3D printing soft elastic photosensitive resin composition and preparation method thereof

文档序号：526395 发布日期：2021-06-01 浏览：16次中文

阅读说明：本技术 一种3d打印软弹光敏树脂组合物及其制备方法 (3D printing soft elastic photosensitive resin composition and preparation method thereof ) 是由臧圣彪程继业曹玉阳晋云全纪学顺于 2019-11-29 设计创作，主要内容包括：本发明提供一种3D打印软弹光敏树脂组合物及其制备方法。组合物含聚酰胺改性聚氨酯丙烯酸酯树脂、带有(甲基)丙烯酸酯基官能团光固化稀释单体、光引发剂、助剂。其中聚酰胺改性聚氨酯丙烯酸酯树脂由多异氰酸酯、活泼氢聚合物、多元酸、氨基丙烯酸酯化合物反应得到。本发明软弹光敏树脂拉伸强度高,断裂伸长率大,收缩率低,黏度小,易于打印,可满足手环,鞋材等软弹穿戴市场性能需求。(The invention provides a 3D printing soft elastic photosensitive resin composition and a preparation method thereof. The composition comprises polyamide modified polyurethane acrylate resin, a photocuring diluent monomer with a (methyl) acrylate functional group, a photoinitiator and an auxiliary agent. Wherein the polyamide modified polyurethane acrylate resin is obtained by reacting polyisocyanate, active hydrogen polymer, polybasic acid and amino acrylate compound. The soft elastic photosensitive resin has the advantages of high tensile strength, large elongation at break, low shrinkage, low viscosity and easy printing, and can meet the requirements of soft elastic wearing market performance of bracelets, shoe materials and the like.)

1. A 3D printing soft elastic photosensitive resin composition, wherein the soft elastic photosensitive resin composition comprises:

based on the total mass of the photosensitive resin composition.

2. The composition of claim 1, wherein resin I has one or more of the following structures:

wherein R is₁Is a short-chain alkane structure containing 0 to 7 carbon atoms; r₂、R₅Is residue of polyether amine without terminal amino; r₃Diisocyanate to remove the residue of-NCO; r₄Is the residue after reaction of one amino group in the amino-terminated acrylate.

3. The composition as claimed in claim 1 or 2, wherein the resin I is synthesized from raw materials comprising polyisocyanate A, active hydrogen-containing polymer B, polybasic acid C and amino acrylate compound D;

and/or the molar ratio of A, B, C, D functional groups is (1-4), (1.5-3) and (0.5-2).

4. Composition according to any one of claims 1 to 3, characterized in that the polyisocyanate A in the resin I is one or more of aliphatic, aromatic and araliphatic diisocyanates, preferably HDI, H₁₂One or more of MDI, IPDI, TDI, and TMXDI;

and/or the polymer B in the resin I is bifunctional and/or trifunctional amino-terminated polyether, preferably amino-terminated polyether with the number average molecular weight of 1000-5000, and more preferably D2000 and/or T3000;

and/or the polybasic acid C in the resin I is a short-chain dicarboxylic acid containing 0-7 carbon atoms, preferably oxalic acid and/or adipic acid, and more preferably oxalic acid;

and/or the compound D in the resin I is acrylic ester containing amino, preferably tert-butylaminoethyl methacrylate (TBAEMA).

5. The composition according to any one of claims 1 to 4, wherein the monomer II is one or more of polyethylene glycol diacrylate, lauryl methacrylate, cyclotrimethylolpropane formal acrylate, trimethylolpropane trimethacrylate and ethoxylated pentaerythritol triacrylate.

6. The composition according to any one of claims 1 to 5, wherein the photoinitiator III is one or more of 2,4, 6-trimethylbenzoyl-phosphine dioxide (TPO), bis (2,4,6) -trimethylbenzoyl phenyl phosphine oxide (819) and 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphine oxide (TEPO).

7. The composition as claimed in any one of claims 1 to 6, wherein the assistant V is one or more of a defoaming agent, a polymerization inhibitor, a color paste and a rheological assistant.

8. A method of preparing the 3D printing soft elastic photosensitive resin composition according to any one of claims 1 to 7.

9. The method of claim 8, comprising the steps of:

(1) adding the polymer B and the polybasic acid C into a solvent, and reacting to obtain an amino-terminated amide polymer; cooling, adding polyisocyanate A, and reacting to obtain a prepolymer capped with isocyanate groups;

(2) adding a compound D into the prepolymer, and evaporating a solvent after reaction to obtain resin I;

(3) and mixing the resin I with the monomer II, the photoinitiator III and the auxiliary agent V to obtain the target composition.

10. The preparation method according to claim 9, wherein the polymer B and the polybasic acid C are reacted for 4-8h in the step (1), and the reaction temperature is 200-240 ℃;

and/or, cooling to 70-120 ℃ in the step (1);

and/or the molar ratio of NCO in the polyisocyanate A added in the step (1) relative to the amino groups is 2: 1;

and/or the reaction time after the polyisocyanate A is added in the step (1) is 1-3 h.

11. The process according to claim 9, wherein the amino group in the compound D added in the step (2) is equimolar to the NCO group of the prepolymer;

and/or, reacting the step (2) at the temperature of 60-90 ℃ until the NCO content is less than 0.1%.

12. Use of the photosensitive resin composition according to any one of claims 1 to 7 or the photosensitive resin composition prepared by the preparation method according to any one of claims 8 to 11 for the field of 3D printing;

preferably, the composition is used as a 3D printing soft elastic photosensitive resin.

Technical Field

The invention relates to the field of 3D printing materials, in particular to a 3D printing soft elastic photosensitive resin composition and a preparation method thereof.

Background

The 3D printing technology, also known as additive manufacturing technology or rapid prototyping technology, is a technology that converts a three-dimensional model into a simple two-dimensional planar model by using a computer, and then controls a prototyping process to convert a material into a complex molding. The method overcomes the defects of large forming difficulty, long period, resource waste and low efficiency of the traditional processing mode. The photocuring forming process is one of 3D printing technologies, and is a process of solidifying resin by using liquid photosensitive resin as a raw material and radiating the resin by a light source under the control of a computer, and curing and forming layer by layer. At present, different scanning modes are mainly classified into a stereolithography rapid prototyping technology (SLA) and a projection type three-dimensional printing technology (DLP), wherein the former prints in a dot scanning mode, and the latter prints in a surface scanning mode, so that the former forming speed is obviously slower than the latter.

According to the curing and forming mode of photosensitive resin for 3D printing, the method is mainly divided into two types: radical photosensitive resin and cationic photosensitive resin. The free radical type is mainly that acrylate resin is polymerized into a high molecular compound after double bonds are broken by the initiation of free radicals; its advantages are high photosensitivity, high shrinkage, easy deformation and low precision. The cation type is mainly that the epoxy resin decomposes protonic acid under the action of ultraviolet light through a cation initiator to initiate epoxy group ring-opening polymerization; its advantages are high resistance to oxygen inhibition, less breaking and shrinkage, low internal stress, high adhesion, low reaction speed and poor initial shaping.

At present, the application direction of soft elastic materials in the 3D printing market gradually becomes the market mainstream, and the hard materials such as models and product verification are changed into the wearing fields such as bracelets and shoe materials. Patent CN201810009627.1 discloses an elastic photosensitive resin for DLP 3D printing and a preparation method thereof, wherein the product performance of the embodiment has the tensile strength of up to 6.5MPa and the elongation of up to 120%. Patent CN201510604989.1 discloses a 3D printing photosensitive resin material containing macromolecular elastomer, the most preferred embodiment of which is obtained by conventional methods of electronic universal stretching machine and liquid density test: the tensile strength is 14.98MPa, the elongation at break is 82 percent, and the density is 1.35g/cm³. The mechanical properties of the alloy cannot meet the increasing market demands. Therefore, based on market demand and the shortage of soft elastic materials, a demand has been soughtThe application of materials with high tensile strength and excellent elongation at break to the wearing market becomes more urgent.

Disclosure of Invention

The invention aims to overcome the defects of a 3D printing soft elastic material, and provides a novel 3D printing soft elastic photosensitive resin composition which is high in tensile strength, large in elongation at break, low in shrinkage, low in viscosity, easy to print and capable of meeting the requirements of wearing market performance of soft elastic materials such as bracelets and shoe materials.

In order to achieve the above objects and achieve the above technical effects, the invention adopts the following technical scheme:

a 3D printing soft elastic photosensitive resin composition, the soft elastic photosensitive resin composition comprising:

based on the total mass of the photosensitive resin composition.

In the invention, the resin I has one or more of the following structures:

In the invention, the resin I is synthesized from raw materials comprising polyisocyanate A, polymer B containing active hydrogen, polybasic acid C and acrylate compound D.

In the invention, the molar ratio of the A, B, C and D functional groups is (1-4): (1.5-3): 1, (0.5-2).

In the invention, the polyisocyanate A in the resin I is one or more of aliphatic, aromatic and araliphatic diisocyanate, preferably HDI and H₁₂One or more of MDI, IPDI, TDI, and TMXDI.

In the invention, the polymer B in the resin I is bifunctional and/or trifunctional amino-terminated polyether, preferably amino-terminated polyether with the number average molecular weight of 1000-5000, and more preferably D2000 and/or T3000.

In the invention, the polybasic acid C in the resin I is short-chain dicarboxylic acid containing 0-7 carbon atoms, preferably oxalic acid and/or adipic acid, and more preferably oxalic acid.

In the invention, the compound D in the resin I is acrylic ester containing amino, preferably tert-butylaminoethyl methacrylate (TBAEMA).

In the invention, the monomer II is one or more of polyethylene glycol diacrylate, lauryl methacrylate, cyclotrimethylolpropane methylal acrylate, trimethylolpropane trimethacrylate and ethoxylated pentaerythritol triacrylate.

In the invention, the photoinitiator III is one or more of 2,4, 6-trimethylbenzoyl-phosphine dioxide (TPO), bis (2,4,6) -trimethylbenzoyl phenyl phosphine oxide (819) and 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphine oxide (TEPO).

In the invention, the assistant V is one or more of a defoaming agent, a polymerization inhibitor, a color paste and a rheological assistant.

The invention also aims to provide a preparation method of the 3D printing soft elastic photosensitive resin composition.

A method for preparing the 3D printing soft elastic photosensitive resin composition.

In the invention, the preparation method comprises the following steps:

(2) adding a compound D into the prepolymer, and evaporating a solvent after reaction to obtain resin I;

(3) and mixing the resin I with the monomer II, the photoinitiator III and the auxiliary agent V to obtain the target composition.

In the invention, the reaction time of the polymer B and the polybasic acid C in the step (1) is 4-8h, and the reaction temperature is 200-240 ℃.

In the invention, the temperature in the step (1) is reduced to 70-120 ℃.

In the present invention, the molar ratio of NCO to amino groups in the polyisocyanate A charged in the step (1) is 2: 1.

In the invention, the reaction time after the polyisocyanate A is added in the step (1) is 1-3 h.

In the present invention, a solvent such as DMF is added in step (1).

In the present invention, the amino group in the compound D added in the step (2) is equimolar to the NCO group of the prepolymer.

In the invention, in the step (2), the reaction is carried out at the temperature of 60-90 ℃ until the NCO content is less than 0.1%.

In the invention, the mixing in the step (3) is to stir at high speed in a stirrer, and to stir uniformly, then to stand for defoaming. As known, common additives such as defoaming agent and color paste can be added during mixing, and a common stirring process is adopted, for example, stirring is carried out for 1 hour at 40 ℃ and at the rotating speed of 700 r/min.

Still another object of the present invention is to provide a use of the above 3D printing soft elastic photosensitive resin composition.

An application of the photosensitive resin composition, wherein the resin is used in the field of 3D printing;

preferably, the composition is used as a 3D printing soft elastic photosensitive resin.

The invention has the beneficial effects that:

(1) different functional groups in the resin are in the same main chain or branched chain structure, the compatibility is good, wherein the amide group can endow the material with excellent flexibility, the urea bond can endow the material with excellent soft elastic performance, the defects that the flexibility and the soft elastic performance of the material in the existing market are insufficient or only have single performance are overcome, the maximum tensile strength can reach 20MPa, the elongation at break is 216%, and the Shore hardness is about 70A.

(2) The resin provided by the invention can be directly used for printing, and has the advantages of high printing success rate, good touch effect of samples and stable overall dimension.

Detailed Description

The present invention will be described in further detail with reference to examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and are not intended to limit the present invention.

The main raw materials are from the following sources:

tetramethylxylylene diisocyanate (TMXDI): cyanogen special chemical industry and industrial products.

Isophorone diisocyanate (IPDI): wanhua chemical products and industrial products.

Amino terminated polyether D2000 (number average molecular weight 2000): hensman, industrial.

Amino terminated polyether T3000 (number average molecular weight 3000): hensman, industrial.

T-butylaminoethyl methacrylate (TBAEMA): shanghai and Chuang, industrial products.

Lauryl methacrylate: korea, American source chemical industry and industrial products.

Polyethylene glycol diacrylate: korea, American source chemical industry and industrial products.

Trimethylolpropane trimethacrylate: korea, American source chemical industry and industrial products.

Bornyl methacrylate: jinan Yuan Xiang chemical industry and industrial products.

N-vinylpyrrolidone: alatin, reagent grade.

1, 4-cyclohexanedimethanol divinyl ether: chemical and industrial products of Nanjing Kangman forest.

Diethoxybisphenol a diacrylate: shanghai Linggui chemical industry and industrial products.

Photoinitiator 1173/369: tianjin, an industrial product for a long time.

Tertiary amine type benzoic acid esters: alatin, reagent grade.

Toluene: alatin, reagent grade.

Lithium initiator: alatin, reagent grade.

Isoprene: shanghai Yi chemical industry and industrial products.

Ethylene oxide: shandong and Xia chemical products and industrial products.

P-hydroxyanisole: alatin, reagent grade.

2,4, 6-trimethylbenzoyl-diphenylphosphinic oxide: tianjin, an industrial product for a long time.

Bis (2,4, 6-trimethylbenzoyl) -phenylphosphoric oxide: tianjin, an industrial product for a long time.

N, N-dimethylformamide DMF: alatin, reagent grade.

Adipic acid: alatin, reagent grade.

Oxalic acid: alatin, reagent grade.

Defoaming agent: BYK 1790, Industrial product.

Color paste: craine, industrial.

The main equipment is as follows:

temperature control device: a heat collection type constant temperature heating magnetic stirrer, which consolidates the instrument for China.

A stirring device: stirring motor, IKA.

A rotary evaporator: RE-52AA, Shanghai Yangrong Biochemical Instrument plant.

Hardness: high hardness 7 rubber durometer, shanghai hexa rhombi instrument works.

Acid value test: acid value auto-titrator, Shanghai Leima.

NCO test: according to standard HGT2409-1992, di-n-butylamine titration, model 905 autopotentiometric titrator, Switzerland.

And (3) tensile test: according to standard ISO527, INSTRON 5966 electronic universal material testing machine, the tensile rate is 50 mm/min.

And (3) testing the surface of the sample: the tactile sensation.

Example 1

Preparing polyamide modified urethane acrylate resin I-1.

Adding 500ml of DMF into a reaction bottle provided with a stirring device, a temperature control device and a condensing device, then adding 200g of aminopolyether (D2000) and 4.5g of oxalic acid, introducing inert protective gas, reacting for 8 hours at 200 ℃, cooling to 70 ℃ after measuring that the acid value is 0, adding 22.23g of IPDI, reacting for 1 hour, controlling the temperature to 60 ℃, then adding 18.5g of tert-butylaminoethyl methacrylate, reacting for 1 hour, measuring the NCO content of the prepolymer to be 0.03 percent by n-butylamine titration, stopping the reaction, transferring the material to a rotary evaporator, and distilling out the DMF solvent to obtain the polyamide modified polyurethane acrylate resin I-1.

Example 2

Preparing polyamide modified urethane acrylate resin I-2.

Adding 500ml of DMF into a reaction bottle provided with a stirring device, a temperature control device and a condensing device, then adding 300g of aminopolyether (D2000) and 4.5g of oxalic acid, introducing inert protective gas, reacting for 4 hours at 240 ℃, cooling to 100 ℃ after measuring that the acid value is 0, adding 44.46g of IPDI, reacting for 3 hours, controlling the temperature to 70 ℃, then adding 37g of tert-butylaminoethyl methacrylate, reacting for 1 hour, measuring the NCO content of the prepolymer to be 0.019% by an n-butylamine titration method, stopping the reaction, transferring the material to a rotary evaporator, and distilling out the DMF solvent to obtain the polyamide modified polyurethane acrylate resin I-2.

Example 3

Preparing polyamide modified urethane acrylate resin I-3.

Adding 500ml of DMF into a reaction bottle provided with a stirring device, a temperature control device and a condensing device, then adding 150g of aminopolyether (D2000) and 4.5g of oxalic acid, introducing inert protective gas, reacting for 6 hours at 220 ℃, cooling to 70 ℃ after measuring that the acid value is 0, adding 11.12g of IPDI, reacting for 2 hours, controlling the temperature to 80 ℃, then adding 9.25g of tert-butylaminoethyl methacrylate, reacting for 1 hour, measuring the NCO content of the prepolymer to be 0.015% by an n-butylamine titration method, stopping the reaction, transferring the material to a rotary evaporator, and distilling out the DMF solvent to obtain the polyamide modified polyurethane acrylate resin I-3.

Example 4

Preparing polyamide modified urethane acrylate resin I-4.

Adding 500ml of DMF into a reaction bottle provided with a stirring device, a temperature control device and a condensing device, then adding 300g of aminopolyether (T3000) and 6.75g of adipic acid, introducing inert protective gas, reacting for 6 hours at 220 ℃, cooling to 100 ℃ after measuring that the acid value is 0, adding 33.35g of IPDI, reacting for 1 hour, controlling the temperature to 90 ℃, then adding 27.75g of tert-butylaminoethyl methacrylate, reacting for 1 hour, measuring the NCO content of the prepolymer to be 0.014 by an n-butylamine titration method, stopping the reaction, transferring the material to a rotary evaporator, and distilling out the DMF solvent to obtain the polyamide modified polyurethane acrylate resin I-4.

Example 5

Preparing polyamide modified urethane acrylate resin I-5.

Adding 500ml of DMF into a reaction bottle provided with a stirring device, a temperature control device and a condensing device, then adding 100g of aminopolyether (D2000), 150g of aminopolyether (T3000) and 5.63g of oxalic acid, introducing inert protective gas, reacting for 6 hours at 200 ℃, cooling to 90 ℃, adding 27.79g of IPDI, reacting for 2 hours, controlling the temperature to 75 ℃, then adding 23.13g of tert-butylaminoethyl methacrylate, reacting for 1 hour, measuring the NCO content of the prepolymer to be 0.012 percent by n-butylamine titration, stopping the reaction, transferring the material to a rotary evaporator, and distilling out the DMF solvent to obtain the polyamide modified polyurethane acrylate resin I-5.

Example 6

Preparing polyamide modified urethane acrylate resin I-6.

Adding 500ml of DMF into a reaction bottle provided with a stirring device, a temperature control device and a condensing device, then adding 200g of aminopolyether (D2000) and 7.3g of adipic acid, introducing inert protective gas, reacting for 5 hours at 200 ℃, cooling to 110 ℃ after measuring that the acid value is 0, adding 22.23g of IPDI, reacting for 3 hours, controlling the temperature to 80 ℃, then adding 18.5g of tert-butylaminoethyl methacrylate, reacting for 1 hour, measuring the NCO content of the prepolymer to be 0.016% by an n-butylamine titration method, stopping the reaction, transferring the material to a rotary evaporator, and distilling out the DMF solvent to obtain the polyamide modified polyurethane acrylate resin I-6.

Example 7

Preparing polyamide modified urethane acrylate resin I-7.

Adding 500ml of DMF into a reaction bottle provided with a stirring device, a temperature control device and a condensing device, then adding 200g of aminopolyether (D2000) and 7.3g of adipic acid, introducing inert protective gas, reacting for 5 hours at 200 ℃, cooling to 110 ℃ after measuring that the acid value is 0, adding 24.43g of TMXDI, reacting for 2 hours, controlling the temperature to 80 ℃, then adding 18.5g of tert-butylaminoethyl methacrylate, reacting for 1 hour, measuring the NCO content of the prepolymer to be 0.016% by an n-butylamine titration method, stopping the reaction, transferring the material to a rotary evaporator, and distilling out the DMF solvent to obtain the polyamide modified polyurethane acrylate resin I-7.

Example 8