TW202216817A - Resin and ink - Google Patents

Abstract

Resin has a chemical structure of, wherein Core is formed by reacting a multi-hydroxy compound and a plurality of hydroxy-containing epoxy compounds, and the multi-hydroxy compound and the hydroxy-containing epoxy compounds have a molar ratio of 1:6 to 1:20. R1 is C1-5 alkylene group, each of R2 independently includes, H or, wherein at least one R2 is, or R3 is C1-5 alkyl group; n=1-3; x=8-24; y=0-8; and x+y=16-24. The resin can be used in an ink.

Description

Resin and Ink

This disclosure pertains to inks, and more particularly to resins contained in inks.

UV-curable inks are gradually replacing traditional solvent-based inks, which have the advantages of environmental protection, safety, energy saving, material saving, rapid customization and digital automation. In the past, UV-curable inks were mainly used in hard board substrates (such as PCB) or panel protective coatings with high hardness and enhanced protective layers. After the current UV-curable ink is formed into a coating, it lacks flexibility and cannot be applied to soft substrates such as PI or PU films. As for 3D printing and inkjet printing, fast curing and low shrinkage are required, which cannot be achieved by current UV-curable inks. In summary, there is an urgent need for new UV-curable inks and coatings to meet the above requirements.

，其中Core係由多羥基化合物與多個含羥基的環氧化合物反應而成，且多羥基化合物與含羥基的環氧化合物之莫耳比為1:6至1:20；R ¹係C _1-5的烷撐基；R ²各自包括

、

、

、

、H或

，其中至少一R ²係

、

、

、或

；R ³為C _1-5的烷基； n=1-3；x=8-24；y=0-8；x+y=16-24。 The resin provided by an embodiment of the present invention has a chemical structure of

, wherein the Core is formed by the reaction of a polyhydroxy compound and a plurality of hydroxyl-containing epoxy compounds, and the molar ratio of the polyhydroxy compound and the hydroxyl-containing epoxy compound is 1:6 to 1:20; R ¹ is C _{1 -5} alkylene; R ² each includes

,

,

,

, H or

, in which at least one R ² series

,

,

,or

; R ³ is a C _1-5 alkyl group; n=1-3; x=8-24; y=0-8; x+y=16-24.

In some embodiments, the polyol includes three hydroxyl groups, and the molar ratio of the polyol to the hydroxyl-containing epoxy compound is between 1:6 and 1:15.

In some embodiments, the polyol includes four hydroxyl groups, and the molar ratio of the polyol to the hydroxyl-containing epoxy compound is between 1:8 and 1:20.

In some embodiments, the polyol includes pentaerythritol, 2-methyl-1,3-propanediol, 1,1,1-trimethylolpropane, 1,4-cyclohexanedimethanol, 1,3-butane Diol, neopentyl glycol, dimer of the above, trimer of the above, or polymer of the above.

In some embodiments, the hydroxyl-containing epoxy compound is an aliphatic epoxy compound.

In some embodiments, the hydroxyl-containing epoxy compound includes glycidol, 3-ethyl-3-oxetanemethanol, 3-alkyl-3-(hydroxyalkoxy)oxetane, 3, 3-bis(hydroxyalkyl)oxetane, or a combination of the above.

In some embodiments, the resin has 6 to 16 acrylate end groups.

，其中Core係由多羥基化合物與多個含羥基的環氧化合物反應而成，且多羥基化合物與含羥基的環氧化合物之莫耳比為1:6至1:20；R ¹係C _1-5的烷撐基；R ²各自包括

、

、

、

、H或

，其中至少一R ²係

、

、

、或

；R ³為C _1-5的烷基；； n=1-3；x=8-24；y=0-8；以及x+y=16-24；其中樹脂與紫外線硬化單體的重量比例介於100:30至100:5000之間，而樹脂與光起始劑的重量比例介於100:30至100:500之間。 An ink provided by an embodiment of the present invention includes: a resin; an ultraviolet curing monomer; and a photoinitiator, wherein the chemical structure of the resin is:

, wherein the Core is formed by the reaction of a polyhydroxy compound and a plurality of hydroxyl-containing epoxy compounds, and the molar ratio of the polyhydroxy compound and the hydroxyl-containing epoxy compound is 1:6 to 1:20; R ¹ is C _{1 -5} alkylene; R ² each includes

,

,

,

, H or

, in which at least one R ² series

,

,

,or

; R ³ is a C _1-5 alkyl group; n=1-3; x=8-24; y=0-8; between 100:30 and 100:5000, and the weight ratio of resin to photoinitiator is between 100:30 and 100:500.

In some embodiments, the resin has 6 to 16 acrylate end groups.

In some embodiments, the ink further includes an additive, and the weight ratio of the resin to the additive is between 100:20 and 100:200.

。Core係由多羥基化合物與多個含羥基的環氧化合物反應而成。R ¹係C _1-5的烷撐基；R ²各自包括

、

、

、

、H或

，其中至少一R ²係

、

、

、或

；R ³為C _1-5的烷基；； n=1-3；x=8-24；y=0-8；x+y=16-24。 The chemical structure of the resin provided by an embodiment of the present disclosure is:

. Core is formed by the reaction of a polyhydroxy compound with a plurality of hydroxyl-containing epoxy compounds. R ¹ is a C _1-5 alkylene group; R ² each includes

,

,

,

, H or

, in which at least one R ² series

,

,

,or

; R ³ is C _1-5 alkyl;; n=1-3; x=8-24; y=0-8; x+y=16-24.

In one embodiment, the molar ratio of polyhydroxy compound to hydroxyl-containing epoxy compound is between 1:6 and 1:20. For example, when the polyol has three hydroxyl groups, the molar ratio of the polyol to the hydroxyl-containing epoxy compound is between 1:6 and 1:15. For example, when the polyol has four hydroxyl groups, the molar ratio of the polyol to the hydroxyl-containing epoxy compound is between 1:8 and 1:20. If the proportion of hydroxyl-containing epoxy compounds is too low, sufficient branched ether chains cannot be provided. If the proportion of the hydroxyl group-containing epoxy compound is too high, the subsequent reaction processing will be difficult due to the excessively high branched ether chain.

For example, the reaction of a polyol with a hydroxyl-containing epoxy to form a Core can be as follows:

In the above formula, a can be 2, 3, 4, or more, ie, the number of hydroxyl groups of the polyol. The center X of the polyhydroxy compound of the above formula is a quaternary carbon, but the present disclosure is not limited thereto. For example, the center of the polyol can be a _C2-10 alkyl group, a _C3-10 cycloalkyl group, a _C6-10 aryl group, or a _C5-10 heteroaryl group. For example, the polyol can be pentaerythritol, 2-methyl-1,3-propanediol, 1,1,1-trimethylolpropane, 1,4-cyclohexanedimethanol, 1,3-butanediol Alcohol, neopentyl glycol, dimer of the above, trimer of the above, or polymer of the above. The hydroxyl-containing epoxy compound of the above formula is glycidol, but the present disclosure is not limited thereto. For example, the hydroxyl-containing epoxy compound can be an aliphatic epoxy compound such as glycidol, 3-ethyl-3-oxetanemethanol, 3-alkyl-3-(hydroxyalkoxy)oxa Cyclobutane or 3,3-bis(hydroxyalkyl)oxetane, the like, or a combination of the foregoing. In the above reaction formula, all the hydroxyl groups of the polyhydroxy compound undergo a ring-opening reaction with the epoxy group of the hydroxyl-containing epoxy compound to form a first-generation intermediate product G1, and all the hydroxyl groups of the intermediate product G1 are further reacted with the hydroxyl-containing epoxy compound. The epoxy group undergoes a ring-opening reaction to form the second-generation intermediate G2. In one embodiment, part of the hydroxyl groups of the polyol and part of the hydroxyl groups of the intermediate product G1 may not react with the epoxy groups of the hydroxyl-containing epoxy compound. In other words, the terminal hydroxyl group of the dendrimer is less than or equal to a*2*2. In one embodiment, the dendrimers are not limited to the second generation intermediate G2. It can then undergo a ring-opening reaction with the epoxy group of the hydroxyl-containing epoxy compound to form a third-generation intermediate, a fourth-generation intermediate, or a more-generation intermediate, and so on.

The above-mentioned core Core (such as the intermediate molecule G2) can be reacted with multiple chain extenders such as cyclic lactones as follows:

的數目如x=8-24，且x+y=16-24。不論如何，核心至少有部分羥基與環內酯反應，以達鏈延長的效果。若x的數目過低(鏈延長的比例不足)，則包含樹脂的墨水在成膜後無法有效提伸膜材的可撓性。 In the above formula, n may be 1 to 3. In one embodiment, the core Core (eg, the intermediate molecule G2) may have some hydroxyl groups that do not participate in the chain extension reaction of the cyclic lactone ring-opening, that is, the number of R is H, such as y=0-8. As for R after chain extension reaction with cyclic lactone ring opening is

The number of such as x=8-24, and x+y=16-24. In any case, at least some of the hydroxyl groups of the core react with the cyclic lactone to achieve chain extension. If the number of x is too low (the ratio of chain extension is insufficient), the resin-containing ink cannot effectively improve the flexibility of the film material after film formation.

An endcapping group such as acrylic acid, methacrylic acid, glycidyl methacrylate, 2-aminoacrylic acid, or the like can then be taken to react with the chain-extending molecule to form a resin. If acrylic acid is used, the above reaction can be as follows:

。在其他實施例中，部分羥基不與丙烯酸反應，即部分的R'為H或

。此時可採用其他封端劑如C _2-6的酸類(如乙酸或丙酸)或酸酐類(如醋酸酐或順丁烯二酸酐)與上述化合物反應，將部分或全部殘留的羥基轉為酯基。以酸酐(其他封端劑)為例，上述反應如下式。雖然下式中所有殘留的羥基均與酸酐反應形成酯基，但其他實施例可殘留少量羥基未反應。在下式中，R ³可為C _1-5的烷基。

In the above formula, some of the unchained hydroxyl groups (if present, such as the functional group corresponding to y) can be reacted with the acrylate, while part of the chain-extended hydroxyl group (such as the functional group corresponding to x) can be reacted with the acrylate. In some embodiments, all hydroxyl groups are reacted with acrylic acid ie R' is not H or

. In other embodiments, some of the hydroxyl groups do not react with acrylic acid, ie, some of the R' are H or

. At this time, other end-capping agents such as C _2-6 acids (such as acetic acid or propionic acid) or acid anhydrides (such as acetic anhydride or maleic anhydride) can be used to react with the above compounds to convert part or all of the remaining hydroxyl groups into ester group. Taking acid anhydride (other capping agent) as an example, the above reaction is as follows. Although all of the remaining hydroxyl groups in the following formula are reacted with the acid anhydride to form ester groups, other embodiments may leave a small amount of hydroxyl groups unreacted. In the following formula, R ³ can be a C _1-5 alkyl group.

In one embodiment, the molar ratio of polyol to capping agent is between 1:6 and 1:20. If the ratio of the capping agent is too low, there will be too many uncapped hydroxyl groups, resulting in high molecular viscosity, which is unfavorable for subsequent applications. If the ratio of the end-capping agent is too high, the end-capping esterification reaction cannot proceed if the number of hydroxyl functional groups is exceeded. In some embodiments, the resin has 6 to 16 acrylate end groups. If the number of acrylate end groups is too small, the cross-linking reaction functional group ratio per molecule will be low, resulting in poor reactivity in subsequent ink applications.

An ink provided by an embodiment of the present disclosure includes: the above-mentioned resin, an ultraviolet curing monomer, and a photoinitiator. For example, the UV curing monomer may be 1,6-hexanediol diacrylate, isobornyl acrylate, trimethylolpropane triacrylate, or the like. In one embodiment, the weight ratio of the resin to the UV-curable monomer may be between 100:30 and 100:5000. If the weight ratio of the UV curing monomer is too low, the viscosity of the ink will be too high, the compatibility with the photoinitiator will be poor, and the processing application will be poor. If the weight ratio of the ultraviolet curing monomer is too high, the physical properties after photocuring will be poor, and application characteristics cannot be provided. In one embodiment, the photoinitiator can be (2,4,6-trimethylbenzyl)diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzyl) ) diphenylphosphine oxide or 2-hydroxy-2-methyl-1-phenyl-1-propanone. In one embodiment, the weight ratio of resin to photoinitiator may be between 100:30 and 100:500. If the weight ratio of the photoinitiator is too low, the curing effect is incomplete and cannot be applied. If the weight ratio of the photoinitiator is too high, it is easy to cause poor stability of the ink, and the material is too brittle and easy to crack after curing.

In some embodiments, the ink further includes an additive, and the weight ratio of the resin to the additive is between 100:20 and 100:200. For example, the additives can be adhesion aids, leveling agents, inhibitors, surfactants, fillers, pigments, or combinations thereof. Adhesion additives can improve the adhesion between the ink and the substrate, leveling agents can make the thickness of the coating uniform, inhibitors can provide ink storage stability, surfactants can uniformly disperse the composition in the ink, and fillers can increase The mechanical properties of the ink after film formation, and the pigment can change the appearance color of the ink film after formation. If the amount of additives is too large, the physical properties of the ink after curing will be deteriorated.

The above inks can be coated on soft substrates such as plastic, paper, or leather, and are flexible after being hardened by light. The coating method of the above ink can be spin coating, dip coating, roller coating, spray coating, line coating, or other feasible methods.

In order to make the above-mentioned content and other objects, features, and advantages of the present disclosure more obvious and easy to understand, the following specific embodiments are described in detail as follows: [ Embodiment ]

Preparation Example 1 (Preparation of resin core Core) 10.2 g of pentaerythritol (0.075 mole) was dissolved in 250.0 mL of 1,4-dioxane, and then 88 mL of potassium methoxide (25% methanol solution, 0.3 mole) was added, Stir well under nitrogen for 0.5 hours at room temperature. The temperature was raised to 75°C to 80°C, then 59.9 mL of glycidol (0.9 mole) was added to the above solution, stirred uniformly for 12 hours, and then separated into two layers after standing. After removing the upper layer (clear solvent layer), add 50 mL of methanol and cation exchange resin to neutralize to neutrality. The cation exchange resin was removed by filtration, and after the crude product was concentrated under reduced pressure to remove the solvent, 69.25 g of resin core DPPolG2 was obtained (yield 90%). The mass spectrometer and titration showed that the single resin core DPPolG2 molecule was formed by the reaction of one pentaerythritol and 12 glycidols (G1=4, G2=8), and had 16 terminal hydroxyl groups. According to GPC measurement, the weight-average molecular weight of the resin core DPPolG2 is between 802 and 1320. Through titration, the hydroxyl value of the resin core DPPolG2 was between 870 and 922 mgKOH/g. The structure of the resin core DPPolG2 is as follows:

Preparation Example 2 (Chain Extension) Dissolve 35.8 g of the resin core DPPolG2 (33 mmole) prepared in Preparation Example 1 in 60.0 g of cyclocaprolactone (528 mmole), and then add 0.06 g of stannous isooctoate (0.15 mmole) . The above reactants were stirred uniformly and heated to between 90°C and 120°C. After refluxing for about 16 hours, the temperature was lowered to room temperature to obtain a chain-extended resin DPPolG2-CA. According to ESI-MS measurement, the chain-extended resin DPPolG2-CA molecule has 16 cyclic lactone chain extension groups. The chain-extended resin DPPolG2-CA has an m/z of 1425.8334 (2851.6668/2) and contains a cyclic lactone chain extension repeating unit signal with an m/z of 114 (ie, 16 cyclic lactone chain extension groups). The above reaction is as follows:

Preparation Example 3 (end capping) Dissolve 94.1 g of the chain-extended resin DPPolG2-CA (33 mmole) prepared in Preparation Example 2 in 110.0 mL of toluene, and then add 19.0 g of acrylic acid (264 mmole) and 5.0 g of methyl methacrylate. sulfonic acid (52.8 mmole) and 1.31 g of p-methoxyphenol (10.56 mmole). A Dean-Stark apparatus was set up for the water removal reaction. The above reactants were stirred uniformly and air was continuously passed through, and heated to between 85°C and 90°C. After about 1.5 hours of reaction, 23.8 g of glacial acetic acid (396 mmole) was added to react for another 1.5 hours. After cooling to about 40°C, concentrated under reduced pressure, and the toluene solvent was removed to obtain a crude product. The crude product was extracted three times with 250 mL of ethyl acetate and 250 mL of pure water, and the organic layer was taken. The organic layer was concentrated under reduced pressure to remove the solvent to obtain 97.2 g of the resin DPPolG2-CAMA. According to the measurement by nuclear magnetic resonance spectrometer, the resin DPPolG2-CAMA molecule has 6 to 8 terminal acrylate groups and 10 to 12 acetate groups. The resin DPPolG2-CAMA is terminated with acrylate and acetate. The viscosity of resin DPPolG2-CAMA at 25°C is 350-510 cPs as measured by viscometer (Brookfield DV2T). The above reaction is as follows:

Preparation Example 4 (chain extension followed by epoxy ring opening) 10.2 g of pentaerythritol (0.075 mole) was dissolved in 34.2 g of cyclocaprolactone (0.3 mole) and 0.03 g of stannous isooctanoate (0.075 mmole) was added. The above reactants were stirred uniformly and heated to between 90°C and 120°C. After refluxing for about 16 hours, the temperature was lowered to room temperature to obtain the product Penta-CA. Through the measurement of nuclear magnetic resonance spectrometer and mass spectrometer, it can be known that the product Penta-CA molecule has 4 cyclic lactone chain extension groups. Take 44.3g of Penta-CA (0.075 mole) and dissolve it in 250.0 mL of 1,4-dioxane, then add 88 mL of potassium methoxide (25% methanol solution, 0.3 mole), stir at room temperature with nitrogen Evenly 0.5 hours. Be warmed up to 75 ℃-80 ℃ and then add 59.9 mL of glycidol (0.9 mole) to the above solution and stir evenly for 12 hours, cool to room temperature, remove the solvent by concentrating under reduced pressure, measure by mass spectrometer, there is no expected product molecular weight, This synthetic procedure fails to yield the expected product with multiple terminal acrylate groups.

Preparation example 5 (direct end capping without chain extension) Dissolve 10.0 g of the resin core DPPolG2 (9.76 mmole) prepared in Preparation Example 1 in 20.0 mL of toluene, and then add 11.25 g of acrylic acid (156.08 mmole), 1.52 g of methanesulfonic acid (15.76 mmole) and 0.182 g of p-methoxyphenol (1.46 mmole). A Dean-Stark apparatus was set up for the water removal reaction. The above reactants were stirred uniformly and air was continuously passed through, and heated to between 85°C and 90°C. The reaction is about 3 hours. After the reaction, the mixture was cooled to room temperature and concentrated under reduced pressure, and the toluene solvent was removed to obtain a crude product. The crude product was extracted three times with 50.0 mL of ethyl acetate and 50 mL of pure water, and the organic layer was taken. The organic layer was concentrated under reduced pressure to remove the solvent to obtain 12.1 g of resin DPPolG2-16AA. According to the measurement by nuclear magnetic resonance spectrometer, the single resin DPPolG2-16AA molecule has 12 to 16 terminal acrylate groups. According to GPC measurement, the weight average molecular weight of resin DPPolG2-16AA is 2340.76, and the PDI is 2.37. Through viscometer (Brookfield DV2T) measurement, the viscosity of resin DPPolG2-16AA at 25°C is 862 cps.

Example 1-1 Take 20 parts by weight of the resin DPPolG2-CAMA of Preparation Example 3, 15 parts by weight of trimethylolpropane triacrylate (TMPTA), 25 parts by weight of 1,6-hexanediol diacrylate (HDDA), 20 parts by weight of After mixing 10 parts by weight of ethoxyethoxyethyl acrylate (EOEOEA), 10 parts by weight of an adhesion aid, and 10 parts by weight of a photoinitiator, an ink was formed. The viscosity of the above ink at 25°C is 18.9 cps (measured by Brookfield DV2T). Coat the above ink on the polyurethane film with a coating rod of F060FKB9 to form a wet film with a thickness of 16 microns. The wet film is irradiated with ultraviolet rays to harden into a film. After curing, the 100 grids of the film can reach 5B (ASTM-D3359). The flexural resistance of the film after hardening was measured by ASTM-D2813. The flexural resistance of the hardened film material can reach 60,100 times.

Comparative Example 1-1 Take 20 parts by weight of polyurethane resin DR-U384 (purchased from Changxing Materials), 15 parts by weight of TMPTA, 25 parts by weight of HDDA, 20 parts by weight of EOEOEA, 10 parts by weight of adhesion aid, and 10 parts by weight of light After the starter is mixed, the ink is formed. The viscosity of the above ink at 25°C is 127.8 cps (measured by Brookfield DV2T). Coat the above ink on the polyurethane film with a coating rod of F060FKB9 to form a wet film with a thickness of 16 microns. The wet film is irradiated with ultraviolet rays to harden into a film. After curing, the 100 grids of the film can reach 5B (ASTM-D3359). The flexural resistance of the film after hardening was measured by ASTM-D2813. The flexural resistance of the hardened film material can reach 50,100 times, but cannot reach 60,100 times.

Comparative Example 2-1 Take 20 parts by weight of polyester dendritic resin 6363 (purchased from Changxing Materials), 15 parts by weight of TMPTA, 25 parts by weight of HDDA, 20 parts by weight of EOEOEA, 10 parts by weight of adhesion aid, and 10 parts by weight of light After the initiators are mixed, an ink is formed. The viscosity of the above ink at 25°C is 33.6 cps (measured by Brookfield DV2T). Coat the above ink on the polyurethane film with a coating rod of F060FKB9 to form a wet film with a thickness of 16 microns. The wet film is irradiated with ultraviolet rays to harden into a film. After curing, the 100 grids of the film can reach 5B (ASTM-D3359). The flexural resistance of the film after hardening was measured by ASTM-D2813. The flexural resistance of the hardened film material can reach 40,100 times, but cannot reach 50,100 times.

Comparative Example 3-1 Take 20 parts by weight of resin DPPolG2-16AA of Preparation Example 5, 15 parts by weight of TMPTA, 25 parts by weight of HDDA, 20 parts by weight of EOEOEA, 10 parts by weight of adhesion aid, and mix with 10 parts by weight of photoinitiator Then, ink is formed. The viscosity of the above ink at 25°C is 34.1 cps (measured by Brookfield DV2T). Coat the above ink on the polyurethane film with a coating rod of F060FKB9 to form a wet film with a thickness of 16 microns. The wet film is irradiated with ultraviolet rays to harden into a film. After curing, the 100 grids of the film can reach 5B (ASTM-D3359). The flexural resistance of the film after hardening was measured by ASTM-D2813. The flexural resistance of the hardened film material can reach 50,100 times, but cannot reach 60,100 times. It can be seen from Example 1-1 and Comparative Example 3-1 that the chain-extended resin can effectively increase the number of times of flexural resistance of the film.

Example 1-2 Take 5 parts by weight of the resin DPPolG2-CAMA of Preparation Example 3, 15 parts by weight of urethane acrylate resin (PUA), 12 parts by weight of TMPTA, 20 parts by weight of HDDA, 13 parts by weight of tetrahydrofuran acrylate (THFA), 12 parts by weight of Ink was formed by mixing isobornyl acrylate (IBOA), 5 parts by weight of adhesion aid, 8 parts by weight of photoinitiator, and 10 parts by weight of white toner by weight. The viscosity of the above inks at 50°C is 10.5 cps (measured by Brookfield DV2T). The above ink was coated on the polyimide film with a coating bar of F060FKB9 to form a wet film with a thickness of 16 microns. The wet film is irradiated with ultraviolet rays to harden into a film. After curing, the 100 grids of the film can reach 5B (ASTM-D3359). The flexural resistance of the film after hardening was measured by ASTM-D2176. The flexural resistance of the hardened film material can reach 20,100 times.

Comparative Example 1-2 Take 5 parts by weight of polyurethane resin DR-U384, 15 parts by weight of PUA, 12 parts by weight of TMPTA, 20 parts by weight of HDDA, 13 parts by weight of THFA, 12 parts by weight of IBOA, 5 parts by weight of adhesion aid, 8 Ink was formed by mixing the photoinitiator in parts by weight and 10 parts by weight of white toner. The viscosity of the above ink at 50°C is 15.8 cps (measured by Brookfield DV2T). The above ink was coated on the polyimide film with a coating bar of F060FKB9 to form a wet film with a thickness of 16 microns. The wet film is irradiated with ultraviolet rays to harden into a film. After curing, the 100 grids of the film can reach 5B (ASTM-D3359). The flexural resistance of the film after hardening was measured by ASTM-D2176. The flexural resistance of the hardened film material can reach 16,100 times, but cannot reach 20,100 times.

Comparative Example 2-2 Take 5 parts by weight of polyester dendritic resin 6363, 15 parts by weight of PUA, 12 parts by weight of TMPTA, 20 parts by weight of HDDA, 13 parts by weight of THFA, 12 parts by weight of IBOA, 5 parts by weight of adhesion aid, 8 parts by weight of the photoinitiator was mixed with 10 parts by weight of the white toner to form an ink. The viscosity of the above ink at 50°C is 11.1 cps (measured by Brookfield DV2T). The above ink was coated on the polyimide film with a coating bar of F060FKB9 to form a wet film with a thickness of 16 microns. The wet film is irradiated with ultraviolet rays to harden into a film. After curing, the 100 grids of the film can reach 5B (ASTM-D3359). The flexural resistance of the film after hardening was measured by ASTM-D2176. The flexural resistance of the cured film can reach 8100 times, but cannot reach 10100 times.

Comparative Example 3-2 Take 5 parts by weight of the resin DPPolG2-16AA of Preparation Example 5, 15 parts by weight of PUA, 12 parts by weight of TMPTA, 20 parts by weight of HDDA, 13 parts by weight of THFA, 12 parts by weight of IBOA, and 5 parts by weight of adhesion aid. Ink was formed after mixing with 10 parts by weight of white toner, 8 parts by weight of photoinitiator, and 10 parts by weight of white toner. The viscosity of the above ink at 50°C is 12.3 cps (measured by Brookfield DV2T). The above ink was coated on the polyimide film with a coating bar of F060FKB9 to form a wet film with a thickness of 16 microns. The wet film is irradiated with ultraviolet rays to harden into a film. After curing, the 100 grids of the film can reach 5B (ASTM-D3359). The flexural resistance of the film after hardening was measured by ASTM-D2176. The flexural resistance of the hardened film material can reach 10,100 times, but cannot reach 16,100 times. It can be seen from Example 1-2 and Comparative Example 3-2 that the chain-extended resin can effectively increase the number of times of flexural resistance of the film.

Although the present disclosure has been disclosed above with several preferred embodiments, it is not intended to limit the present disclosure. Anyone with ordinary knowledge in the technical field may make any changes without departing from the spirit and scope of the present disclosure. Therefore, the scope of protection of this disclosure should be determined by the scope of the appended patent application.

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Claims (10)

A resin whose chemical structure is:

, wherein Core is formed by the reaction of a polyhydroxy compound and a plurality of hydroxyl-containing epoxy compounds, and the molar ratio of the polyhydroxy compound and these hydroxyl-containing epoxy compounds is 1:6 to 1:20; R ¹ is a C _1-5 alkylene group; R ² each includes

,

,

,

, H or

, in which at least one R ² series

,

,

,or

; R ³ is a C _1-5 alkyl group; n=1-3; x=8-24; y=0-8; x+y=16-24. The resin of claim 1, wherein the polyhydroxy compound includes three hydroxyl groups, and the molar ratio of the polyhydroxy compound to the hydroxyl-containing epoxy compounds is between 1:6 and 1:15. The resin of claim 1, wherein the polyhydroxy compound includes four hydroxyl groups, and the molar ratio of the polyhydroxy compound to the hydroxyl-containing epoxy compounds is between 1:8 and 1:20. The resin of claim 1, wherein the polyhydroxy compound comprises pentaerythritol, 2-methyl-1,3-propanediol, 1,1,1-trimethylolpropane, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 3-Butanediol, neopentyl glycol, a dimer of the above, a trimer of the above, or a polymer of the above. The resin of claim 1, wherein the hydroxyl-containing epoxy compounds are aliphatic epoxy compounds. The resin of claim 1, wherein the hydroxyl-containing epoxy compounds include glycidol, 3-ethyl-3-oxetanemethanol, 3-alkyl-3-(hydroxyalkoxy)oxetane alkane, 3,3-bis(hydroxyalkyl)oxetane, or a combination thereof. The resin of claim 1 having 6 to 16 acrylate end groups. An ink comprising: a resin; a UV-curable monomer; and a photoinitiator, wherein the resin has a chemical structure of:

, wherein Core is formed by the reaction of a polyhydroxy compound and a plurality of hydroxyl-containing epoxy compounds, and the molar ratio of the polyhydroxy compound and these hydroxyl-containing epoxy compounds is 1:6 to 1:20; R ¹ is a C _1-5 alkylene group; R ² each includes

,

,

,

, H or

, in which at least one R ² series

,

,

,or

; R ³ is a C _1-5 alkyl group; n=1-3; x=8-24; y=0-8; and x+y=16-24; wherein the weight of the resin and the UV-curable monomer The ratio is between 100:30 and 100:5000, and the weight ratio of the resin to the photoinitiator is between 100:30 and 100:500. The ink of claim 8, wherein the resin has 6 to 16 acrylate end groups. The ink of claim 8 further comprises an additive, and the weight ratio of the resin to the additive is between 100:20 and 100:200.