CN104765251A - High-toughness photosensitive resin for 3D printing and preparation method thereof. - Google Patents

Abstract

The invention provides a photosensitive resin for high-toughness 3D printing and a preparation method thereof, which includes four parts: a photosensitive resin (a tough photosensitive resin and a rigid photosensitive resin), a reactive diluent, a photoinitiator and an auxiliary agent. In the invention, tough photosensitive resin (tough polyurethane acrylate and epoxy-modified polyurethane) is firstly synthesized, and then mixed with rigid photosensitive resin, reactive diluent, photoinitiator and auxiliary agent. One or more of polypropylene oxide ether diol, polytetrahydrofuran ether diol, hydroxyl-terminated polybutadiene, hydroxyl-terminated styrene-butadiene rubber, hydroxyl-terminated nitrile rubber, and hydroxyl-terminated polysiloxane for tough photosensitive resins The mixture is prepared as the soft segment of the polymer, toluene diisocyanate or isophorone diisocyanate as the hard segment of the polymer, and is prepared by capping with hydroxyethyl acrylate or glycidyl alcohol. This photosensitive resin is suitable for DLP or SLA 3D printers. It is used to modify the existing 3D printing photosensitive resin so that it has excellent bending strength and can directly print out elastic models.

Description

A kind of photosensitive resin for 3D printing with high toughness and preparation method thereof

technical field

The invention belongs to the field of polymer materials, in particular to a photosensitive resin mixture and a preparation method thereof, which can be used in the field of 3D printing. the

Background technique

The 3D printing technologies that use photosensitive resin as printing materials mainly include: stereolithography (Stereolithography, SLA), DLP projection type three-dimensional printing process (Digital Light Processing, DLP) and ultra-thin layer thick photosensitive resin injection molding technology (Connex500 system , Objet Geometries). The printing process is to determine the three-dimensional model in the computer, and then deliver it to the 3D printer. The printing process uses ultraviolet light to irradiate the liquid photosensitive resin, and the layers are formed layer by layer. the

The photosensitive resin used for 3D printing needs to be cured quickly under the exposure conditions of the 3D printer, and it also needs to meet the printing process of the printer and have a certain degree of fluidity. These are the basic requirements for photosensitive resins to be used in 3D printers. At present, there is a single variety of photosensitive resins used in 3D printers in China, mainly resins with high hardness, but this type of resin has the disadvantages of insufficient toughness, poor impact resistance, and fragility. A new research and development direction. the

The shortcomings of the photosensitive resin used in SLA 3D printers are particularly prominent. Due to the use of epoxy resin with good stability, it has high strength but is very brittle, and the printed model is easy to break and bend and break. Toughening is a requirement for SLA-type 3D printing photosensitive resins, and blending with high-toughness photosensitive resins is also a solution. the

Contents of the invention

Aiming at the shortage of current 3D printing photosensitive resins, the present invention provides a high-toughness 3D printing photosensitive resin and a preparation method thereof, which can be directly used in 3D printing, or blended with other 3D printing photosensitive resins to increase its toughness. the

In order to achieve the above purpose, the technical solution adopted in the present invention is: a high-toughness 3D printing photosensitive resin, its components and proportions are as follows:

(1) Tough photosensitive resin 10-40%

(2) Rigid photosensitive resin 0～40%

(3) Active diluent 20-60%

(4) Photoinitiator 1～12%

(5) Auxiliary 0.2～3%

The (1) tough photosensitive resin is composed of one or more of urethane acrylate and epoxy-modified polyurethane resin; wherein, urethane acrylate and epoxy-modified polyurethane resin adopt polyether polyol, hydroxyl-terminated polybutylene One or a mixture of diene, hydroxy-terminated styrene-butadiene rubber, hydroxy-terminated nitrile rubber, and hydroxy-terminated polysiloxane is used as the soft segment of the polymer. the

The (2) rigid photosensitive resin is composed of one or more of epoxy resin, epoxy acrylate, and polyurethane acrylate. Wherein, the epoxy resin is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate, 3,3'-(oxybismethylene)bis(3-ethyl ) oxetane, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, bis((3,4-epoxycyclohexyl)methyl)adipate, trihydroxy Methylpropane Triglycidyl Ether, Bisphenol A Epoxy Resin, O-Cresol Novolac Epoxy Resin. the

The (3) reactive diluent is tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, Pentaerythritol Triacrylate, Polyethylene Glycol Diacrylate, Hydroxyethyl Methacrylate, Hydroxyethyl Acrylate, Cyclotrimethylolpropane Methylal Acrylate, Isobornyl Acrylate, 4-Hydroxybutyl Vinyl Ether , 4-vinyl epoxy cyclohexane, vinyl pyrrolidone, diethylene glycol divinyl ether, 4-vinyl epoxy cyclohexane, cyclic ether (3,3'-[oxybismethylene] Bis[3-ethyl]oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxy Heterobutane, 1,4 bis[(3-ethyl-3-oxymethylene oxetane) methyl] benzene), one or a mixture of cyclic lactones (propylene glycol carbonate) . the

The (4) photoinitiator is one or a mixture of acetophenone derivatives, aromatic ketones, triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, Ciba Irgacure 784 . the

The acetophenone derivatives are 1-hydroxycyclohexylacetophenone, α,α-dimethyl-α-hydroxyacetophenone, p-isopropylphenyl-2-hydroxydimethylacetone-1;

The aromatic ketones are benzophenone, chlorinated benzophenone, acrylated benzophenone, 4-phenylbenzophenone, 2-chlorinated thioxanthone, isopropyl thioxanthene ketone, dimethylthioxanthone, diethylthioxanthone, dichlorothioxanthone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. the

The (5) additives are Tego Foamex N, Tego Airex 900, Tego Airex 910, Tego Airex 920, Tego Airex 940, Tego Airex 955, Tego Airex of Tego (Evonik Degussa (China) Investment Co., Ltd.) 962, Tego Airex 980, Tego Flow 300, Tego Flow 370, Tego Glide 100, Tego Glide 435, Tego Glide 440, Tego Rad 2100, Tego Rad 2500, Tego Wet 270 or a combination of several. the

A method for preparing a high-toughness 3D printing photosensitive resin, the specific steps are as follows:

1. Preparation of tough photosensitive resin:

Take diol compound (polyether polyol, hydroxyl-terminated polybutadiene, hydroxyl-terminated styrene-butadiene rubber, hydroxyl-terminated nitrile rubber, hydroxyl-terminated polysiloxane or a mixture of several), add diisocyanate (Toluene diisocyanate or isophorone diisocyanate) compound, the molar ratio of diisocyanate to diol compound is 2:1, mix quickly at 5-25°C for 15 minutes, then heat up to 40-80°C, and react 2 ~4 hours to obtain an isocyanate terminated prepolymer. the

Add hydroxyethyl acrylate to the above-mentioned isocyanate-terminated prepolymer, the molar ratio of hydroxyethyl acrylate to diol compound is 2:1, continue to react for 2 to 6 hours, and discharge to obtain tough polyurethane acrylate. the

Or add glycidol to the above-mentioned isocyanate-terminated prepolymer, the molar ratio of glycidol to diol compound is 2:1, continue to react for 2 to 6 hours, and discharge to obtain epoxy-modified polyurethane. the

2. Stir and mix the tough photosensitive resin synthesized above with a certain amount of rigid photosensitive resin, reactive diluent, photoinitiator, and auxiliary agent at 25-40°C for 15-30 minutes to obtain a 3D printing photosensitive resin. the

Detailed ways:

Example 1: A high-toughness free radical type 3D printing photosensitive resin and its preparation

First, a tough polyurethane acrylate was synthesized: take 1 mol of diol compound hydroxyl-terminated polybutadiene, add it to 2 mol of toluene diisocyanate, mix rapidly at 10°C for 15 minutes, then raise the temperature to 40°C, and react for 2.5 hours. Add 2mol hydroxyethyl acrylate to the above product, continue to react for 4 hours to obtain tough polyurethane acrylate. the

Take 40g of the tough resin synthesized above, mix it with 50g of tripropylene glycol diacrylate, 5g of 1-hydroxycyclohexylacetophenone, 4g of benzophenone, 0.3g of Tego Glide 100, and 0.7g of Tego Rad 2100 at 25°C In 30 minutes, the 3D printing photosensitive resin was obtained. the

Example 2: A high-toughness free radical type 3D printing photosensitive resin and its preparation

First, a tough polyurethane acrylate was synthesized: take 1 mol of diol compound polypropylene oxide ether diol, add 2 mol of toluene diisocyanate, mix rapidly at 10°C for 15 minutes, then raise the temperature to 40°C, and react for 2.5 hours. Add 2mol hydroxyethyl acrylate to the above product, continue to react for 4 hours to obtain tough polyurethane acrylate. the

Take 30g of the tough resin synthesized above, mix with 10g bisphenol A diacrylate, 15g pentaerythritol triacrylate, 20g cyclotrimethylolpropane formal acrylate, 13g tripropylene glycol diacrylate, 5g1-hydroxycyclohexyl Acetophenone, 4g benzophenone, 1.5g Tego Glide 100, 1.5g Tego Rad 2100 were stirred and mixed at 25°C for 30 minutes to obtain a 3D printing photosensitive resin. the

Example 3: A high-toughness free radical-cation hybrid 3D printing photosensitive resin and its preparation

First, a tough epoxy-modified polyurethane is synthesized: take 1 mol of diol compound hydroxyl-terminated polysiloxane, add it to 2 mol of toluene diisocyanate, mix rapidly at 10°C for 15 minutes, then raise the temperature to 50°C, and react for 3 hours. Add 2mol glycidol to the above product, and continue to react for 4 hours to obtain tough epoxy-modified polyurethane. the

Take 20g of the toughness resin synthesized above, and 15g 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate, 10g bisphenol A epoxy resin, 30g trimethylolpropane triacrylate , 15g of isobornyl acrylate, 5g of photoinitiator triarylsulfonium hexafluorophosphate, 4.8g of 1-hydroxycyclohexylacetophenone, and 0.2g of Tego Flow 300 were stirred and mixed at 40°C for 30 minutes to obtain a 3D printing photosensitive resin. the

Example 4: A high-toughness free radical-cation hybrid 3D printing photosensitive resin and its preparation

First synthesize a tough epoxy-modified polyurethane: take 1 mol of diol compound hydroxyl-terminated polytetrahydrofuran ether, add 2 mol of isophorone diisocyanate, mix quickly at 25°C for 20 minutes, then raise the temperature to 80°C, and react for 3 hours . Add 2mol glycidol to the above product, and continue to react for 4 hours to obtain tough epoxy-modified polyurethane. the

Get the toughness resin 40g of above-mentioned synthesis, with 15g 4,5-epoxycyclohexane-1,2-diglycidyl carboxylate, 5g o-cresol novolac epoxy resin, 20g pentaerythritol triacrylate, 10g vinylpyrrolidone, 1g 1-hydroxycyclohexylacetophenone, 3g 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4g triarylsulfonium hexafluoroantimonate, 2g Tego Flow 300 were stirred and mixed at 35°C for 20 Minutes to get 3D printing photosensitive resin. the

Example 5: A high-toughness free radical-cation hybrid 3D printing photosensitive resin and its preparation

First, a tough epoxy-modified polyurethane was synthesized: take 1 mol of diol compound hydroxyl-terminated polybutadiene, add 2 mol of toluene diisocyanate, mix rapidly at 15°C for 20 minutes, then raise the temperature to 50°C, and react for 3 hours. Add 2mol glycidol to the above product, and continue to react for 4 hours to obtain tough epoxy-modified polyurethane. the

Take 25g of the tough photosensitive resin synthesized above, and 15g 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 15g bisphenol A epoxy resin, 30g pentaerythritol triacrylate, 6g vinylpyrrolidone , 1g 1-hydroxycyclohexylacetophenone, 3g 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4g Ciba Irgacure 784, 1g Tego Flow 300 were stirred and mixed at 40°C for 15 minutes to obtain 3D Print photosensitive resin. the

Claims (9)

1. a high tenacity 3D printed photosensitive resin, is characterized in that: each component and percentage by weight as follows:

(1) toughness photosensitive resin 10 ~ 40%;

(2) rigidity photosensitive resin 0 ~ 40%;

(3) reactive diluent 20 ~ 60%;

(4) light trigger 1 ~ 12%;

(5) auxiliary agent 0.2 ~ 3%.

2. high tenacity 3D printed photosensitive resin according to claim 1, is characterized in that: described (1) toughness photosensitive resin is made up of a kind of or two kinds the potpourri in urethane acrylate, epoxy modified polyurethane resin; Wherein, urethane acrylate and epoxy modified polyurethane resin adopt one or several the potpourri in polyoxypropylene glycol, PTMG, end hydroxy butadiene, end hydroxy styrene-butadiene rubber, hydroxy'terminated butadiene nitrile rubber, hydroxy-terminated polysiloxane as soft section of component of polymkeric substance, toluene diisocyanate or isophorone diisocyanate are as the hard section component of polymkeric substance, and hydroxy-ethyl acrylate or epoxy prapanol are that end-capping reagent is prepared from.

3. high tenacity 3D printed photosensitive resin according to claim 1, is characterized in that: described (2) rigidity photosensitive resin is made up of epoxy resin; Wherein, described epoxy resin is 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl formic ether, 3,3'-(oxygen base dimethylene) two (3-ethyl) oxetanes, 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl ester, two ((3,4-epoxycyclohexyl) methyl) adipate, trihydroxymethylpropanyltri diglycidyl ether, bisphenol A epoxide resin, o-cresol formaldehyde epoxy resin.

4. high tenacity 3D printed photosensitive resin according to claim 1, is characterized in that: described (3) reactive diluent is tri (propylene glycol) diacrylate, hexanediyl ester, bisphenol a diacrylate, Tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethyleneglycol diacrylate, hydroxyethyl methylacrylate, hydroxy-ethyl acrylate, ring trimethylolpropane dimethoxym ethane acrylate, isobornyl acrylate, 4-hydroxy butyl vinyl ether, 4 vinyl epoxy cyclohexane, vinyl pyrrolidone, diethylene glycol divinyl ether, 4 vinyl epoxy cyclohexane, cyclic ethers (3,3'-[oxygen base dimethylene] two [3-ethyl] oxetanes, 3-ethyl-3-hydroxymethyl-oxetane, 3-ethyl-3-[(2-ethyl hexyl oxy) methyl] oxetanes, two [(3-ethyl-3-Oxymethylene oxa-ring fourth) methyl] benzene of Isosorbide-5-Nitrae), one or several potpourri in cyclic lactone (propylene carbonate).

5. high tenacity 3D printed photosensitive resin according to claim 1, it is characterized in that: described (4) light trigger is acetophenone derivs (1-hydroxy cyclohexylphenyl benzoylformaldoxime, α, alpha-alpha-dimethyl-alpha-hydroxyacetophenone, p-isopropyl phenyl-2-hydroxyl dimethyl acetone-1), fragrance ketone (benzophenone, chlorinated diphenyl ketone, acrylated benzophenone, 4-phenyl benzophenone, 2-chlorination thioxanthone, isopropyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, two chlorothiaxanthenones, 2, 4, 6-trimethylbenzoy-dipheny phosphine oxide), triaryl hexafluorophosphoric acid sulfosalt, triaryl sulphur hexafluoro antimonate, the potpourri of one or more in Ciba Irgacure 784.

6. high tenacity 3D printed photosensitive resin according to claim 1, it is characterized in that: described (5) auxiliary agent is the Tego Foamex N of enlightening high (Evonik Degussa (China) Co., Ltd.), Tego Airex 900, Tego Airex 910, Tego Airex 920, Tego Airex 940, Tego Airex 955, Tego Airex 962, Tego Airex 980, Tego Flow 300, Tego Flow 370, Tego Glide 100, Tego Glide 435, Tego Glide 440, Tego Rad 2100, Tego Rad 2500, one or several composition in Tego Wet 270.

7. the preparation method of the high tenacity 3D printed photosensitive resin described in any one of claim 1-6, is characterized in that it comprises the following steps:

(1) preparation of toughness photosensitive resin:

Get diatomic alcohol compounds, add in diisocyanate cpd, diisocyanate (one in toluene diisocyanate, isophorone diisocyanate) is 2:1 with the mol ratio of diatomic alcohol compounds (one or several the potpourri in polyoxypropylene glycol, PTMG, end hydroxy butadiene, end hydroxy styrene-butadiene rubber, hydroxy'terminated butadiene nitrile rubber, hydroxy-terminated polysiloxane), 5 ~ 25 DEG C of rapid mixing 15 minutes, then 40 ~ 80 DEG C are warmed up to, react 2 ~ 4 hours, obtain ending isocyanate prepolymer;

Hydroxy-ethyl acrylate or epoxy prapanol is added in above-mentioned ending isocyanate prepolymer, the mol ratio of hydroxy-ethyl acrylate/epoxy prapanol and diatomic alcohol compounds is 2:1, continue reaction 2 ~ 6 hours, discharging obtains flexible polyurethane acrylate or epoxy modified polyurethane;

(2) the toughness photosensitive resin of above-mentioned synthesis and a certain amount of rigidity photosensitive resin, reactive diluent, light trigger, auxiliary agent are uniformly mixed 15 ~ 30 minutes at 25 ~ 40 DEG C, obtain 3D printed photosensitive resin.

8. the application of the high tenacity photosensitive resin according to any one of claim 1-6 in other 3D printed photosensitive resin of modification.

9. the application of high tenacity photosensitive resin directly in stereolithography rapid shaping according to any one of claim 1-6.