CN111961435A - Transfer adhesive, preparation method of transfer adhesive, shell assembly, processing method of shell assembly and electronic equipment - Google Patents

Transfer adhesive, preparation method of transfer adhesive, shell assembly, processing method of shell assembly and electronic equipment Download PDF

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CN111961435A
CN111961435A CN202010867206.XA CN202010867206A CN111961435A CN 111961435 A CN111961435 A CN 111961435A CN 202010867206 A CN202010867206 A CN 202010867206A CN 111961435 A CN111961435 A CN 111961435A
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acrylate resin
transfer printing
glue
rough blank
transfer
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CN111961435B (en
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周传玉
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Oppo Chongqing Intelligent Technology Co Ltd
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Oppo Chongqing Intelligent Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The application discloses an ultraviolet curing transfer printing adhesive and a preparation method thereof, a shell assembly and a processing method thereof, and electronic equipment. The ultraviolet light curing transfer printing glue comprises: 15-50 wt% of a difunctional acrylate resin; 10-30 wt% of a hexafunctional acrylate resin; 10-35 wt% of a nine-functional acrylate resin; 10-35 wt% of a reactive diluent; 1-5 wt% of a photoinitiator; and 0.5-2 wt% of auxiliary agent, wherein wt% represents weight percentage. Therefore, the ultraviolet curing transfer printing adhesive has the advantages of good adhesion and high toughness, has strong adhesion after 3D high-pressure bending, is not easy to crack, and can be well applied to the rear cover of the 3D battery.

Description

Transfer adhesive, preparation method of transfer adhesive, shell assembly, processing method of shell assembly and electronic equipment
Technical Field
The application relates to the field of ultraviolet curing materials, in particular to transfer glue and a preparation method thereof, a shell assembly and a processing method thereof, and electronic equipment.
Background
At present, the battery rear cover is usually provided with an ultraviolet curing transfer glue layer, and the ultraviolet curing transfer glue layer can be provided with textures so as to improve the appearance expressive force of the battery rear cover. However, the current ultraviolet curing transfer glue is generally only suitable for the rear cover of a 2D or 2.5D battery, and when the traditional ultraviolet curing transfer glue is applied to the rear cover of a 3D battery, the adhesion of the traditional ultraviolet curing transfer glue is poor after the traditional ultraviolet curing transfer glue is bent under a 3D high pressure, and a large-area front surface or arc-edge cracks are easily generated, so that the traditional ultraviolet curing transfer glue cannot be applied to the rear cover of the 3D battery.
Disclosure of Invention
In one aspect of the present application, an ultraviolet curing transfer adhesive is provided. The ultraviolet light curing transfer printing glue comprises: 15-50 wt% of a difunctional acrylate resin; 10-30 wt% of a hexafunctional acrylate resin; 10-35 wt% of a nine-functional acrylate resin; 10-35 wt% of a reactive diluent; 1-5 wt% of a photoinitiator; and 0.5-2 wt% of auxiliary agent, wherein wt% represents weight percentage. Therefore, the ultraviolet curing transfer printing adhesive has the advantages of good adhesion and high toughness, has strong adhesion after 3D high-pressure bending, is not easy to crack, and can be well applied to the rear cover of the 3D battery.
In another aspect of the present application, the present application provides a method for preparing the aforementioned uv curable transfer paste. The method comprises the following steps: respectively weighing difunctional acrylate resin, hexafunctional acrylate resin, nine functional acrylate resin, reactive diluent, photoinitiator and auxiliary agent according to the mass content; mixing the photoinitiator and the reactive diluent to obtain a mixed solution; mixing the difunctional acrylate resin, the hexafunctional acrylate resin and the nonafunctional acrylate resin with the mixed solution to obtain a dispersion liquid; and mixing the auxiliary agent with the dispersion liquid to obtain the ultraviolet curing transfer printing adhesive. Therefore, the ultraviolet curing transfer printing adhesive obtained by the method has the advantages of good adhesion and high toughness, has strong adhesion after 3D high-pressure bending, is not easy to crack, and can be well applied to the rear cover of the 3D battery.
In another aspect of the present application, a housing assembly is presented. The housing assembly includes: the plastic base body comprises a main body surface and a side wall connected with the main body surface, wherein a bending angle between the side wall and a plane where the main body surface is located is larger than 30 degrees, and an accommodating space is defined by the main body surface and the side wall; the UV adhesive transfer printing layer covers the plastic base body and is positioned in the accommodating space, and the UV adhesive transfer printing layer is formed by utilizing the ultraviolet light curing transfer printing adhesive; the color effect layer is arranged on one side, away from the plastic matrix, of the UV glue transfer printing layer. Therefore, the shell assembly has a good appearance effect, high structural stability and long service life.
In another aspect of the present application, a method of manufacturing the housing assembly described above is provided. The method comprises the following steps: providing a plastic substrate rough blank, wherein the plastic substrate rough blank is of a plane structure; forming a UV glue transfer printing layer rough blank on one side of the plastic base body rough blank, wherein the UV glue transfer printing layer rough blank is formed by utilizing the ultraviolet light curing transfer printing glue; forming a color effect layer rough blank on one side of the UV adhesive transfer printing layer rough blank, which is far away from the plastic base body rough blank, so as to obtain a shell assembly rough blank; and bending the shell component rough blank to obtain the shell component. Therefore, the shell assembly obtained by the method has the advantages of good appearance effect, high structural stability and long service life.
In another aspect of the present application, an electronic device is presented. The electronic device includes: the housing assembly described above; display screen and mainboard, the display screen with the mainboard is located in casing assembly's accommodation space, the display screen with the mainboard electricity is connected. Thus, the electronic device has all of the features and advantages of the housing assembly described above, which will not be described in detail herein. Generally speaking, the electronic equipment has good appearance effect, and the shell assembly has high structural stability and long service life.
Drawings
The above and/or additional aspects and advantages of the present application will become apparent and readily appreciated from the following description of the examples taken in conjunction with the accompanying drawings, in which:
FIG. 1 shows a schematic flow diagram of a method for preparing an UV curable transfer adhesive according to one example of the present application;
FIG. 2 shows a schematic structural view of a housing assembly according to one example of the present application;
FIG. 3 shows a schematic flow diagram of a method of making a housing assembly according to one example of the present application;
fig. 4 shows a schematic structural diagram of an electronic device according to an example of the application.
Description of reference numerals:
100: a plastic substrate; 110: a main body surface; 120: a side wall; 200: a UV glue transfer layer; 300: a color effect layer; 1000: a housing assembly.
Detailed Description
Reference will now be made in detail to examples of the present application, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The examples described below with reference to the drawings are illustrative only for the purpose of explaining the present application and are not to be construed as limiting the present application.
In one aspect of the present application, an ultraviolet curing transfer adhesive is provided. According to an example of the present application, the ultraviolet light curing transfer paste includes: 15-50 wt% of difunctional acrylate resin, 10-30 wt% of hexafunctional acrylate resin, 10-35 wt% of nine functional acrylate resin, 10-35 wt% of reactive diluent, 1-5 wt% of photoinitiator and 0.5-2 wt% of auxiliary agent, wherein wt% represents weight percentage. Therefore, the ultraviolet curing transfer printing adhesive has the advantages of good adhesion and high toughness, has strong adhesion after 3D high-pressure bending, is not easy to crack, and can be well applied to the rear cover of the 3D battery. The weight percentage is the percentage of the mass of each component to the total mass of the ultraviolet curing transfer printing glue.
Traditional ultraviolet curing rendition is glued and is mainly applied to behind 2D or 2.5D's the battery in the lid, if with traditional ultraviolet curing rendition glue use behind the 3D battery in the lid, when carrying out 3D high pressure bending process to the ultraviolet curing rendition glue after the solidification, lead to ultraviolet curing rendition to glue to take place the membrane and split, and the ultraviolet curing rendition glue also worsens with the adhesive force between the battery after the lid base member, can't use behind the 3D battery in.
The ultraviolet curing transfer printing glue is improved through components of the ultraviolet curing transfer printing glue and the proportion of each component, and specifically, the ultraviolet curing transfer printing glue adopts difunctional acrylate resin, hexafunctionality acrylate resin and nonafunctionality acrylate resin as a main body, and adds reactive diluent, photoinitiator and auxiliary agent, and each component meets proper mass content, so that the ultraviolet curing transfer printing glue has high toughness and good adhesiveness. Transfer printing is glued with this ultraviolet curing rendition and is glued on the base member of lid behind the 3D battery, and carry out 3D high pressure bending treatment along with the base member, obtain lid behind the 3D battery, the UV in the lid behind the 3D battery is glued the rendition layer on the surface, arc limit and R angle department are all crackles, carry out the adhesive force test to the UV in the lid behind the 3D battery rendition layer under conventional conditions and boiling condition respectively, adhesive force between UV glue rendition layer and the lid base member behind the battery is 5B, strong adhesive force has, therefore, this ultraviolet curing rendition is glued can be fine use in lid behind the 3D battery.
In addition, the ultraviolet curing transfer printing adhesive has the advantages of good demolding performance, high curing speed, low energy consumption, high curing degree, low shrinkage rate, low thermal expansion coefficient, low water absorption, good plating performance, excellent thermal stability and the like.
The following describes the components of the uv curable transfer paste in detail according to specific examples of the present application:
according to examples of the present application, the di-functional acrylate resin, the hexa-functional acrylate resin, and the nona-functional acrylate resin may each independently include at least one of a urethane acrylate resin, an epoxy acrylate resin, a polyester acrylate resin, a photo-curable pure acrylic resin, and a polyolefin acrylate resin. The main material of the ultraviolet curing transfer printing glue has wide sources and is easy to obtain.
The term "photo-curable acrylic resin" refers to an acrylic resin containing a photo-curable monomer.
In the present application, the structural formula of the difunctional acrylate resin is:
Figure BDA0002649847390000031
the structural formula of the hexa-functionality acrylate resin is as follows:
Figure BDA0002649847390000041
the structural formula of the nine-functional acrylate resin is as follows:
Figure BDA0002649847390000042
wherein X is H or CH3，
R is R1Or R2，
R1Is composed of
Figure BDA0002649847390000043
Or
Figure BDA0002649847390000044
R2Is composed of
Figure BDA0002649847390000045
V1Is composed of
Figure BDA0002649847390000046
Or
Figure BDA0002649847390000047
V2Is composed of
Figure BDA0002649847390000048
Or
Figure BDA0002649847390000049
Or
Figure BDA00026498473900000410
V3Is composed of
Figure BDA00026498473900000411
Or
Figure BDA00026498473900000412
Or
Figure BDA00026498473900000413
Or
Figure BDA00026498473900000414
According to an example of the present application, the difunctional acrylate resin is preferably at least one of a urethane acrylate resin and a polyester acrylate resin, and more preferably, the difunctional acrylate resin is an aliphatic urethane acrylate or an aliphatic polyester acrylate resin, or a mixture of an aliphatic urethane acrylate and an aliphatic polyester acrylate resin mixed in an arbitrary ratio. The difunctional acrylate resin of the above type has good adhesiveness and plating property, after the ultraviolet curing transfer printing glue is cured to form a UV glue transfer printing layer, the adhesive force between the UV glue transfer printing layer and the rear cover base body of the battery can be improved, and the adhesive force between the UV glue transfer printing layer and a subsequently arranged film layer (such as a film coating layer) can be improved, so that when the 3D high-pressure bending is performed, the adhesive force between the UV glue transfer printing layer and the rear cover base body of the battery and the film coating layer is stronger, and the difunctional acrylate resin can be well applied to the rear cover of the 3D battery.
According to specific examples of the present application, the difunctional aliphatic urethane acrylate resin may be double bond Doublemer553, Changxing 6112-100, Changxing 6131-1, Saduoma CN9001NS, Saduoma CN2921, Nichigan chemical UV 3000B. The difunctional aliphatic polyester acrylate resin may be Sadoma CN7001N, Changxing 6340, Sonuda SD1088, Sonuda SD1208, Boxing B-509B.
According to examples herein, the difunctional acrylate resin may be present in an amount of 15 to 50 wt%, such as 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, based on the total mass of the uv curable transfer paste. The inventor finds that poor adhesion of the ultraviolet curing transfer printing adhesive can be caused when the content of the difunctional acrylate resin is too low (for example, less than 15 wt%), fog cracks are easily generated when the cured ultraviolet curing transfer printing adhesive is bent under 3D high pressure when the content of the difunctional acrylate resin is too high (for example, more than 50 wt%), and pockmarks are easily formed when the cured ultraviolet curing transfer printing adhesive is electroplated subsequently, so that the appearance is affected. According to the ultraviolet curing transfer printing adhesive, the content of the difunctional acrylate resin is set in the range, so that the ultraviolet curing transfer printing adhesive has excellent adhesiveness, and cracks are not easily formed when the ultraviolet curing transfer printing adhesive is bent at a high pressure in 3D.
According to an example of the present application, the hexafunctional acrylate resin is preferably a urethane acrylate resin, and more preferably, the hexafunctional acrylate resin is an aliphatic urethane acrylate resin. The six-functionality-degree acrylate resin has the advantages of high curing speed, high crosslinking density, good demolding performance, high toughness and the like, and after the ultraviolet curing transfer printing glue is cured to form the UV glue transfer printing layer, the UV glue transfer printing layer can keep good toughness when being bent at high pressure of 3G, and the phenomenon that the UV glue transfer printing layer cracks at positions such as the surface, the arc edge, the R angle (namely the bending angle) and the like of the rear cover of the battery is prevented.
According to a specific example of the present application, the hexafunctional aliphatic urethane acrylate resin may be bosch B-619B, tameric 9063, songda SD7546, Double bond Double 571.
According to an example of the present application, the hexa-functional acrylate resin may be contained in an amount of 10 to 30 wt%, such as 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, based on the total mass of the uv curable transfer paste. The inventors found that when the content of the hexa-functional acrylate resin is too low (e.g., less than 10 wt%), the cured uv-curable transfer adhesive is prone to form haze cracks when bent at a high 3D pressure, and when the content of the hexa-functional acrylate resin is too high (e.g., greater than 30 wt%), the cured uv-curable transfer adhesive is prone to form linear cracks when bent at a high 3D pressure, and the conventional adhesion is also poor. According to the application, the content of the six-functionality-degree acrylate resin is set in the range, so that the cured ultraviolet curing transfer printing adhesive is not easy to form cracks when bent under 3D high pressure.
According to an example of the present application, the nine-functional acrylate resin is preferably at least one of a urethane acrylate resin and a polyester acrylate resin, and more preferably, the nine-functional acrylate resin is an aliphatic urethane acrylate resin or an aliphatic polyester acrylate resin, or a mixture of an aliphatic urethane acrylate resin and an aliphatic polyester acrylate resin mixed in an arbitrary ratio. The nine-functionality-degree acrylate resin has the advantages of good demolding performance, low curing energy, quick curing, low thermal expansion coefficient after curing, low water absorption, good thermal stability and the like, and after the ultraviolet curing transfer printing adhesive is cured to form a UV adhesive transfer printing layer, the UV adhesive transfer printing layer enables the rear cover of the battery to have good environmental resistance performances such as cold and hot impact, constant temperature and humidity and the like.
According to specific examples of the present application, the nine-functional aliphatic urethane acrylate resin may be Haohui HP6919, Double bond Double588, Sadoma CN9013NS, Boxing B-908. Nine-functional aliphatic polyester acrylate resin may be selected from the group consisting of TEMELITI 9028, TEMELITI 8209, and CHANGXING DR-528.
According to an example of the present application, the content of the nine-functional acrylate resin may be 10 to 35 wt%, such as 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, based on the total mass of the ultraviolet light-curable transfer paste. The inventors found that when the content of the nine-functional acrylate resin is too low (e.g., less than 10 wt%), the cured uv-curable transfer adhesive is prone to form haze cracks when bent at a high 3D pressure, and when the content of the nine-functional acrylate resin is too high (e.g., greater than 35 wt%), the cured uv-curable transfer adhesive is prone to form linear cracks when bent at a high 3D pressure, and the conventional adhesion is also poor. According to the application, the content of the nine-functionality acrylate resin is set in the range, so that the cured ultraviolet curing transfer printing adhesive is not easy to form cracks when bent under 3D high pressure.
The inventors found that when the contents of the di-, hexa-and nona-functional acrylate resins respectively satisfy the above ranges, the uv curable transfer paste has a higher crosslinking density, and the adhesion of the uv curable transfer paste is better as the crosslinking density increases. When the content of the acrylate resin is out of the above range of the present application, the adhesion of the uv curable transfer paste may be reduced.
According to examples herein, the reactive diluent may include at least one of a monofunctional monomer and a multifunctional monomer. The single functional group monomer has certain corrosivity and can bite into the rear cover base body of the battery, so that the solidified UV adhesive transfer printing layer and the rear cover base body of the battery form a rivet structure, and the adhesive force between the UV adhesive transfer printing layer and the rear cover base body of the battery is improved. The polyfunctional monomer can improve the crosslinking density of the ultraviolet curing transfer printing glue, so that the ultraviolet curing transfer printing glue has stronger integrity after being cured, is easy to peel off from a mould, and the high crosslinking density is also favorable for improving the adhesive force between the UV glue transfer printing layer and the battery rear cover matrix.
According to an example of the present application, the monofunctional monomer may include at least one of tetrahydrofuran acrylate, 4-t-butylcyclohexyl acrylate, cyclotrimethylolpropane formal acrylate, isobornyl methacrylate, isobornyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl ethoxylated acrylate, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, 4-acryloylmorpholine. The monofunctional monomer is used for adjusting the viscosity of a system, has the capability of corroding a rear cover base body of the battery (for example, the rear cover base body of the battery is a composite plate of PMMA and PC, and the monofunctional monomer can corrode a PC surface), and improves the adhesive force between the UV adhesive transfer layer and the rear cover base body of the battery.
According to an example of the present application, the multifunctional monomer may include at least one of diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tricyclodecane dimethanol diacrylate, dioxane diacrylate, 1,4 butanediol diacrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate. The multifunctional monomer is used for diluting the resin, and contributes to improving the crosslinking density of a system.
According to examples herein, the reactive diluent may be included in an amount of 10 to 35 wt%, such as 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, based on the total mass of the uv curable transfer paste. Therefore, the resin can be well diluted, and the adhesion of the ultraviolet curing transfer printing glue can be improved, and the ultraviolet curing transfer printing glue can be conveniently demoulded.
According to the present application, the reactive diluent may be composed of a plurality of monomers, such as one monofunctional monomer and two multifunctional monomers, and the ratio of the plurality of monomers may be adjusted according to the specific coating process of the uv curable transfer paste on the mold due to the certain viscosity of the reactive diluent, and is not limited herein.
According to examples of the application, the photoinitiator may include IRGACURE500 (a mixture of 1-hydroxycyclohexyl phenyl ketone and diphenyl ketone), Doubcure 1256, 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinyl benzyl) butanone (369), bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (819), 2-Isopropylthioxanthone (ITX), 2, 4-Diethylthioxanthone (DETX), 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone (907), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzoin dimethyl ether (651), Benzophenone (BP), ethyl 2,4, 6-trimethylbenzoylphosphonate (TPO-L), 4' -bis (diethylamino) benzophenone (EMK), methyl o-benzoylbenzoate (OMBB). The photoinitiator plays a role in initiating free radical ultraviolet polymerization. The UV glue transfer printing layer is formed by ultraviolet curing transfer printing glue through twice curing, and therefore the photoinitiator is a mixed photoinitiator, so that the ultraviolet curing transfer printing glue can be cured and released when being cured for the first time, and can be fully cured when being cured for the second time.
The number in parentheses is the material name.
According to examples herein, the photoinitiator may be present in an amount of 1-5 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, based on the total mass of the uv curable transfer paste. Therefore, the ultraviolet curing transfer printing glue has good curing performance.
According to an example of the present application, the battery back cover substrate may have an ultraviolet light resistant aid, whereby the aging of the battery back cover may be delayed. Because the ultraviolet curing transfer glue is cured through the rear cover matrix of the battery during the first curing, and the ultraviolet curing transfer glue after the first curing is directly cured during the second curing, when the rear cover matrix of the battery contains the ultraviolet-resistant auxiliary agent, the photoinitiator is also required to be a mixed photoinitiator so as to meet different curing conditions.
According to the examples of the present application, the ratio between the plurality of photoinitiators can be adjusted according to the conditions of the two-time curing and the material of the substrate of the rear cover of the battery, and is not limited herein.
According to examples of the present application, the auxiliary may include at least one of a leveling agent and an adhesion promoter. Wherein, the flatting agent makes ultraviolet curing rendition glue easily coat for ultraviolet curing rendition glue after the coating has smooth surface, and in the coating process, the flatting agent can migrate to the mould surface, and after ultraviolet curing rendition glue solidification, easily drawing of patterns, and the flatting agent makes ultraviolet curing rendition glue have good wettability to the lid base member behind the battery, thereby makes the lid base member behind the corrosion battery that monofunctional group monomer in the reactive diluent can be fine. The adhesion promoter is used for improving the adhesion performance of the ultraviolet curing transfer printing glue, so that the UV glue transfer printing layer and the battery rear cover base body have strong adhesion.
According to examples of the present application, the leveling agent may include at least one of BYK-345, BYK-346, BYK-348, BYK-353, BYK-356, BYK-359, BYK-361, BYK-373, BYK-380, BYK-381, TEGO-370, TEGO-2100, TEGO-RAD2010, TEGO-RAD2200N, TEGO-RAD2250, TEGO-RAD2500, NTEGO-RAD2300, TEGO-FLOW425, TEGO-GLIDE440, TEGO-GLIDE490, TEGO-GLIDE 435. The leveling agent plays a role in wetting the rear cover substrate of the battery, and provides good construction and leveling performance.
According to examples herein, the adhesion promoter may include at least one of double bond Doublemer9122, double bond Doublemer9166, sartomer SR9050, sartomer SR9051NS, sartomer SR9053, changxing PA 9039. The adhesion promoter plays a role in improving the adhesion between the UV adhesive transfer printing layer and the base body of the rear cover of the battery.
According to examples of the present application, the content of the auxiliary agent may be 0.5 to 2 wt%, such as 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, based on the total mass of the ultraviolet light curing transfer paste. This can further improve the adhesion and release properties of the ultraviolet-curable transfer paste.
In conclusion, the ultraviolet curing transfer printing glue has the following advantages:
1. the ultraviolet curing transfer printing adhesive adopts the acrylate resins with different functionalities (two functionalities, six functionalities and nine functionalities) as a main body, so that the ultraviolet curing transfer printing adhesive meets the toughness and adhesive force performance of the transfer printing adhesive under 3D high pressure, and has the advantages of rapid curing, high reaction degree, low curing energy, low shrinkage rate, low thermal expansion coefficient and the like.
2. This application adopts the reactive diluent of monofunctional group monomer and polyfunctional group monomer collocation, both can corrode behind the battery lid base member for UV after the solidification glues rendition layer and battery and covers the base member behind and form the rivet structure, improves the adhesive force between the two, can reduce system viscosity again, improves the density of cross-linking, makes the ultraviolet curing rendition glue after the first solidification easily drawing of patterns.
3. This application adopts the collocation of flatting agent and adhesion promoter, easily construction, and satisfies the wetting property, can further strengthen again behind UV glue transfer printing layer and the battery the adhesive force between the lid base member.
4. This application adopts mixed type photoinitiator for ultraviolet curing rendition glue can solidify when the first solidification from the type, can fully solidify when the solidification of second time.
5. The ultraviolet curing transfer printing glue does not contain a solvent, is high in curing speed and low in energy consumption.
In conclusion, the ultraviolet curing transfer glue can be widely applied to pattern transfer of the rear covers of 3D batteries of various electronic products.
In another aspect of the present application, the present application provides a method for preparing the above-described uv curable transfer paste. According to an example of the present application, with reference to fig. 1, the method comprises:
s100: respectively weighing difunctional acrylate resin, hexafunctional acrylate resin, nine functional acrylate resin, reactive diluent, photoinitiator and auxiliary agent according to predetermined mass content
In this step, various components for forming the ultraviolet curing transfer paste are weighed. The mass contents of the components and the specific materials used for the components have been described in detail above, and are not described in detail here.
S200: mixing a photoinitiator and an active diluent to obtain a mixed solution
In this step, a photoinitiator and a reactive diluent are mixed to obtain a mixed solution. According to the application example, the photoinitiator and the reactive diluent are stirred to obtain the mixed solution, the stirring speed can be 300-500r/min, and the stirring time can be 15-30 min. Thereby, the photoinitiator can be completely dissolved in the reactive diluent.
S300: mixing the difunctional acrylate resin, the hexafunctional acrylate resin and the nonafunctional acrylate resin with the mixed solution to obtain dispersion liquid
In this step, a bifunctional acrylate resin, a hexafunctional acrylate resin, and a nonafunctional acrylate resin are mixed with the mixed solution to obtain a dispersion liquid. According to an example of the application, the dispersion is obtained by stirring the acrylate resin and the mixed solution, the stirring speed can be 500-800r/min, such as 500r/min, 550r/min, 600r/min, 650r/min, 700r/min, 750r/min, 800r/min, and the stirring time can be 30-60min, such as 30min, 35min, 40min, 45min, 50min, 55min, 60 min. It should be noted that the stirring speed of the present application is designed according to the difunctional acrylate resin, the hexafunctional acrylate resin and the nonafunctional acrylate resin, and the inventors found that when the stirring speed is less than 500r/min, the acrylate resin is not uniformly dispersed, which affects the performance of the final ultraviolet light curing transfer adhesive, and when the stirring speed is more than 800r/min, the dispersion liquid has a problem of local heating, which also affects the performance of the final ultraviolet light curing transfer adhesive. This application sets up stirring speed and stirring time in above-mentioned within range, can obtain even dispersion for the ultraviolet curing rendition is glued and is obtained good performance.
S400: mixing the auxiliary agent and the dispersion liquid to obtain the ultraviolet curing transfer printing adhesive
In the step, the auxiliary agent is mixed with the dispersion liquid to obtain the ultraviolet curing transfer printing adhesive. According to the examples of the application, the mixing time of the auxiliary and the dispersion can be 1-2 h. Therefore, the auxiliary agent and the dispersion liquid can be fully mixed to obtain the ultraviolet curing transfer printing glue.
According to an example of the present application, the method further comprises: and filtering and vacuum defoaming the mixed auxiliary agent and dispersion liquid to obtain the final ultraviolet curing transfer printing glue, wherein the mesh number of the filter cloth used in the filtering process can be 200-300 meshes. Therefore, gel blocks or gel particles in the resin can be filtered, impurities in the photoinitiator can be filtered, the ultraviolet curing transfer printing glue is prevented from being influenced by the substances, and the appearance of the rear cover of the battery is prevented from being influenced by the substances.
The inventor finds that in the preparation process of the traditional ultraviolet curing transfer printing adhesive, acrylate resin, an active diluent, a photoinitiator and an auxiliary agent are usually mixed at the same time, and because the photoinitiator is solid and the viscosity of the acrylate resin is high, the problem that the photoinitiator cannot be completely dissolved exists in the preparation process, in the subsequent filtering process, the undissolved photoinitiator can be filtered, so that the amount of the photoinitiator in the final ultraviolet curing transfer printing adhesive is insufficient, the curing degree of the ultraviolet curing transfer printing adhesive is influenced, and the performance of the ultraviolet curing transfer printing adhesive is further influenced. The application mixes the photoinitiator and the reactive diluent, so that the luminous initiator is completely dissolved in the reactive diluent, and then the acrylate resin is added to ensure the curing performance of the ultraviolet curing transfer printing adhesive.
In addition, the inventor finds that the auxiliary agent has water absorption, and if the auxiliary agent is added firstly, the dispersion of the acrylate resin is influenced, so that the auxiliary agent is added after the acrylate resin is uniformly mixed with the mixed solution.
In another aspect of the present application, a housing assembly is presented. According to an example of the present application, with reference to fig. 2, the housing assembly comprises: the plastic substrate 100 includes a main body surface 110 and a sidewall 120 connected to the main body surface 110, a bending angle between the sidewall 120 and a plane where the main body surface 110 is located is greater than 30 degrees (refer to α in fig. 2), such as 50 degrees, 70 degrees, 90 degrees, and 105 degrees, and the main body surface 110 and the sidewall 120 define an accommodating space, the UV glue transfer layer 200 covers the plastic substrate 100 and is located in the accommodating space, the UV glue transfer layer 200 is formed by using the ultraviolet curing transfer glue described above, and the color effect layer 300 is disposed on a side of the UV glue transfer layer 200 away from the plastic substrate 100. Utilize the UV of the ultraviolet curing transfer printing glue formation of preceding description to glue the rendition layer and have higher toughness and good adhesion, consequently, when the UV glues the rendition layer setting on the plastic base member that the angle of bending is greater than 30 degrees, can not appear the crackle etc. and have stronger adhesive force between the plastic base member, and the UV glues also has stronger adhesive force between rendition layer and the colour effect layer (like the coating layer), make the housing assembly have good outward appearance effect and higher structural stability, prolong housing assembly's life. In addition, the UV glue transfer printing layer has excellent thermal stability, lower water absorption rate and lower thermal expansion coefficient, so that the shell assembly has excellent cold and hot shock resistance and constant temperature and humidity resistance.
Note that the housing assembly is the battery back cover described above.
It should be noted that the term "bending angle" in this application refers to an angle between the side wall and the main body surface (α shown in fig. 2), specifically, an angle between the side wall and the plane of the main body surface. In some examples of the present application, the main body surface of the plastic substrate may be a plane surface, or may also be a curved surface. When the main body surface comprises a plane part and an arc surface part, the plane where the main body surface is located is the plane where the plane part is located, and when the whole main body surface is the arc surface, the plane where the main body surface is located is the plane where the tangent line of the highest point of the protrusion of the main body surface is located. The side wall may also be a plane or an arc surface, and when the outer surface (the surface on the side away from the accommodating space) of the side wall is an arc surface, the maximum value of the included angles between the tangent line at any point on the outer surface of the side wall and the plane of the main body surface is the bending angle (α shown in fig. 2) at the side wall. The plastic base body has a larger bending angle, so that structures such as a middle frame and the like can be omitted, and an integrated shell assembly is obtained.
According to an example of the present application, the plastic substrate 100 may be a composite plate of PMMA and PC, and the UV paste transfer layer 200 is disposed on the PC surface side. Therefore, the UV adhesive transfer printing layer has strong adhesive force with the plastic matrix, and the PMMA is used as an appearance surface, so that the shell assembly has high hardness and wear resistance.
The thickness of the plastic substrate is not particularly limited, and those skilled in the art can design the plastic substrate according to the thickness commonly used for the housing assembly. For example, the plastic substrate may have a thickness of 0.5mm, 0.64mm, or 0.8 mm.
According to examples of the present application, the plastic matrix may contain an ultraviolet light resistant aid. Thus, the aging of the housing assembly can be delayed. The specific components of the ultraviolet light-blocking auxiliary are not particularly limited, and for example, an ultraviolet light-blocking auxiliary capable of absorbing ultraviolet light of 370nm or less can be used.
According to an example of the present application, the UV paste transfer layer 200 may have a texture. Therefore, the appearance diversity of the shell assembly can be improved.
In another aspect of the present application, a method of manufacturing the housing assembly described above is provided. According to an example of the present application, with reference to fig. 3, the method comprises:
s500: providing a plastic substrate blank
In this step, a plastic substrate blank is provided. According to the example of the application, the plastic base rough blank is of a planar structure, the UV glue transfer printing layer rough blank and the color effect layer rough blank are sequentially formed on the planar plastic base rough blank in the subsequent step, finally bending treatment is carried out, the planar plastic base rough blank is bent to form a plastic base with a main body surface and a side wall, and the bending angle of the plastic base is larger than 30 degrees so as to form a 3D structure.
The material and thickness of the plastic substrate blank have been described in detail above, and are not described in detail herein.
S600: forming a UV glue transfer printing layer rough blank on one side of the plastic base rough blank
In this step, a UV paste transfer layer blank is formed on one side of the plastic substrate blank. According to an example of the present application, the UV paste transfer layer is formed using the ultraviolet curing transfer paste described above. Thus, the UV glue transfer layer has at least one of the following advantages: easy demoulding during the transfer process; the curing degree is high; the shrinkage rate is low, and the rough blank of the plastic matrix is not easy to warp in the transfer printing process; the thermal expansion coefficient is low, the toughness is high, cracking is not easy to occur after subsequent bending treatment, and the adhesive force between the adhesive and a plastic matrix rough blank is strong; the plating property is good, and the paint has stronger adhesive force with a subsequent color effect layer rough blank; the heat stability and the water resistance are excellent, so that the formed shell assembly has good cold and hot shock resistance and constant temperature and humidity resistance.
According to an example of the application, the UV paste transfer layer blank may be formed by: firstly, coating ultraviolet curing transfer printing glue on a mould, and covering a plastic substrate rough blank on one side of the ultraviolet curing transfer printing glue, which is far away from the mould. After the plastic substrate rough blank is covered with the ultraviolet curing transfer printing glue, the ultraviolet curing transfer printing glue can be uniformly flattened on a mould in a rolling way. Subsequently, the ultraviolet light curing transfer printing glue is subjected to first curing to form a transfer printing glue rough blank, and the transfer printing glue rough blank is separated from the mold (namely the plastic substrate rough blank with the transfer printing glue rough blank is stripped from the mold). And finally, carrying out secondary curing on the transfer printing glue rough blank to obtain a UV glue transfer printing layer rough blank. From this, first solidification can make ultraviolet curing rendition glue have certain degree of solidification, and easily peel off from the mould, carry out the second solidification to the rendition glue rough blank, can make the micromolecule on rendition glue rough blank surface continue the solidification or volatilize, make the ultraviolet curing rendition glue fully solidify, reduce the defect on UV glue rendition layer rough blank surface, for follow-up colour effect layer rough blank provides good contact surface, be favorable to improving the adhesive force between UV glue rendition layer rough blank and the colour effect layer rough blank.
According to the application example, the mold is provided with the texture pattern, so that the formed UV glue transfer printing layer rough blank is provided with the texture pattern, and the variety of the appearance of the shell assembly can be improved.
According to an example of the application, the energy of the first curing may be 1500-2The energy of the second curing can be 800-2. Wherein, first solidification can adopt the LED lamp to solidify, and the LED lamp is cold light source, and the heat is low, consequently, the difficult plastic matrix blank warpage that arouses of curing process, and can adopt higher energy to solidify, make ultraviolet curing rendition glue have certain solidification degree, and easily peel off from the mould. The second curing can be carried out by a mercury lamp and lower energy, so that the energy consumption is reduced.
According to an example of the present application, before forming the UV paste transfer layer blank, the method may further include: printing mirror silver ink on one side of the plastic substrate rough blank, and then forming a UV glue transfer printing layer rough blank on one side of the plastic substrate rough blank with the mirror silver ink, wherein a pattern formed by the mirror silver ink can be used as an identification pattern.
S700: forming a color effect layer rough blank on one side of the UV adhesive transfer printing layer rough blank far away from the plastic matrix rough blank to obtain a shell component rough blank
In the step, a color effect layer rough blank is formed on one side, away from the plastic base body rough blank, of the UV glue transfer printing layer rough blank, and a shell assembly rough blank is obtained. According to an example of the present application, the color effect layer blanks may include a coated layer blank and a bottom cover ink layer blank, wherein the coated layer blank is disposed on a side of the UV glue transfer layer blank remote from the plastic substrate blank, and the bottom cover ink layer blank is disposed on a side of the coated layer blank remote from the UV glue transfer layer blank. Thereby, a color effect can be obtained for the housing assembly.
The method for forming the coating layer blank and the base ink layer blank is not particularly limited, and may be designed by those skilled in the art according to the circumstances. For example, a coating layer blank is formed by vacuum plating, and a base ink layer blank is formed by printing.
According to an example of the present application, before forming the coating layer blank, the method may further include: and (3) carrying out ion source treatment on the UV adhesive transfer layer rough blank in advance, and then forming a coating layer rough blank on one side of the UV adhesive transfer layer rough blank, which is far away from the plastic substrate rough blank. The UV glue transfer printing layer rough blank is subjected to ion source treatment, namely, the surface activation treatment is carried out on the UV glue transfer printing layer rough blank, so that the dyne value of the UV glue transfer printing layer rough blank can be improved, and the adhesive force between the UV glue transfer printing layer rough blank and the coating film layer rough blank is further improved.
S800: bending the shell component rough blank to obtain the shell component
In this step, the shell assembly blank is subjected to a bending process to obtain a shell assembly. According to the embodiment of the application, the rough blank of the plastic substrate is bent to form the plastic substrate, the rough blank of the UV glue transfer layer is bent to form the UV glue transfer layer, and the rough blank of the color effect layer is bent to form the color effect layer, wherein the plastic substrate has a main body surface and a side wall connected with the main body surface, a bending angle between the side wall and a plane where the main body surface is located is larger than 30 degrees, and the rough blank of the plastic substrate, the rough blank of the UV glue transfer layer and the rough blank of the color effect layer are synchronously bent, so that the bending angle between the UV glue transfer layer and the color effect layer is also larger than 30 degrees, and the rough blank of the UV glue transfer layer has high toughness and excellent adhesiveness, so that cracks are not easy to appear after bending treatment, and the rough blank of the UV glue transfer layer and the rough blank of the plastic substrate and the color effect layer have strong adhesive force, so that the housing assembly has good appearance effect, and the housing assembly has high, the service life of the shell assembly is prolonged.
According to an example of the present application, the pressure of the bending process may be 6-8kgf, and the temperature of the bending process may be 120-. Therefore, the shell assembly rough blank can be bent into the shell assembly with the bending angle larger than 30 degrees.
According to an example of the present application, after the bending process is performed on the shell assembly blank, a cutting process (e.g., CNC machining) may also be performed to machine the shell assembly into a desired shape.
In another aspect of the present application, an electronic device is presented. According to an example of the present application, referring to fig. 4, the electronic device includes: the housing assembly 1000, the display screen and the motherboard (not shown in the figure) are described above, the display screen and the motherboard are located in the accommodating space of the housing assembly 1000, and the display screen and the motherboard are electrically connected. Therefore, the electronic device has all the characteristics and advantages of the shell assembly described above, which are not described herein again, and in general, the electronic device has a good appearance effect, and the shell assembly has high structural stability and a long service life.
According to examples of the application, the electronic device may be any of various types of computer system devices that are mobile or portable and perform wireless communications. In particular, the electronic device may be a mobile or smart phone, a portable gaming device, a laptop computer, a personal digital assistant, a portable internet appliance, a music player, and a data storage device, other handheld devices, and devices such as a watch.
The present invention is described below with reference to specific examples, which are intended to illustrate the present invention and should not be construed as limiting the scope of the present invention. The examples do not specify particular techniques or conditions, according to techniques or conditions described in the literature in the field or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The ultraviolet light curing transfer printing glue comprises:
40 wt% of a difunctional acrylate resin;
10 wt% of a hexafunctional acrylate resin;
15 wt% of a nine-functional acrylate resin;
30 wt% of a reactive diluent;
4 wt% of a photoinitiator; and
1 wt% of an auxiliary agent.
The above difunctional acrylate resin: daily UV3000B (a di-official aliphatic urethane acrylate resin) was used.
The above six-functional acrylate resin: tri-methyl 9063 (six-membered aliphatic urethane acrylate resin) was used.
The nine-functional acrylate resin described above: haohui HP6919 (nine-tube aliphatic urethane acrylate resin) was used.
The active diluent comprises: the monofunctional group monomer adopts 4-acryloyl morpholine and dicyclopentenyl ethoxylated acrylate; the bifunctional monomer adopts 1, 6-hexanediol diacrylate, and the three diluents are mixed according to the mass ratio of 1:1:1 to form the final reactive diluent.
The above photoinitiator: 1-hydroxy-cyclohexyl benzophenone (184) and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) are adopted, and the two photoinitiators are mixed according to the mass ratio of 1:3 to form the final photoinitiator.
The auxiliary agent is as follows: the leveling agent adopts TEGO-GLIDE 435; the double-bond Doublemer9122 is adopted as the adhesion promoter, and the leveling agent and the adhesion promoter are mixed according to the mass ratio of 1:1 to form the final additive.
Example 2
The ultraviolet light curing transfer printing glue comprises:
25 wt% of a difunctional acrylate resin;
25 wt% of a hexafunctional acrylate resin;
15 wt% of a nine-functional acrylate resin;
30 wt% of a reactive diluent;
3 wt% of a photoinitiator; and
2 wt% of an auxiliary agent.
The above difunctional acrylate resin: the two difunctional acrylate resins are mixed according to the mass ratio of 2:1 to form the final difunctional acrylate resin by adopting Sadoma CN9001NS (two-officinal aliphatic polyurethane acrylate resin) and Boxing B-509B (difunctional aliphatic polyester acrylate resin).
The above six-functional acrylate resin: sonanda SD7546 (six-membered aliphatic urethane acrylate resin) was used.
The nine-functional acrylate resin described above: the Changxing DR528 (nine-officinal aliphatic urethane acrylate resin) is adopted.
The active diluent comprises: the monofunctional group monomer adopts N, N-dimethylacrylamide and tetrahydrofuran acrylate; the bifunctional monomer adopts tripropylene glycol diacrylate, and the three diluents are mixed according to the mass ratio of 1:1:1 to form the final reactive diluent.
The above photoinitiator: the final photoinitiator is formed by mixing 2,4, 6-trimethyl benzoyl ethyl phosphonate and IRGACURE500 according to the mass ratio of 2: 1.
The auxiliary agent is as follows: the leveling agent adopts BYK-345; the adhesion promoter adopts Sadoma SR9050, and the leveling agent and the adhesion promoter are mixed according to the mass ratio of 2:1 to form a final auxiliary agent.
Example 3
The ultraviolet light curing transfer printing glue comprises:
20 wt% of a difunctional acrylate resin;
20 wt% of a hexafunctional acrylate resin;
20 wt% of a nine-functional acrylate resin;
35 wt% of a reactive diluent;
4.5 wt% of a photoinitiator; and
0.5 wt% of an auxiliary agent.
The above difunctional acrylate resin: sadoma CN7001N (a two-part aliphatic polyester acrylate resin) is used.
The above six-functional acrylate resin: tri-methyl 9063 (six-membered aliphatic urethane acrylate resin) was used.
The nine-functional acrylate resin described above: double588 (nine-membered aliphatic urethane acrylate resin) and Termeili 9028 (nine-membered aliphatic polyester acrylate resin) are adopted, and the two nine-functionality acrylate resins are mixed according to the mass ratio of 1:2 to form the final nine-functionality acrylate resin.
The active diluent comprises: the single functional group monomer adopts dicyclopentenyl acrylate and N-vinyl-2-pyrrolidone; the bifunctional monomer adopts ethoxylated trimethylolpropane triacrylate, and the three diluents are mixed according to the mass ratio of 2:2:1 to form the final reactive diluent.
The above photoinitiator: the final photoinitiator is formed by mixing bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and 2-phenylbenzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone according to the mass ratio of 3.5: 1.
The auxiliary agent is as follows: the leveling agent adopts TEGO-GLIDE 435; the double-bond Doublemer9122 is adopted as the adhesion promoter, and the leveling agent and the adhesion promoter are mixed according to the mass ratio of 3:2 to form the final additive.
Comparative example 1
The ultraviolet light curing transfer printing glue comprises:
50 wt% of a difunctional acrylate resin;
47.5 wt% of a reactive diluent;
2 wt% of a photoinitiator; and
0.5 wt% of an auxiliary agent.
The above difunctional acrylate resin: 100 (two-part aliphatic polyester acrylate resin) Changxing 6112 is adopted.
The active diluent comprises: the monofunctional group monomer adopts N, N-dimethylacrylamide and N-vinyl-2-pyrrolidone; the bifunctional monomer adopts 1, 6-hexanediol diacrylate, and the three diluents are mixed according to the mass ratio of 2:1:2 to form the final reactive diluent.
The above photoinitiator: 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) are adopted, and the two photoinitiators are mixed according to the mass ratio of 2:1 to form the final photoinitiator.
The auxiliary agent is as follows: BYK353 was used as the leveling agent.
Comparative example 2
The ultraviolet light curing transfer printing glue comprises:
40 wt% of a difunctional acrylate resin;
25 wt% of a hexafunctional acrylate resin;
30 wt% of a reactive diluent;
4 wt% of a photoinitiator; and
1 wt% of an auxiliary agent.
The di-functional acrylate resin, the hexa-functional acrylate resin, the reactive diluent, the photoinitiator, and the auxiliary in this comparative example were the same as those described above in example 1, respectively.
Comparative example 3
The ultraviolet light curing transfer printing glue comprises:
40 wt% of a difunctional acrylate resin;
25 wt% of a nine-functional acrylate resin;
30 wt% of a reactive diluent;
4 wt% of a photoinitiator; and
1 wt% of an auxiliary agent.
The di-functional acrylate resin, the nine-functional acrylate resin, the reactive diluent, the photoinitiator, and the auxiliary in this comparative example were the same as those described above in example 1, respectively.
Comparative example 4
The ultraviolet light curing transfer printing glue comprises:
30 wt% of a hexafunctional acrylate resin;
35 wt% of a nine-functional acrylate resin;
30 wt% of a reactive diluent;
4 wt% of a photoinitiator; and
1 wt% of an auxiliary agent.
The hexa-functional acrylate resin, the nine-functional acrylate resin, the reactive diluent, the photoinitiator, and the auxiliary in this comparative example were the same as those described above in example 1, respectively.
Comparative example 5
The ultraviolet light curing transfer printing glue comprises:
40 wt% of a difunctional acrylate resin;
35 wt% of a hexafunctional acrylate resin;
20 wt% of a reactive diluent;
4 wt% of a photoinitiator; and
1 wt% of an auxiliary agent.
The di-functional acrylate resin, the hexa-functional acrylate resin, the reactive diluent, the photoinitiator, and the auxiliary in this comparative example were the same as those described above in example 1, respectively.
Comparative example 6
The ultraviolet light curing transfer printing glue comprises:
40 wt% of a difunctional acrylate resin;
40 wt% of a nine-functional acrylate resin;
15 wt% of a reactive diluent;
4 wt% of a photoinitiator; and
1 wt% of an auxiliary agent.
The di-functional acrylate resin, the nine-functional acrylate resin, the reactive diluent, the photoinitiator, and the auxiliary in this comparative example were the same as those described above in example 1, respectively.
Comparative example 7
The ultraviolet light curing transfer printing glue comprises:
20 wt% of a difunctional acrylate resin;
15 wt% of a hexafunctional acrylate resin;
40 wt% of a nine-functional acrylate resin;
20 wt% of a reactive diluent;
4 wt% of a photoinitiator; and
1 wt% of an auxiliary agent.
The di-functional acrylate resin, the hexa-functional acrylate resin, the nine-functional acrylate resin, the reactive diluent, the photoinitiator, and the auxiliary agent in this comparative example were the same as those described above in example 1, respectively.
The ultraviolet curing transfer printing glues of examples 1 to 3 and comparative examples 1 to 7 were respectively subjected to performance tests, the ultraviolet curing transfer printing glues of examples 1 to 3 and comparative examples 1 to 7 were used to manufacture housing assemblies, and the performance of each housing assembly was respectively tested, the test results are shown in table 1 to table 3, table 1 is the test results of examples 1 to 3, table 2 is the test results of comparative examples 1 to 3, and table 3 is the test results of comparative examples 4 to 7.
TABLE 1
Figure BDA0002649847390000171
Figure BDA0002649847390000181
TABLE 2
Figure BDA0002649847390000182
Figure BDA0002649847390000191
TABLE 3
Figure BDA0002649847390000192
Figure BDA0002649847390000201
The performance test method and the equipment are as follows:
1. and (3) testing the demolding property:
the transferred mold and composite plate were cut into 125mm × 25mm rectangles, subjected to a90 ° peel force test, and the magnitude of the peel force was recorded.
2. Bending test:
the diameter of the cylindrical shaft is 75mm, 65mm, 55mm and 45mm, one surface of the composite board, which is provided with UV glue (namely ultraviolet curing transfer glue), is attached to the cylinder (namely PMMA surface faces outwards), the cracking condition of the UV glue is tested, and 2 samples are measured.
3. And (3) testing the grids:
(1) a sharp blade was used to scribe 10 x 10 small 1mm x 1mm cells in a designated area, each scribe line penetrating the composite panel.
(2) The surface fragments are brushed clean by using dust-free cloth or a hairbrush, the small grids are adhered by using 3M610 adhesive paper and are flattened, air bubbles are extruded out, static pressure is carried out for more than 5 seconds, the product is kept still, and the single side of the adhesive tape is quickly pulled up at an angle of 90 degrees.
4. And (3) hardness testing:
the hardness of the final product was determined by scratching and scratching the surface of the sample with an eraser after 3 lines 1.0. + -. 0.2cm long were drawn on the surface of the sample with a Mitsubishi pencil (UNI series) at an angle of 45 degrees under a load of 1000 gf.
5. Cure shrinkage (density method) test:
density before UV glue curing rho1Density after curing to form film2Volume change before and after curing is (ρ)1-ρ2)/ρ1。
6. Infrared determination of degree of cure (double bond conversion):
a carbonyl peak (C ═ O) of the UV gel, wherein the peak is positioned near 1720cm-1 and is used as an internal standard fixed peak; the carbon-carbon (C-H) out-of-plane bending vibration peak on the carbon-carbon double bond is taken as a change peak and is positioned near 810cm < -1 >.
Status of state Area of peak position C ═ O Peak position ═ C-H area Area ratio
Before curing A1720 A810 (A810/A1720) before curing
After curing A1720 A810 (A810/A1720) after curing
Figure BDA0002649847390000211
7. Water absorption test:
weighing a certain weight m1Soaking the cured transfer printing adhesive film in deionized water at 25 ℃ for 24h, taking out, wiping the adhesive film by using a dust-free cloth, and measuring the weight m2The water absorption is the weight change before and after (m)2-m1)/m1。
8. Dyne value assay:
and (3) marking a line (the length is 10-20mm) on the non-texture surface of the UV adhesive by using an arcotest pen with a certain dyne value, standing for 5s, and observing whether the marked line shrinks into a water bead shape or not.
9. The glass transition temperature, the thermal expansion coefficient, the elastic modulus, the thermal weight loss and the water drop angle are respectively measured by DSC, TMA, DMA, TGA, a water drop angle tester and other equipment tests.
The test conditions for the above properties were as follows:
1. ultraviolet aging conditions:
in the QUV aging oven, the lamp power is set to 0.63W/m2Placing the sample into a test box, directly irradiating ultraviolet rays for 4 hours at the temperature of 60 ℃, then condensing for 4 hours at the temperature of 50 ℃, taking out the sample after 6 cycles (48 hours), cooling for 2 hours at normal temperature, inspecting the surface of the shell component, and performing adhesion test.
2. And (3) constant temperature and humidity conditions:
in the constant temperature and humidity chamber, the temperature is set as follows: 65. + -. 1 ℃ humidity: 91-95% RH, 96h, and 2h after normal temperature recovery, observing and performing an adhesion test.
3. Cold and hot shock conditions:
in a cold and hot impact box, the low temperature is set to minus 40 ℃ plus or minus 2 ℃/1h, and the temperature is transferred to the high temperature within 1min, and the temperature is 75 ℃ plus or minus 2 ℃/1h, so that a cycle is formed. Time: and (4) carrying out 20 cycles for 40h, recovering at normal temperature for 2h, checking, and carrying out an adhesion test.
And (3) analyzing a test result:
as can be seen from tables 1 and 2, compared with the conventional UV adhesive, the UV adhesive of the present application has significantly improved mold release, curing degree and adhesion, significantly reduced thermal expansion coefficient, shrinkage rate and water absorption, and no crack after high-pressure bending, so that the housing assembly has good appearance and high structural stability, and the housing assembly has good ultraviolet aging resistance, thermal shock resistance and constant temperature and humidity resistance (examples 1 to 3 are compared with comparative example 1).
Compared with the comparative example 2, the UV adhesive disclosed by the example 1 has the advantages that the demolding property and the adhesion are remarkably improved, no crack is generated after high-pressure bending, and the thermal expansion coefficient, the shrinkage rate, the curing degree and the water absorption rate are equivalent to those of the comparative example 2.
Compared with the comparative example 3, the UV adhesive disclosed by the example 1 has the advantages that the demolding property and the adhesion are remarkably improved, no crack is generated after high-pressure bending, and the thermal expansion coefficient, the shrinkage rate, the curing degree and the water absorption rate are equivalent to those of the comparative example 3.
As can be seen from tables 1 and 3, in example 1, compared with comparative example 4, the UV paste of the present application has significantly improved adhesion, and no crack is generated after high pressure bending, and the case assembly of comparative example 4 cannot be used.
Compared with the comparative example 5, the UV adhesive disclosed by the example 1 has the advantages that the demolding property and the adhesion are remarkably improved, no crack is generated after high-pressure bending, and the thermal expansion coefficient, the shrinkage rate, the curing degree and the water absorption rate are equivalent to those of the comparative example 5.
Compared with the comparative example 6, the UV adhesive of the example 1 has the advantages that the adhesive force is remarkably improved, no crack is generated after high-pressure bending, and the demolding property, the thermal expansion coefficient, the shrinkage rate, the curing degree and the water absorption rate are equivalent to those of the comparative example 6.
Compared with the comparative example 7, the UV adhesive disclosed by the example 1 has the advantages that the adhesive force is remarkably improved, no crack is generated after high-pressure bending, and the demolding property, the thermal expansion coefficient, the shrinkage rate, the curing degree and the water absorption rate are equivalent to those of the comparative example 7.
In the description of the present application, the terms "upper", "lower", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of describing the present application but do not require that the present application must be constructed and operated in a specific orientation, and thus, cannot be construed as limiting the present application.
Various examples and features of different examples described in this specification can be combined and combined by one skilled in the art without contradiction. In addition, it should be noted that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated, in order to distinguish between two cures.
Although examples of the present application have been shown and described above, it is understood that the above examples are illustrative and are not to be construed as limiting the present application and that variations, modifications, substitutions and alterations in the above examples may be made by those of ordinary skill in the art within the scope of the present application.

Claims (18)

1. An ultraviolet light curing transfer adhesive is characterized by comprising:
15-50 wt% of a difunctional acrylate resin;
10-30 wt% of a hexafunctional acrylate resin;
10-35 wt% of a nine-functional acrylate resin;
10-35 wt% of a reactive diluent;
1-5 wt% of a photoinitiator; and
0.5-2 wt% of auxiliary agent, wherein wt% represents weight percentage.
2. The UV curable transfer adhesive according to claim 1, wherein the difunctional acrylate resin, the hexafunctional acrylate resin and the nonafunctional acrylate resin each independently comprise at least one of a urethane acrylate resin, an epoxy acrylate resin, a polyester acrylate resin, a photo-curable acrylic resin and a polyolefin acrylate resin.
3. The UV-curable transfer adhesive according to claim 1, wherein the reactive diluent comprises at least one of a monofunctional monomer and a multifunctional monomer.
4. The UV-curable transfer paste according to claim 3, wherein said monofunctional monomer comprises at least one of tetrahydrofuran acrylate, 4-t-butylcyclohexyl acrylate, cyclotrimethylolpropane formal acrylate, isobornyl methacrylate, isobornyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl ethoxylate acrylate, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, 4-acryloylmorpholine.
5. The UV curable transfer adhesive according to claim 3, wherein the multifunctional monomer comprises at least one of diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tricyclodecane dimethanol diacrylate, dioxane diacrylate, 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate.
6. The UV-curable transfer paste according to claim 1, wherein the photoinitiator comprises IRGACURE500, Doublecure1256, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinobenzylphenyl) butanone, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, benzoin bismethyl ether, benzoin bis (methyl ether), A mixture of any combination of two or more of benzophenone, ethyl 2,4, 6-trimethylbenzoylphosphonate, 4' -bis (diethylamino) benzophenone and methyl o-benzoylbenzoate.
7. The UV-curable transfer paste according to claim 1, wherein the auxiliary agent comprises at least one of a leveling agent and an adhesion promoter.
8. The UV curable transfer adhesive of claim 7, wherein the leveling agent comprises at least one of BYK-345, BYK-346, BYK-348, BYK-353, BYK-356, BYK-359, BYK-361, BYK-373, BYK-380, BYK-381, TEGO-370, TEGO-2100, TEGO-RAD2010, TEGO-RAD2200N, TEGO-RAD2250, TEGO-RAD2500, NTEGO-RAD2300, TEGO-FLOW425, TEGO-GLIDE440, TEGO-GLIDE490, and TEGO-GLIDE 435.
9. The UV-curable transfer paste according to claim 7, wherein the adhesion promoter comprises at least one of Doublemer9122, Doublemer9166, SR9050, SR9051NS, SR9053, and PA 9039.
10. A method for preparing the uv curable transfer paste according to any one of claims 1 to 9, comprising:
respectively weighing difunctional acrylate resin, hexafunctional acrylate resin, nonafunctional acrylate resin, reactive diluent, photoinitiator and auxiliary agent according to the mass content of claim 1;
mixing the photoinitiator and the reactive diluent to obtain a mixed solution;
mixing the difunctional acrylate resin, the hexafunctional acrylate resin and the nonafunctional acrylate resin with the mixed solution to obtain a dispersion liquid;
and mixing the auxiliary agent with the dispersion liquid to obtain the ultraviolet curing transfer printing adhesive.
11. The method as claimed in claim 10, wherein the stirring speed of the difunctional acrylate resin, the hexafunctional acrylate resin and the nonafunctional acrylate resin during the mixing with the mixed solution is 500-800r/min, and the stirring time is 30-60 min.
12. The method of claim 10, further comprising:
and filtering and vacuum defoaming the mixed assistant and the dispersion liquid, wherein the mesh number of the filtering cloth is 200-300 meshes.
13. A housing assembly, comprising:
the plastic base body comprises a main body surface and a side wall connected with the main body surface, wherein a bending angle between the side wall and a plane where the main body surface is located is larger than 30 degrees, and an accommodating space is defined by the main body surface and the side wall;
a UV glue transfer printing layer, wherein the UV glue transfer printing layer covers the plastic base body and is positioned in the accommodating space, and the UV glue transfer printing layer is formed by utilizing the ultraviolet light curing transfer printing glue of any one of claims 1-9;
the color effect layer is arranged on one side, away from the plastic matrix, of the UV glue transfer printing layer.
14. A method of manufacturing the housing assembly of claim 13, comprising:
providing a plastic substrate rough blank, wherein the plastic substrate rough blank is of a plane structure;
forming a UV glue transfer printing layer rough blank on one side of the plastic base rough blank, wherein the UV glue transfer printing layer rough blank is formed by using the ultraviolet light curing transfer printing glue of any one of claims 1-9;
forming a color effect layer rough blank on one side of the UV adhesive transfer printing layer rough blank, which is far away from the plastic base body rough blank, so as to obtain a shell assembly rough blank;
and bending the shell component rough blank to obtain the shell component.
15. The method as claimed in claim 14, wherein the pressure of the bending process is 6-8kgf and the temperature of the bending process is 120-170 ℃.
16. The method of claim 14, wherein forming the UV glue transfer layer blank comprises:
coating the ultraviolet curing transfer printing glue on a mould, and covering the plastic substrate rough blank on one side of the ultraviolet curing transfer printing glue, which is far away from the mould;
carrying out first curing on the ultraviolet curing transfer printing glue to form a transfer printing glue rough blank, and separating the transfer printing glue rough blank from the mold;
and carrying out secondary curing on the transfer printing glue rough blank to obtain the UV glue transfer printing layer rough blank.
17. The method as claimed in claim 16, wherein the energy of the first curing is 1500-2The energy of the second curing is 800-2。
18. An electronic device, comprising:
the housing assembly of claim 13;
display screen and mainboard, the display screen with the mainboard is located in casing assembly's accommodation space, the display screen with the mainboard electricity is connected.
CN202010867206.XA 2020-08-25 2020-08-25 Transfer adhesive, preparation method of transfer adhesive, shell assembly, processing method of shell assembly and electronic equipment Active CN111961435B (en)

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