Colorful uv glue and preparation method thereof

Abstract

The application relates to the technical field of UV glue and discloses a colored UV glue and a preparation method thereof, the colored UV glue comprising the following raw materials: epoxy-modified acrylate, polyurethane-modified acrylate, acrylic resin, a photoinitiator, a diluent, a defoaming agent, nano color paste, a functional component and a composite additive component. The colored UV glue prepared by adding the functional component into the colored UV glue base material has excellent mechanical properties and oxidation resistance, can avoid the influence of oxidation on the colored UV glue during use, and can prolong the service life of the colored UV glue. The colored UV glue prepared by adding the composite additive component has excellent flexibility and bonding properties, can be crosslinked with the colored UV glue base material, is not easy to be damaged and peeled off when subjected to external force, can form a firm and stable connection with a bonded base material, and has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of UV glue, in particular to a color UV glue and a preparation method thereof. BACKGROUND

[0002] As a new type of material, UV glue has become an important role in intelligent manufacturing due to its unique advantages, and with the growth of market demand, the application of UV glue is also expanding. UV glue is also known as ultraviolet curing glue or photosensitive glue, mainly composed of photosensitive resin, photoinitiator and other additives, which is a kind of adhesive material that can be rapidly cured under ultraviolet irradiation. Through chemical reaction, it can form a firm adhesive layer in a short time to realize the bonding between various materials. UV glue has the advantages of environmental friendliness and fast curing speed. Color UV glue combines ultraviolet curing technology and color characteristics, which is composed of photosensitive resin, pigment, photoinitiator and other additives. Color UV glue can further meet the diversified needs of the market. Color UV glue is currently widely used in handicrafts and decorations, electronic and electrical industries, medical supplies, optics, building decoration, automobile manufacturing and other fields. Color UV glue can also be used for bonding of non-transparent materials, such as bonding of ceramic, metal, stone, plastic and other materials. Therefore, with the continuous development and expansion of the application market of color UV glue, the research on color UV glue is of great significance.

[0003] In the long-term use process, color UV glue is easily affected by oxidation, resulting in delamination between UV glue and the bonded substrate, decreased or failed adhesion leading to peeling, color fading, affecting the appearance, overall performance and service life. Moreover, the color UV glue has poor flexibility, and cannot effectively disperse stress at the bonding interface, resulting in stress concentration and damage to the bonding site, which is prone to cracking and affects the bonding effect. Poor flexibility is more prone to aging. Therefore, the anti-oxidation performance, flexibility, adhesion performance and mechanical properties of color UV glue need to be modified to prolong the service life of color UV glue and meet the application requirements of the industry. Therefore, the present application provides a color UV glue with broad application prospects. SUMMARY

[0004] In order to solve the problems mentioned in the background art, the purpose of the present application is to provide a color UV glue and a preparation method thereof.

[0005] The purpose of the present application can be achieved by the following technical solutions:

[0006] A color UV glue comprises the following raw materials in parts by weight: 20-35 parts of epoxy-modified acrylate, 20-35 parts of polyurethane-modified acrylate, 20-30 parts of acrylic resin, 1-4 parts of photoinitiator, 5-10 parts of diluent, 0.5-2 parts of defoaming agent, 1-4 parts of nano color paste, 2-5 parts of functional component, and 3-6 parts of composite additive component.

[0007] Further, the photoinitiator is any one of 1-hydroxycyclohexyl phenyl ketone, benzophenone or 2-hydroxy-2-methyl-1-phenylpropanone; the diluent is isopropyl alcohol; and the defoaming agent is polydimethylsiloxane.

[0008] Further, the preparation of the functional component comprises the following steps:

[0009] S1. Ultrasonic dispersion of nanocellulose in toluene to form a uniform dispersion, under a nitrogen atmosphere, 2-chloroisocyanate ethyl and catalyst are added, the temperature is raised to 50-60 DEG C, and stirring is carried out for 3-5 h, after the reaction is completed, suction filtration, washing and drying are carried out to obtain modified nanocellulose;

[0010] S2. The modified nanocellulose is added to dimethyl sulfoxide, after uniform dispersion, under a nitrogen atmosphere, 5-hydroxymethyl furfural and alkaline catalyst are added, the temperature is raised to 60-75 DEG C, and reaction is carried out for 4-6 h, after the reaction is completed, suction filtration, washing and drying are carried out to obtain the functional component.

[0011] By adopting the above technical scheme, the surface of nanocellulose contains active hydroxyl groups, which can react with isocyanate groups in the structure of 2-chloroisocyanate ethyl under the action of a catalyst to introduce chlorine substituents on the surface of nanocellulose, thereby obtaining modified nanocellulose, under the action of an alkaline catalyst, the chlorine substituents in the modified nanocellulose can react with active hydroxyl groups in the structure of 5-hydroxymethyl furfural to obtain the functional component. The functional component uses nanocellulose as a base material, nanocellulose has high mechanical strength and can be uniformly dispersed in the base material of the color UV glue, thereby enhancing the binding force between nanocellulose and the base material of the color UV glue and improving the mechanical properties of the color UV glue. In addition, 5-hydroxymethyl furfural is grafted to the modified nanocellulose in a chemical bonding manner, so that the functional component has excellent antioxidant properties, effectively improves the problem of easy migration and precipitation of small-molecule antioxidant substances 5-hydroxymethyl furfural, ensures that the antioxidant substances can act on the base material of the color UV glue for a long time, makes the color UV glue not easy to oxidize, and prevents the color UV glue from falling off due to adhesion decline or failure, thereby prolonging the service life of the color UV glue.

[0012] Further, in S1, the catalyst is dibutyltin dilaurate or stannous octoate.

[0013] Further, in S2, the basic catalyst is potassium carbonate or bicarbonate.

[0014] Further, the preparation of the composite additive component is as follows:

[0015] The hydroxyl-terminated liquid butadiene-styrene rubber is stirred and dispersed in acetone, then carboxymethyl guar gum and the composite catalyst are added, and stirred and reacted at room temperature for 4-6 h. After the reaction is completed, the solvent is removed to collect the product, which is washed and vacuum dried to obtain the composite additive component.

[0016] By using the above technical solution, the terminal hydroxyl group in the structure of the hydroxyl-terminated liquid butadiene-styrene rubber can undergo esterification reaction with the carboxyl group in the structure of the carboxymethyl guar gum under the action of the composite catalyst to obtain the composite additive component. The unsaturated alkenyl group in the structure of the composite additive component can participate in the preparation process of the colored UV glue matrix material, and the composite additive component can crosslink with the colored UV glue matrix material, thereby introducing butadiene-styrene rubber segments with good flexibility into the colored UV glue, which can deform in multiple forms when subjected to external force, thereby enhancing the flexibility of the colored UV glue and preventing it from being damaged and falling off. Meanwhile, the structure of the functional component contains a large number of hydroxyl groups and ester groups generated by reaction, which increases the hydrogen bonding sites, thereby enhancing the interaction force between the colored UV glue and the adherend, making the contact more closely, and forming a firm and stable connection at the interface between the colored UV glue and the adherend, thereby improving the adhesion performance of the colored UV glue.

[0017] Further, the average relative molecular mass of the hydroxyl-terminated liquid butadiene-styrene rubber is 3000.

[0018] Further, the composite catalyst is dicyclohexyl carbodiimide and 4-dimethylamino pyridine with a mass ratio of 2-6:1-1.5.

[0019] A preparation method of a colored UV glue, comprising the following steps:

[0020] Step one, add epoxy-modified acrylate, polyurethane-modified acrylate, and acrylic resin into a stirring kettle, increase the temperature to 60-90℃, then add diluent, defoaming agent, nano color paste, functional component, and composite additive component, and stir for 1-3 h to obtain a mixture;

[0021] Step two, add a photoinitiator to the mixture, stir at a rotation speed of 100-200 r / min for 20-50 min, stand for 1-2 h, then cool and discharge to obtain the colored UV glue.

[0022] Further, in step one, the rotation speed of stirring is 500-650 r / min.

[0023] The beneficial effects of the present application are:

[0024] This invention incorporates functional components and composite additives into the matrix material of a colored UV adhesive, resulting in a colored UV adhesive with a tensile strength of up to 21.4 MPa and a 180° peel strength of 23.4 N / 25 mm. It exhibits excellent adhesion, forming a strong and stable bond with the substrate. Furthermore, it demonstrates superior oxidation resistance and flexibility, preventing oxidation from causing adhesion degradation or failure and subsequent detachment. It is also resistant to damage and detachment under external forces, offering a long service life and broad application prospects.

[0025] Of course, any product implementing this invention does not necessarily need to achieve all of the advantages described above at the same time. Attached Figure Description

[0026] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 The infrared spectrum of the functional components in this invention;

[0028] Figure 2 The infrared spectrum of the composite additive components of this invention is shown. Detailed Implementation

[0029] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] The preparation of functional components in the following embodiments and comparative examples of the present invention is as follows:

[0031] S1. 3g of nanocellulose was ultrasonically dispersed in toluene to form a uniform dispersion. Under a nitrogen atmosphere, 2.6g of ethyl 2-chloroisocyanurate and 0.1g of dibutyltin dilaurate were added. The temperature was raised to 55℃ and stirred for 4h. After the reaction was completed, the mixture was filtered, washed, and dried to obtain modified nanocellulose.

[0032] S2. Add 2.8g of modified nanocellulose to dimethyl sulfoxide and disperse it evenly. Then, under a nitrogen atmosphere, add 2.2g of 5-hydroxymethylfurfural and 0.2g of potassium bicarbonate. Raise the temperature to 70℃ and react for 5h. After the reaction is complete, filter, wash and dry to obtain the functional component.

[0033] Samples were prepared using the potassium bromide pelleting method, and the functional components were analyzed using Fourier transform infrared spectroscopy, such as... Figure 1 As shown, the spectral wavenumber measurement range is 4000 cm⁻¹. -1 -500cm -1 Analysis shows that in the infrared spectrum of the functional components, 3318 cm⁻¹ -1 An absorption peak for NH appeared at 2926-2856 cm⁻¹. -1 Absorption peaks for CH in methyl and methylene groups appeared at 2720 cm⁻¹. -1 An absorption peak for the CH group in the aldehyde group appeared at 1710 cm⁻¹. -1 An absorption peak for C=O in urethane esters appeared at 1672 cm⁻¹. -1 An absorption peak appeared at 1540 cm⁻¹ for the C=O group in the aldehyde group. -1 An absorption peak for CN appeared at 1410 cm⁻¹. -1 An absorption peak for the furan ring appeared at 1134 cm⁻¹. -1 An absorption peak for ether bonds appeared at that location.

[0034] The preparation of the composite additives in the following embodiments and comparative examples of the present invention is shown below:

[0035] 3.2 g of hydroxyl-terminated liquid styrene-butadiene rubber with an average relative molecular mass of 3000 was stirred and dispersed in acetone. Then, 2.6 g of carboxymethyl guar gum, 0.3 g of dicyclohexylcarbodiimide, and 0.1 g of 4-dimethylaminopyridine were added. The mixture was stirred and reacted at room temperature for 6 h. After the reaction was completed, the solvent was removed, the product was collected, washed, and vacuum dried to obtain the composite additive component.

[0036] Samples were prepared using the potassium bromide pelleting method, and the composite additives were analyzed using Fourier transform infrared spectroscopy. Figure 2 As shown, the spectral wavenumber measurement range is 4000 cm⁻¹. -1 -500cm -1 Analysis shows that in the infrared spectrum of the composite additives, 3056 cm⁻¹ -1 An absorption peak for the carbon-hydrogen bond in a carbon-carbon double bond appeared at 3024 cm⁻¹. -1 An absorption peak for the carbon-hydrogen bonds in the benzene ring appeared at 1730 cm⁻¹. -1 An absorption peak for the ester group appeared at 1657 cm⁻¹. -1An absorption peak for the galactose / mannose ring appeared at 1601 cm⁻¹. -1 1492cm -1 An absorption peak for the benzene ring skeleton appeared at 1022 cm⁻¹. -1 An absorption peak for COC in the pyran ring appeared at [location].

[0037] Example 1: Preparation of colored UV adhesive;

[0038] Step 1: Add 20g of epoxy-modified acrylate, 20g of polyurethane-modified acrylate, and 20g of acrylic resin to a mixing tank, raise the temperature to 60℃, and then add 5g of isoacetone, 0.5g of polydimethylsiloxane, 1g of nano-color paste, 2g of functional component, and 3g of composite additive component. Stir at 500r / min for 1h to obtain a mixture.

[0039] Step 2: Add 1g of 1-hydroxycyclohexylphenyl ketone photoinitiator to the mixture, stir for 20min at 100r / min, let stand for 1h, cool and discharge to obtain colored UV adhesive.

[0040] Example 2, Preparation of colored UV adhesive;

[0041] Step 1: Add 25g of epoxy-modified acrylate, 25g of polyurethane-modified acrylate, and 25g of acrylic resin to a mixing tank, raise the temperature to 70℃, and then add 6g of isoacetone, 1g of polydimethylsiloxane, 2g of nano-color paste, 3g of functional component, and 4g of composite additive component. Stir at 550r / min for 2 hours to obtain a mixture.

[0042] Step 2: Add 2g of 1-hydroxycyclohexylphenyl ketone photoinitiator to the mixture, stir at 150r / min for 30min, let stand for 1.5h, cool and discharge to obtain colored UV adhesive.

[0043] Example 3: Preparation of colored UV adhesive;

[0044] Step 1: Add 30g of epoxy-modified acrylate, 30g of polyurethane-modified acrylate, and 30g of acrylic resin to a mixing tank, raise the temperature to 80℃, and then add 8g of isoacetone, 1.5g of polydimethylsiloxane, 3g of nano-color paste, 4g of functional component, and 5g of composite additive component. Stir at 600r / min for 2.5h to obtain a mixture.

[0045] Step 2: Add 3g of 1-hydroxycyclohexylphenyl ketone photoinitiator to the mixture, stir at 175r / min for 40min, let stand for 2h, cool and discharge to obtain colored UV adhesive.

[0046] Example 4: Preparation of colored UV adhesive;

[0047] Step 1: Add 35g of epoxy-modified acrylate, 35g of polyurethane-modified acrylate, and 30g of acrylic resin to a mixing tank, raise the temperature to 90℃, and then add 10g of isopropyl ketone, 2g of polydimethylsiloxane, 4g of nano-color paste, 5g of functional component, and 6g of composite additive component. Stir at 650r / min for 3h to obtain a mixture.

[0048] Step 2: Add 4g of 1-hydroxycyclohexylphenyl ketone photoinitiator to the mixture, stir at 200r / min for 50min, let stand for 2h, cool and discharge to obtain colored UV adhesive.

[0049] Comparative Example 1: Preparation of colored UV adhesive;

[0050] Step 1: Add 25g of epoxy-modified acrylate, 25g of polyurethane-modified acrylate, and 25g of acrylic resin to a mixing tank, raise the temperature to 70℃, and then add 6g of isoacetone, 1g of polydimethylsiloxane, 2g of nano-color paste, and 4g of composite additives. Stir at 550r / min for 2 hours to obtain a mixture.

[0051] Step 2: Add 2g of 1-hydroxycyclohexylphenyl ketone photoinitiator to the mixture, stir at 150r / min for 30min, let stand for 1.5h, cool and discharge to obtain colored UV adhesive.

[0052] Comparative Example 2: Preparation of colored UV adhesive;

[0053] Step 1: Add 25g of epoxy-modified acrylate, 25g of polyurethane-modified acrylate, and 25g of acrylic resin to a mixing tank, raise the temperature to 70℃, and then add 6g of isopropyl ketone, 1g of polydimethylsiloxane, 2g of nano-color paste, and 3g of functional components. Stir at 550r / min for 2 hours to obtain a mixture.

[0054] Step 2: Add 2g of 1-hydroxycyclohexylphenyl ketone photoinitiator to the mixture, stir at 150r / min for 30min, let stand for 1.5h, cool and discharge to obtain colored UV adhesive.

[0055] Comparative Example 3: Preparation of colored UV adhesive;

[0056] Step 1: Add 25g of epoxy-modified acrylate, 25g of polyurethane-modified acrylate, and 25g of acrylic resin to a mixing tank, raise the temperature to 70℃, and then add 6g of isopropyl ketone, 1g of polydimethylsiloxane, 2g of nano-color paste, 3g of nano-cellulose, and 4g of composite additives. Stir at 550r / min for 2 hours to obtain a mixture.

[0057] Step 2: Add 2g of 1-hydroxycyclohexylphenyl ketone photoinitiator to the mixture, stir at 150r / min for 30min, let stand for 1.5h, cool and discharge to obtain colored UV adhesive.

[0058] Comparative Example 4: Preparation of colored UV adhesive;

[0059] Step 1: Add 25g of epoxy-modified acrylate, 25g of polyurethane-modified acrylate, and 25g of acrylic resin to a mixing tank, raise the temperature to 70℃, and then add 6g of isopropyl ketone, 1g of polydimethylsiloxane, 2g of nano-color paste, 3g of functional components, and 4g of hydroxyl-terminated liquid styrene-butadiene rubber. Stir at 550r / min for 2 hours to obtain a mixture.

[0060] Step 2: Add 2g of 1-hydroxycyclohexylphenyl ketone photoinitiator to the mixture, stir at 150r / min for 30min, let stand for 1.5h, cool and discharge to obtain colored UV adhesive.

[0061] Performance testing

[0062] The colored UV adhesives prepared in Examples 1-4 and Comparative Examples 1-4 were subjected to an optical power of 100 mW / cm². 2 After irradiation with a 365nm ultraviolet lamp for 30 seconds, samples conforming to the test specifications were prepared. The tensile strength of the samples was tested according to GB / T 30776-2014 standard to determine the mechanical properties of the colored UV adhesive. The 180° peel strength test was performed according to GB / T 2792-2014 standard to determine the adhesive performance of the colored UV adhesive. The samples were then placed in an 80℃ aging chamber for 72 hours, and the 180° peel strength test was performed again to determine the antioxidant properties of the colored UV adhesive. The flexibility test was performed according to GB / T 1731-2020 standard to determine the flexibility of the colored UV adhesive. The test results are shown in the table below.

[0063]

[0064] As shown in the table above, the colored UV adhesives prepared in Examples 1-4 of this invention possess excellent mechanical properties, adhesive properties, antioxidant properties, and flexibility. Example 2 showed the best test results. Comparative Example 1, lacking functional components, could not utilize the grafting of nanocellulose with the antioxidant 5-hydroxyfurfural to enhance the mechanical and antioxidant properties of the colored UV adhesive; therefore, its mechanical and antioxidant performance test results were poor. Comparative Example 2, lacking composite additives, could not utilize these additives in the preparation process of the colored UV adhesive to introduce flexible styrene-butadiene rubber segments and increase hydrogen bonding sites, thus improving the flexibility and adhesive properties of the colored UV adhesive; therefore, its flexibility and adhesive performance test results were poor. Comparative Example 3, with the addition of nanocellulose and composite additives, showed poor antioxidant performance because the nanocellulose was not grafted with the antioxidant. Comparative Example 4, with the addition of functional components and hydroxyl-terminated liquid styrene-butadiene rubber, could participate in the preparation process of the colored UV adhesive, enhancing flexibility; however, it had few hydrogen bonding sites, resulting in poor adhesive performance test results for the colored UV adhesive.

[0065] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a colored UV adhesive, characterized in that, The raw materials include the following parts by weight: 20-35 parts epoxy-modified acrylate, 20-35 parts polyurethane-modified acrylate, 20-30 parts acrylic resin, 1-4 parts photoinitiator, 5-10 parts diluent, 0.5-2 parts defoamer, 1-4 parts nano-color paste, 2-5 parts functional components, and 3-6 parts composite additives. The preparation method includes the following steps: Step 1: Add epoxy-modified acrylate, polyurethane-modified acrylate, and acrylic resin to a mixing tank, raise the temperature to 60-90℃, and then add diluent, defoamer, nano-color paste, functional components, and composite additives. Stir for 1-3 hours to obtain a mixture. Step 2: Add photoinitiator to the mixture, stir at 100-200 r / min for 20-50 min, let stand for 1-2 h, cool and discharge to obtain colored UV adhesive; The preparation method of the functional component includes the following steps: S1. Disperse nanocellulose in toluene using ultrasound to form a uniform dispersion. Under a nitrogen atmosphere, add ethyl 2-chloroisocyanurate and a catalyst, raise the temperature to 50-60℃ and stir for 3-5 hours. After the reaction is complete, filter, wash, and dry to obtain modified nanocellulose. S2. Modified nanocellulose was added to dimethyl sulfoxide and dispersed evenly. Then, 5-hydroxymethylfurfural and an alkaline catalyst were added under a nitrogen atmosphere. The temperature was raised to 60-75℃ and the reaction was carried out for 4-6 hours. After the reaction was completed, the mixture was filtered, washed, and dried to obtain the functional component. The preparation method of the composite additive component is as follows: Hydroxyl-terminated liquid styrene-butadiene rubber was stirred and dispersed in acetone, then carboxymethyl guar gum and a composite catalyst were added. The mixture was stirred and reacted at room temperature for 4-6 hours. After the reaction was completed, the solvent was removed, the product was collected, washed, and vacuum dried to obtain the composite additive component.

2. The method for preparing a colored UV adhesive according to claim 1, characterized in that, The photoinitiator is any one of 1-hydroxycyclohexylphenyl ketone, benzophenone, or 2-hydroxy-2-methyl-1-phenylpropanone; the diluent is isopropanol; and the defoamer is polydimethylsiloxane.

3. The method for preparing a colored UV adhesive according to claim 1, characterized in that, In S1, the catalyst is dibutyltin dilaurate or stannous octoate.

4. The method for preparing a colored UV adhesive according to claim 1, characterized in that, In S2, the alkaline catalyst is potassium carbonate or potassium bicarbonate.

5. The method for preparing a colored UV adhesive according to claim 1, characterized in that, The average relative molecular mass of the hydroxyl-terminated liquid styrene-butadiene rubber is 3000.

6. The method for preparing a colored UV adhesive according to claim 1, characterized in that, The composite catalyst is a mixture of dicyclohexylcarbodiimide and 4-dimethylaminopyridine in a mass ratio of 2-6:1-1.

5.

7. The method for preparing a colored UV adhesive according to claim 1, characterized in that, In step one, the stirring speed is 500-650 r / min.

8. A colored UV adhesive, characterized in that, It is prepared using the preparation method described in claim 1.

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