3D printing photosensitive resin capable of improving flame retardance and preparation method

Abstract

The invention discloses 3D printing photosensitive resin with improved flame retardance and a preparation method. The 3D printing photosensitive resin with improved flame retardance comprises the following components in parts by weight: guanidine phosphate modified polyurethane acrylate, a monomer, a photoinitiator, an antioxidant, a flame retardant and a filler. The preparation method of the modified polyurethane acrylate comprises the following steps: S1, putting guanidine phosphate containing hydroxyl and polyethylene glycol diisocyanate containing two-NCO into a stirring device, and stirring; s2, polypropylene containing hydroxyl is continuously put into the stirring device; s3, guanidine phosphate is continuously added into the stirring device, and guanidine phosphate modified polyurethane acrylate is prepared. The flame-retardant printing ink has a flame-retardant effect, and the phenomenon that the printing success rate is affected due to additional additive components is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of 3D printing. BACKGROUND

[0002] The technology developed in the present application is applied to LCD 3D printers as 3D printing consumables.

[0003] Traditional light-cured 3D printing consumables are composed of oligomers, monomers and additives, which have the following disadvantages: insufficient flame retardant performance. Moreover, if too much additive is added, it will cause printing failure due to insufficient energy. SUMMARY

[0004] The technical problem to be solved by the present application is to overcome the shortcomings of the prior art, provide a 3D printing photosensitive resin with improved flame retardancy and a preparation method, which has flame retardant effect and reduces the influence of additional additive amount on printing success rate.

[0005] The technical solution adopted by the present application is: The 3D printing photosensitive resin with improved flame retardancy comprises, by weight ratio: Phosphonium modified polyurethane acrylate 40-50 parts; Monomer 50-60 parts; Photoinitiator 1 part; Antioxidant 0.1 part; Flame retardant 0.1 part; Filler 0.1 part; The preparation method of the modified polyurethane acrylate comprises the following steps: S1, put the phosphonium containing hydroxyl and the polyethylene glycol diisocyanate containing two -NCO into the stirring device for stirring, according to the molar ratio, phosphonium: polyethylene glycol diisocyanate = 1:2; The stirring speed is 80-120r / min; The stirring time is in the range of 20-30min; S2, then continue to put the polypropylene containing hydroxyl into the stirring device, wherein the molar ratio of the polyurethane acrylate put into step S2 to the polyethylene glycol diisocyanate in the stirring device is 2:2, the stirring speed is 100-120r / min, and the stirring time is in the range of 1-1.5h; S3, then continue to put the phosphonium into the stirring device, wherein the molar ratio of the newly added phosphonium in step S3 to the polyethylene glycol diisocyanate in the stirring device is 1:2; The stirring speed is 120-130r / min, and the stirring time is in the range of 0.5-1h, and the phosphonium modified polyurethane acrylate is prepared.

[0006] The monomer is one or any combination of monofunctional acrylate, difunctional acrylate and multifunctional acrylate.

[0007] The photoinitiator is one of 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0008] The antioxidant is one of antioxidants 1010 and 2,4-dimethyl-6-tert-butylphenol.

[0009] One of the flame retardants OP935, OP945, AP423, and AP462.

[0010] The filler is sodium borate powder.

[0011] The preparation method of 3D printing photosensitive resin with improved flame retardancy includes the following steps: Modified polyurethane acrylate, monomer, photoinitiator, antioxidant, flame retardant and filler are added to the reaction vessel in the following weight ratios. The mixture is stirred under nitrogen protection and without ultraviolet irradiation. The stirring speed is 80-150 r / min, the stirring time is 2-3 h, and the stirring temperature does not exceed 55℃. When the stirring temperature exceeds 50℃, the stirring speed range is 80-90 r / min.

[0012] Polyethylene glycol diisocyanate contains two -NCO groups, guanidine phosphate, which has flame-retardant properties, contains hydroxyl groups, and polyurethane acrylate contains hydroxyl groups. The two hydroxyl groups react with the two -NCO groups of polyethylene glycol diisocyanate to obtain guanidine phosphate modified polyurethane acrylate.

[0013] Sodium borate powder is both a filler and a flame retardant.

[0014] The beneficial effects of this invention are: it has a flame-retardant effect and reduces the amount of additional additives that would affect the printing success rate. Detailed Implementation Example

[0015] 40 parts of guanidine phosphate-modified polyurethane acrylate; 50 portions of a single unit; 1 part photoinitiator; 0.1 parts antioxidant; 0.1 parts flame retardant; 0.1 parts of filler; The preparation method of modified polyurethane acrylate includes the following steps: S1. Add guanidine phosphate containing hydroxyl groups and polyethylene glycol diisocyanate containing two -NCO groups to a stirring device and stir. According to the molar ratio, guanidine phosphate: polyethylene glycol diisocyanate = 1:2; the stirring speed is 80-120 r / min; the stirring time is 20-30 min. S2. Then continue to add hydroxyl-containing polypropylene to the stirring device, wherein the molar ratio of polyurethane acrylate added in step S2 to polyethylene glycol diisocyanate in the stirring device is 2:2, and the stirring speed is 100r / min, and the stirring time is within 1h. S3. Then, guanidine phosphate is added to the stirring device, wherein the molar ratio of the newly added guanidine phosphate to the polyethylene glycol diisocyanate in the stirring device is 1:2; the stirring speed is 120 r / min, and the stirring time is 0.5 h, to obtain guanidine phosphate modified polyurethane acrylate. Example

[0016] 50 parts of guanidine phosphate-modified polyurethane acrylate; 60 units of single-component agent; 1 part photoinitiator; 0.1 parts antioxidant; 0.1 parts flame retardant; 0.1 parts of filler; The preparation method of modified polyurethane acrylate includes the following steps: S1. Add guanidine phosphate containing hydroxyl groups and polyethylene glycol diisocyanate containing two -NCO groups to a stirring device and stir. According to the molar ratio, guanidine phosphate: polyethylene glycol diisocyanate = 1:2; the stirring speed is 120 r / min; the stirring time is within 30 min. S2. Then continue to add hydroxyl-containing polypropylene to the stirring device, wherein the molar ratio of polyurethane acrylate added in step S2 to polyethylene glycol diisocyanate in the stirring device is 2:2, and the stirring speed is 120 r / min, and the stirring time is within 1.5 h. S3. Then, guanidine phosphate is added to the stirring device, wherein the molar ratio of the newly added guanidine phosphate to the polyethylene glycol diisocyanate in the stirring device is 1:2; the stirring speed is 130 r / min, and the stirring time is 1 h, to obtain guanidine phosphate modified polyurethane acrylate. Example

[0017] 40 parts of guanidine phosphate-modified polyurethane acrylate; 60 units of single-component agent; 1 part photoinitiator; 0.1 parts antioxidant; 0.1 parts flame retardant; 0.1 parts of filler; The preparation method of modified polyurethane acrylate includes the following steps: S1. Add guanidine phosphate containing hydroxyl groups and polyethylene glycol diisocyanate containing two -NCO groups to a stirring device and stir. According to the molar ratio, guanidine phosphate: polyethylene glycol diisocyanate = 1:2; the stirring speed is 80 r / min; the stirring time is within 30 min. S2. Then continue to add hydroxyl-containing polypropylene to the stirring device, wherein the molar ratio of polyurethane acrylate added in step S2 to polyethylene glycol diisocyanate in the stirring device is 2:2, and the stirring speed is 100r / min, and the stirring time is within 1h. S3. Then, guanidine phosphate is added to the stirring device, wherein the molar ratio of the newly added guanidine phosphate to the polyethylene glycol diisocyanate in the stirring device is 1:2; the stirring speed is 130 r / min, and the stirring time ranges from 0.5 to 1 h, to obtain guanidine phosphate modified polyurethane acrylate.

[0018] Comparative Experiment 1 40-50 parts of polyurethane acrylate; 50-60 parts of monomer; 1 part photoinitiator; 0.1 parts antioxidant; 0.1 parts flame retardant; 0.1 parts of filler.

[0019] Comparing Examples 1-3 with Comparative Experiment 1, it was found that Examples 1-3 had a stronger flame-retardant effect than Comparative Experiment 1.

Claims

1. A 3D printing photosensitive resin with improved flame retardancy, characterized in that... According to the weight ratio, it includes: 40-50 parts of guanidine phosphate-modified polyurethane acrylate; 50-60 parts of monomer; 1 part photoinitiator; 0.1 parts antioxidant; 0.1 parts flame retardant; 0.1 parts of filler; The preparation method of modified polyurethane acrylate includes the following steps: S1. Add guanidine phosphate containing hydroxyl groups and polyethylene glycol diisocyanate containing two -NCO groups to a stirring device and stir. According to the molar ratio, guanidine phosphate: polyethylene glycol diisocyanate = 1:2; the stirring speed is 80-120 r / min; the stirring time is 20-30 min. S2. Then continue to add hydroxyl-containing polypropylene to the stirring device, wherein the molar ratio of polyurethane acrylate added in step S2 to polyethylene glycol diisocyanate in the stirring device is 2:2, and the stirring speed is 100-120 r / min, and the stirring time is 1-1.5 h. S3. Then, guanidine phosphate is added to the stirring device, wherein the molar ratio of the newly added guanidine phosphate to the polyethylene glycol diisocyanate in the stirring device is 1:2; the stirring speed is 120-130 r / min, and the stirring time ranges from 0.5 to 1 h, to obtain guanidine phosphate modified polyurethane acrylate.

2. The 3D printing photosensitive resin for improving flame retardancy according to claim 1, characterized in that: The monomer is one or any combination of monofunctional acrylates, difunctional acrylates, and polyfunctional acrylates. The 3D printing photosensitive resin for improving flame retardancy according to claim 2 is characterized in that: the photoinitiator is one of 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. The 3D printing photosensitive resin for improving flame retardancy according to claim 3 is characterized in that: the antioxidant is one of antioxidant 1010 and 2,4-dimethyl-6-tert-butylphenol. The 3D printing photosensitive resin for improving flame retardancy according to claim 4 is characterized in that it contains one of the flame retardants OP935, OP945, AP423, and AP462.

3. The 3D printing photosensitive resin for improving flame retardancy according to claim 5, characterized in that: The filler is sodium borate powder.

4. The method for preparing the flame-retardant 3D printing photosensitive resin as described in any one of claims 1-6, characterized in that... The process includes the following steps: according to the weight ratio, guanidine phosphate modified polyurethane acrylate, monomer, photoinitiator, antioxidant, flame retardant and filler are added into the reactor in sequence. The mixture is stirred under nitrogen protection and without ultraviolet irradiation. The stirring speed is 80-150 r / min, the stirring time is 2-3 h, and the stirring temperature does not exceed 55℃. When the stirring temperature exceeds 50℃, the stirring speed range is 80-90 r / min.