiment of the present disclosure. The glass window includes: a glass plate, an exterior trim as recited above, and an edge encapsulation around an edge of the glass plate, wherein the exterior trim is fixed to the glass window via the edge encapsulation.

In another preferred embodiment, an edge of the plastic exterior trim (i.e., the bright bar) is provided with an edge encapsulation-modified polyurethane coating-plastic bright bar-edge encapsulation structure.

In another aspect, an injection molding method for forming a glass window is provided according to an embodiment of the present disclosure. The injection molding method includes: placing a glass plate and a exterior trim having a modified polyurethane coating on a surface thereof, which are placed together, in a mold； injecting the molding material as recited above into a mold cavity； and cooling the molding material which is injection molded to form an edge encapsulation around the edge of the glass plate.

Accordingly, the present disclosure has following advantages:

In comparison with existing vehicle glass windows, the bright bar of the present disclosure, which has a modified polyurethane coating on its surface, has a better crack resistance performance. Moreover, the injection molding method for forming the vehicle glass window of the present disclosure is simple in process and low in cost, thus it can be well applied to manufacture the vehicle glass window with excellent crack resistance performance.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a schematic diagram of a structure of an exterior trim according to an embodiment of the present disclosure； and

Figure 2 is a schematic diagram of a structure of a vehicle glass window according to an embodiment of the present disclosure.

DETAILED DESCRIPTION OF EMBODIMENTS

Exterior Trim

In an aspect, an embodiment of the present disclosure provides an exterior trim including: a substrate and a modified polyurethane coating disposed on a surface of the substrate.

Modified Polyurethane Coating

In the exterior trim of the present disclosure, a thickness of the modified polyurethane coating may be, but not limited to, 10 microns to 200 microns. Raw materials of the modified polyurethane coating include:

(A) Isocyanate

Each molecule of the isocyanate has three or more isocyanate groups, wherein the isocyanate groups include, but not limited to,

wherein, R denotes

(B) Long Chain Alkyl Alcohol

A number of carbon atoms included in the long chain alkyl alcohol ranges from 10 to 25. The long chain alkyl alcohol includes, but not limited to, tridecanol, tetradecanol, hexadecyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene monostearate, polyoxyethylene hexadecyl ether, polyoxyethylene stearyl ether and glycerol monostearate.

(C) Polycaprolactone-modified (meth) Hydroxy Ethyl Acrylate

The polycaprolactone-modified (meth) hydroxy ethyl acrylate has a formula as follow:

where, R’denotes methyl or H； and n＝1-25, optionally, n＝2-5；

wherein, by mole, hydroxyl in the long chain alkyl alcohol (B) : the isocyanate groups in the isocyanate (A) : hydroxy in the polycaprolactone-modified (meth) hydroxy ethyl acrylate (C) ＝ 1 : (3-50) : (2-60) .

Additives

The additives include:

0.01 to 5％by weight of an anti-scratch agent, wherein the anti-scratch agent includes, but not limited to, organic beads and inorganic beads, and the organic beads include, but not limited to, polymethyl methacrylate, polyurethane, nylon, and rubber；

0.01 to 1％by weight of a catalyst, wherein the catalyst is optionally 0.1 to 0.5 ％by weight, and the catalyst includes, but not limit to, dibutyltin dilaurate and dibutyl tin diethyl n-hexanoate；

0.01 to 1％by weight of an antistatic agent, wherein the antistatic agent includes, but not limited to, an antistatic agent including lithium, sodium or potassium salt, a cationic antistatic agent including amine salt or quaternary ammonium salt, and a nonpolar antistatic agent including C8 to C12 alkyl or alkaryl；

0.01 to 1％by weight of a polymerization inhibitor, wherein the polymerization inhibitor includes, but not limited to, hydroquinone monomethyl ether； and

a solvent serving as a balance, wherein the solvent includes, but not limited to, xylene, ketone and ester, the ketone includes, but not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and the ester includes, but not limited to, ethyl acetate, propyl acetate, isobutyl acetate and butyl acetate；

wherein the raw materials of the modified polyurethane coating are 100％by weight.

Substrate

In the exterior trim provided by the present disclosure, the substrate may be made of metal or non-metal. When the substrate is made of non-metal, a material of the substrate may be, but not limited to, plastic. The plastic may be, but not limited to, polyacrylic acid or polymethyl methacrylate. When the substrate is made of metal, the material of the substrate may be, but not limited to, aluminum or steel.

Furthermore, when the substrate is made of metal, a metal oxide layer or an epoxy resin coating may be disposed between the substrate and the polyurethane coating.

Glass Window

In another aspect, an embodiment of the present disclosure provides a vehicle glass window. In the glass window, a glass plate, the exterior trim as recited above and an edge encapsulation around an edge of the glass plate are included, wherein the exterior trim is fixed to the glass window via the edge encapsulation.

In the present disclosure, when the substrate of the exterior trim is plastic, an edge of the exterior trim is provided with an edge encapsulation-modified polyurethane coating-exterior trim-edge encapsulation structure.

Injection Molding Method for Forming Glass Window

In another aspect, an embodiment of the present disclosure provides an injection molding method for forming a glass window.

The injection molding method includes: placing a glass plate and a exterior trim having a modified polyurethane coating on a surface thereof, which are placed together, in a mold； injecting the molding material as recited above into a mold cavity； and cooling the molding material which is injection molded to form an edge encapsulation around an edge of the glass plate.

Raw materials of the modified polyurethane coating include:

(C) polycaprolactone-modified (meth) hydroxy ethyl acrylate has a formula as follow:

where, R’denotes methyl or H； and n＝1-25.

The glass window prepared according to the method recited above, an edge of the exterior trim is provided with an edge encapsulation-modified polyurethane coating-exterior trim-edge encapsulation structure.

The present disclosure will be illustrated as follow with reference to the drawings.

Figure 1 is a schematic structural view of an exterior trim according to an embodiment of the present disclosure. As shown in Figure 1, the exterior trim includes a substrate 100 and a modified polyurethane coating 110 disposed on a surface of the substrate 100.

Fig. 2 is a schematic structural view of a vehicle glass window according to an embodiment of the present disclosure. As shown in Figure 2, the glass window includes: a glass plate 140, an edge encapsulation 120 around an edge of the glass plate 140, and an exterior trim 130 fixed to the glass window via the edge encapsulation 120, wherein the exterior trim 130 has a modified polyurethane coating 110.

Embodiments

The invention will be further illustrated with reference to specific embodiments. The following embodiments are provided to illustrate and describe the present disclosure and but not to limit scope of the disclosure. In the following embodiments, test methods which are not given a specific condition are implemented according to conventional conditions or in accordance with conditions recommended by the manufacturer. All percentages and parts are measured by weight unless otherwise indicated.

Embodiment 1: preparing a vehicle B-pillar exterior trim

The preparing process includes following steps:

(1) Preparing a modified polyurethane (where, by mole, hydroxyl in the long chain alkyl alcohol (B) : the isocyanate groups in the isocyanate (A) : hydroxy in the polycaprolactone-modified (meth) hydroxy ethyl acrylate (C) ＝ 1: 3: 2) .

Specifically, 60 parts of toluene and 10 parts of stearyl alcohol are added to a reaction kettle and stirred at 40℃ until the stearyl alcohol is sufficiently dissolved. Thereafter, 37 parts of 1, 6-hexamethylene diisocyanate (molecular weight is 168) are added, heated to 70℃ and stirred for 30 minutes. Thereafter, 0.02 parts of dibutyltin laurate are added and continuously stirred for 3 hours at an unchanged temperature. Thereafter, 25 parts of polycaprolactone modified hydroxyethyl acrylate (molecular weight is 344) , 0.02 parts of dibutyltin laurate and 0.02 parts of hydroquinone monomethyl ether are added and stirred for 3 hours until the reaction is completed. Then, 60 parts of toluene and 5 parts of PMMA organic beads are added and dispersed uniformly to obtain the modified polyurethane coating.

(2) Preparing the vehicle B-pillar exterior trim

Step 1: using PC (polycarbonate) produced by Bayer (i.e., Bayer Corporation) to form the B-pillar exterior trim by means of injection molding.

Step 2: uniformly applying the modified polyurethane prepared above to a surface of the exterior trim by means of manual spraying.

Step 3: placing the exterior trim prepared in Step 2 in an oven to solidify at a curing temperature of 80℃ and a curing time of 40 minutes.

Performance Test

Experiment 1: Scratching (10N, 5cm/s) several times on a PMMA surface of the assembly using a steel brush under a room temperature (e.g., 23℃) and observing.

Experiment 2: Scratching (10N, 5cm/s) several times on a PMMA surface of the assembly using a steel brush under a low temperature (e.g., -18℃) and observing.

Experiment 3: Scratching (10N, 5cm/s) several times on a PMMA surface of the assembly using a steel brush under a high temperature (e.g., 50℃) and observing.

Experiment 4: Implementing a temperature cycling aging to the assembly, wherein an aging condition is:

-30℃ 3 Hours

23℃ 0.5 Hours

80℃ 3 Hours

23℃ 0.5 Hours

The cycle was repeated 20 times, and then the assembly is taken out and stays at the room temperature for 24 hours. Thereafter, Experiment 1 is repeated.

Experiment 5: Implementing a low temperature aging to the assembly, wherein an aging condition is:

-40℃ 336 Hours

80℃ 3 Hours.

Test Result:

For Experiments 1 and 4, the scratch produced on the sample prepared according to Embodiment 1 disappears within 20 seconds.

For Experiment 2, the scratch produced on the sample prepared according to Embodiment 1 disappears within 3 minutes.

For Experiment 3, the scratch produced on the sample according to Embodiment 1 disappears within 10 seconds.

For Experiment 5, the sample prepared according to Embodiment 1 will not crack.

From the above recited Experiments 1 to 4, it can be seen that the plastic exterior trim having the modified polyurethane coating on its surface has excellent scratch repair performance.

From the above recited Experiment 5, it can be seen that the plastic exterior trim having the modified polyurethane coating on its surface has excellent crack resistance performance.

Embodiment 2: preparing glass window

The preparing process includes following steps:

(2) Injection molding method for forming glass window

Step 1: producing a piece of 3.85mm toughened glass (i.e., green glass) using a conventional KT (main component is polystyrene) line.

Step 2: forming a bright bar using the Evonik manufactured PLEXIGLAS 8N PMMA (polymethyl methacrylate) by means of injection molding.

Step 3: uniformly applying the modified polyurethane prepared above to a surface of the bright bar by means of manual spraying.

Step 4: placing the bright bar prepared in Step 3 into a molding cavity of a window edge encapsulation injection mold reserved for the bright bar, and then placing the piece of toughened glass prepared in Step 1 and other sub-components into corresponding positions of the molding cavity, respectively.

Step 5: injecting a PVC (polyvinyl chloride) material into the molding cavity at a conventional PVC injection temperature (e.g., 185 ℃) , and removing the assembly from the mold after a holding time (e.g., 5-20 seconds) .

Embodiment 3: preparing glass window

The preparing process includes following steps:

(1) Preparing a modified polyurethane (where, by mole, hydroxyl in the long chain alkyl alcohol (B) : the isocyanate groups in the isocyanate (A) : hydroxy in the polycaprolactone-modified (meth) hydroxy ethyl acrylate (C) ＝ 1: 50: 60) .

Specifically, 50 parts of toluene and 2 parts of stearyl alcohol are added to a reaction kettle and stirred at 40℃ until the stearyl alcohol is sufficiently dissolved. Thereafter, 120 parts of 1, 6-hexamethylene diisocyanate (molecular weight is 168) are added, heated to 70℃ and stirred for 30 minutes. Thereafter, 0.02 parts of dibutyltin laurate are added and continuously stirred for 3 hours at an unchanged temperature. Thereafter, 150 parts of polycaprolactone modified hydroxyethyl acrylate (molecular weight is 344) , 0.02 parts of dibutyltin laurate and 0.02 parts of hydroquinone monomethyl ether are added and stirred for 3 hours until the reaction is completed. Then, 270 parts of toluene are added to obtain the modified polyurethane coating.

The injection molding method for forming the glass window can refer to that of Embodiment 1.

Embodiment 4: preparing glass window

The preparing process includes following steps:

(1) Preparing a modified polyurethane (where, by mole, hydroxyl in the long chain alkyl alcohol (B) : the isocyanate groups in the isocyanate (A) : hydroxy in the polycaprolactone-modified (meth) hydroxy ethyl acrylate (C) ＝ 1: 12 : 3) .

Specifically, 50 parts of toluene and 10 parts of stearyl alcohol are added to a reaction kettle and stirred at 40℃ until the stearyl alcohol is sufficiently dissolved. Thereafter, 50 parts of isocyanurate modified 1, 6-hexamethylene diisocyanate are added, heated to 70℃ and stirred for 30 minutes. Thereafter, 0.02 parts of dibutyltin laurate are added and continuously stirred for 3 hours at an unchanged temperature. Thereafter, 85 parts of polycaprolactone modified hydroxyethyl acrylate (molecular weight is 689) , 0.02 parts of dibutyltin laurate and 0.02 parts of hydroquinone monomethyl ether are added and stirred for 3 hours until the reaction is completed. Then, 80 parts of toluene are added and to obtain the modified polyurethane coating.

Embodiment 5: preparing glass window

The preparing process includes following steps:

(1) Preparing a modified polyurethane (where, by mole, hydroxyl in the long chain alkyl alcohol (B) : the isocyanate groups in the isocyanate (A) : hydroxy in the polycaprolactone-modified (meth) hydroxy ethyl acrylate (C) ＝ 1: 20 : 8) .

Specifically, 50 parts of toluene and 5 parts of hexadecyl alcohol are added to a reaction kettle and stirred at 40℃ until the hexadecyl alcohol is sufficiently dissolved. Thereafter, 50 parts of biuret modified 1, 6-hexamethylene diisocyanate are added, heated to 70℃ and stirred for 30 minutes. Thereafter, 0.02 parts of dibutyltin laurate are added and continuously stirred for 3 hours at an unchanged temperature. Thereafter, 100 parts of polycaprolactone modified hydroxyethyl acrylate (molecular weight is 689) , 0.02 parts of dibutyltin laurate and 0.02 parts of hydroquinone monomethyl ether are added and stirred for 3 hours until the reaction is completed. Then, 80 parts of toluene are added and to obtain the modified polyurethane coating.

Embodiment 6: preparing glass window

The preparing process includes following steps:

(1) Preparing a modified polyurethane (where, by mole, hydroxyl in the long chain alkyl alcohol (B) : the isocyanate groups in the isocyanate (A) : hydroxy in the polycaprolactone-modified (meth) hydroxy ethyl acrylate (C) ＝ 1: 26 : 8) .

Specifically, 45 parts of toluene and 5 parts of behenyl alcohol are added to a reaction kettle and stirred at 40℃ until the behenyl alcohol is sufficiently dissolved. Thereafter, 60 parts of trimethylolpropane adduct modified 1, 6-hexamethylene diisocyanate are added, heated to 70℃ and stirred for 30 minutes. Thereafter, 0.02 parts of dibutyltin laurate are added and continuously stirred for 3 hours at an unchanged temperature. Thereafter, 90 parts of polycaprolactone modified hydroxyethyl acrylate (molecular weight is 689) , 0.02 parts of dibutyltin laurate and 0.02 parts of hydroquinone monomethyl ether are added and stirred for 3 hours until the reaction is completed. Then, 70 parts of toluene and 1 part of antistatic agent are added and mixed uniformly to obtain the modified polyurethane coating.

Embodiment 7: preparing glass window

The preparing process includes following steps:

(1) Preparing a modified polyurethane (where, by mole, hydroxyl in the long chain alkyl alcohol (B) : the isocyanate groups in the isocyanate (A) : hydroxy in the polycaprolactone-modified (meth) hydroxy ethyl acrylate (C) ＝ 1: 7 : 2) .

Specifically, 70 parts of toluene and 10 parts of behenyl alcohol are added to a reaction kettle and stirred at 40℃ until the behenyl alcohol was sufficiently dissolved. Thereafter, 50 parts of trimethylolpropane adduct modified isophorone diisocyanate are added, heated to 70℃ and stirred for 30 minutes. Thereafter, 0.02 parts of dibutyltin laurate are added and continuously stirred for 3 hours at an unchanged temperature. Thereafter, 25 parts of polycaprolactone modified hydroxyethyl acrylate (molecular weight is 344) , 0.02 parts of dibutyltin laurate and 0.02 parts of hydroquinone monomethyl ether are added and stirred for 3 hours until the reaction is completed. Then, 60 parts of toluene and 5 parts of PMMA organic beads are added and dispersed uniformly to obtain the modified polyurethane coating.

Comparative Example 1

The preparing process includes following steps:

(1) Injection method for forming glass window

Step 1: producing a piece of 3.85mm toughened glass (green glass) using a conventional KT line.

Step 2: forming a bright bar using the Evonik manufactured PLEXIGLAS 8N PMMA by means of injection molding.

Step 3: placing the bright bar prepared in Step 2 into a molding cavity of a window edge encapsulation injection mold reserved for the bright bar, and then placing the toughened glass prepared in Step 1 and other sub-components into corresponding positions of the molding cavity, respectively.

Step 4: injecting a PVC material into the molding cavity at a conventional PVC injection temperature (e.g., 185 ℃) , and removing the assembly from the mold after a holding time (e.g., 5-20 seconds) .

Comparative Example 2

The preparing process includes following steps:

(1) Injection molding method for forming glass window

Step 1: producing a piece of 3.85mm toughened glass (green glass) using a conventional KT (main component is polystyrene) line.

Step 4: injecting a PVC material (polyvinyl chloride) into the molding cavity at a conventional PVC injection temperature (e.g., 185 ℃) , and removing the assembly from the mold after a holding time (e.g., 5-20 seconds) .

Step 5: uniformly applying the modified polyurethane prepared above to a surface of the bright bar by means of manual spraying.

Performance Test

-30℃ 3 Hours

23℃ 0.5 Hours

80℃ 3 Hours

23℃ 0.5 Hours

-40℃ 336 Hours

80℃ 3 Hours.

Test Result:

For all of the above experiments, the scratch produced on the sample prepared according to comparative example 1 does not disappear.

For Experiments 1 and 4, the scratch produced on the samples prepared according to Embodiments 1 to 6 disappears within 20 seconds.

For Experiment 2, the scratch produced on the samples prepared according to Embodiments 1 to 6 disappears within 3 minutes.

For Experiment 3, the scratch produced on the samples prepared according to Embodiments 1 to 6 disappears within 10 seconds.

For Experiment 5, the samples prepared according to Embodiments 1 to 6 will not crack, and 10％of the sample prepared according to comparative example 1 will crack.

From the above recited Experiments 1 to 4, it can be seen that the plastic bright bar having the modified polyurethane coating on its surface has excellent scratch repair performance.

From the above recited Experiment 5, it can be seen that the plastic bright bar having the modified polyurethane coating on its surface has excellent crack resistance performance.

In addition, Experiments 4 and 5 are conducted on comparative example 2, and it is found that about 3％of the sample prepared according to comparative example 2 will crack. The crack resistance performance of the sample prepared according to comparative example 2 is better than that of the sample prepared according to comparative example 1, but worse than that of the samples prepared according to Embodiments 1 to 6. The experimental results show that the steps of the preparing process of the modified polyurethane coating have an effect to the crack resistance performance of the plastic bright bar having the modified polyurethane coating. Optionally, the modified polyurethane coating is prepared before the injection molding, which will further improve the crack resistance performance of the plastic bright bar having the modified polyurethane coating.

Embodiment 8: preparing glass window

The preparing process includes following steps:

(1) preparing of the modified polyurethane can refer to that of Embodiment 1.

(2) Injection molding method for forming glass window

Step 2: forming a bright bar by means of punching an aluminum plate, and implementing an anodizing treatment to a surface of the bright bar.

Step 3: uniformly applying the modified polyurethane prepared above to the surface of the bright bar by means of manual spraying.

Step 4: placing the bright bar prepared in Step 3 into a molding cavity of a window edge encapsulation injection mold reserved for the bright bar, and then placing the toughened glass prepared in Step 1 and other sub-components into corresponding positions of the molding cavity, respectively.

Embodiment 9: preparing glass window

The preparing process includes following steps:

Specifically, 60 parts of toluene and 10 parts of stearyl alcohol are added to a reaction kettle and stirred at 40℃ until the stearyl alcohol is sufficiently dissolved. Thereafter, 37 parts of hexamethylene diisocyanate (molecular weight is 168) are added, heated to 70℃ and stirred for 30 minutes. Thereafter, 0.02 parts of dibutyltin laurate are added and continuously stirred for 3 hours at an unchanged temperature. Thereafter, 25 parts of polycaprolactone modified hydroxyethyl acrylate (molecular weight is 344) , 0.02 parts of dibutyltin laurate and 0.02 parts of hydroquinone monomethyl ether are added and stirred for 3 hours until the reaction is completed. Then, 60 parts of toluene and 5 parts of PMMA organic beads are added and dispersed uniformly to obtain the modified polyurethane coating.

(2) Injection molding method for forming glass window

Step 2: forming a bright bar by means of punching an aluminum plate, and electroplating a surface of the bright bar with an epoxy material.

Step 5: injecting a PVC (polyvinyl chloride) material into the molding cavity at a conventional PVC injection temperature (e.g., 185℃) , and removing the assembly from the mold after a holding time (e.g., 5-20 seconds) .

Performance Test

-30℃ 3 Hours

23℃ 0.5 Hours

80℃ 3 Hours

23℃ 0.5 Hours

Test Result:

For Experiments 1 and 4, the scratch produced on the samples prepared according to Embodiments 1 and 2 disappears within 20 seconds.

For Experiment 2, the scratch produced on the samples prepared according to Embodiments 1 and 2 disappears within 3 minutes.

For Experiment 3, the scratch produced on the samples prepared according to Embodiments 1 and 2 disappears within 10 seconds.

From the above recited Experiments 1 to 4, it can be seen that the metal bright bar having the modified polyurethane coating on its surface has excellent scratch repair performance.

It should be noted that the above described embodiments are given for describing rather than limiting the present disclosure, and it is to be understood by those skilled in the art that modifications and variations may be made to the disclosure without departing from the spirit and scope of the present disclosure. Such modifications and variations are considered to be within the scope of the present disclosure and the appended claims.

All documents mentioned in the present disclosure are hereby incorporated by reference as if each individual document was individually incorporated by reference. Furthermore, it is to be understood by those skilled in the art that, various changes and modifications can be made upon a reading of the foregoing teachings of the present disclosure, which also fail into the scope of the claims appended hereto.

Claims

An exterior trim, comprising: a substrate (100) and a modified polyurethane coating (110) disposed on a surface of the substrate (100) , wherein raw materials of the modified polyurethane coating comprise:

(A) isocyanate, wherein each molecule of the isocyanate has three or more isocyanate groups；

(B) long chain alkyl alcohol, wherein a number of carbon atoms comprised in the long chain alkyl alcohol ranges from 10 to 25； and

(C) polycaprolactone-modified (meth) hydroxy ethyl acrylate having a formula as follow:

where, R’ denotes –CH₃ or –H； and n＝1-25, and

by mole, hydroxyl in the long chain alkyl alcohol (B) : the isocyanate groups in the isocyanate (A) : hydroxy in the polycaprolactone-modified (meth) hydroxy ethyl acrylate (C) ＝ 1 : (3-50) : (2-60) .
The exterior trim according to claim 1, wherein the raw materials of the modified polyurethane coating further comprise: 0.01 to 5％by weight of an anti-scratch agent, 0.01 to 1％by weight of a catalyst, 0.01 to 1％by weight of an antistatic agent, 0.01 to 1％by weight of a polymerization inhibitor, and a solvent serving as a balance, where the raw materials of the modified polyurethane coating are 100％by weight.
The exterior trim according to claim 2, wherein the anti-scratch agent comprises: organic beads and inorganic beads.
The exterior trim according to claim 3, wherein the organic beads comprise: polymethyl methacrylate, polyurethane, nylon and rubber.
The exterior trim according to claim 2, wherein the catalyst is 0.1 to 0.5％by weight； and the catalyst comprises: dibutyltin dilaurate and dibutyl tin diethyl n-hexanoate.
The exterior trim according to claim 2, wherein the antistatic agent comprises: an antistatic agent containing lithium, sodium or potassium salt, a cationic antistatic agent containing amine salt or quaternary ammonium salt, and a nonpolar antistatic agent containing C8 to C12 alkyl or alkaryl.
The exterior trim according to claim 2, wherein the polymerization inhibitor comprises: hydroquinone monomethyl ether.
The exterior trim according to claim 2, wherein the solvent comprises: xylene, ketone and ester.
The exterior trim according to claim 8, wherein the ketone comprises: acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone； and the ester comprises: ethyl acetate, propyl acetate, isobutyl acetate and butyl acetate.
The exterior trim according to claim 1, wherein the substrate is made of metal or non-metal.
The exterior trim according to claim 10, wherein the substrate is made of plastic.
The exterior trim according to claim 11, wherein the plastic comprises polyacrylic acid.
The exterior trim according to claim 11, wherein the plastic comprises polymethyl methacrylate.
The exterior trim according to claim 10, wherein the substrate is made of aluminum or steel.
The exterior trim according to claim 1, wherein when the substrate is made of metal, a metal oxide layer or an epoxy resin coating layer is further disposed between the substrate (100) and the modified polyurethane coating (110) .
The exterior trim according to any one of claims 1 to 15, wherein the modified polyurethane coating has a thickness ranging from 10 microns to 200 microns.
The exterior trim according to any one of claims 1 to 15, wherein the isocyanate comprises:

where, R denotes
The exterior trim according to any one claims 1 to 15, wherein the long chain alkyl alcohol comprises: tridecanol, tetradecanol, hexadecyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene monostearate, polyoxyethylene hexadecyl ether, polyoxyethylene stearyl ether and glycerol monostearate.
The exterior trim according to any one of claims 1 to 15, wherein n＝2-5.
A glass window, comprising: a glass plate, the exterior trim according to any one of claims 1 to 19, and an edge encapsulation around an edge of the glass plate, wherein the exterior trim is fixed to the glass window via the edge encapsulation.
The glass window according to claim 20, wherein when the substrate of the exterior trim comprises plastic, an edge of the exterior trim is provided with an edge encapsulation-modified polyurethane coating-plastic bright bar-edge encapsulation structure.
An injection molding method for forming a glass window, comprising:

placing a glass plate and an exterior trim having a modified polyurethane coating on a surface thereof, which are placed together, in a mold；

injecting a molding material into a mold cavity； and

cooling the molding material which is injection molded to form an edge encapsulation around the edge of the glass plate

wherein raw materials of the modified polyurethane coating comprise:

(A) isocyanate, wherein each molecule of the isocyanate has three or more isocyanate groups；

(B) long chain alkyl alcohol, wherein a number of carbon atoms comprised in the long chain alkyl alcohol ranges from 10 to 25； and

(C) polycaprolactone-modified (meth) hydroxy ethyl acrylate having a formula as follow:

where, R’ denotes –CH₃ or –H； and n＝1-25, and

by mole, hydroxyl in the long chain alkyl alcohol (B) : the isocyanate groups in the isocyanate (A) : hydroxy in the polycaprolactone-modified (meth) hydroxy ethyl acrylate (C) ＝ 1 : (3-50) : (2-60) .