阅读说明：本技术 一种耐高温无卤阻燃型3d打印光敏树脂及其制备方法 (High-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin and preparation method thereof ) 是由 何航海 蒋昆 马爱君 唐娜 于 2021-08-10 设计创作，主要内容包括：本发明公开了一种耐高温无卤阻燃型3D打印光敏树脂及其制备方法。一种耐高温无卤阻燃型3D打印光敏树脂,其包括如下质量百分含量的各组分：磷酸酯改性聚氨酯丙烯酸酯低聚物；三(2-羟乙基)异氰脲酸三丙烯酸酯；三环癸烷二甲醇二丙烯酸酯；丙烯酰吗啉；阻燃剂；光引发剂；消泡剂；润湿流平剂；防沉剂；阻聚剂；UV吸收剂。本发明的有益效果是：在保证打印成型的条件下,大大提高的光敏树脂的耐温性跟阻燃性。(The invention discloses a high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin and a preparation method thereof. The high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin comprises the following components in percentage by mass: a phosphate modified urethane acrylate oligomer; tris (2-hydroxyethyl) isocyanurate triacrylate; tricyclodecane dimethanol diacrylate; acryloyl morpholine; a flame retardant; a photoinitiator; defoaming agents; wetting and leveling agent; an anti-settling agent; a polymerization inhibitor; a UV absorber. The invention has the beneficial effects that: under the condition of ensuring printing and forming, the temperature resistance and the flame retardance of the photosensitive resin are greatly improved.)

1. The high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin is characterized by comprising the following components in percentage by mass:

2. the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin according to claim 1, which is characterized in that: the flame retardant is one or a combination of more than one of OP935, OP945, AP423 and AP 462.

3. The high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin according to claim 1, which is characterized in that: the photoinitiator is one or a combination of more of 184, 1173, 369, ITX, TPO and 819.

4. The high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin according to claim 1, which is characterized in that: the defoaming agent is one or a combination of several of BYK019, BYK1790, BYK535 and BYK065 KS 66.

5. The high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin according to claim 1, which is characterized in that: the wetting and leveling agent is one or a combination of BYK333, BYK3570, BYK3720 and BYK 331.

6. The high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin according to claim 1, which is characterized in that: the anti-settling agent is one or a combination of several of BYK410, BYK405, BYK420, BYK2009 and BYK 2013.

7. The high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin according to claim 1, which is characterized in that: the polymerization inhibitor is one or a combination of HQ, PBQ, THQ, HQMME and MTBHQ.

8. The high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin according to claim 1, which is characterized in that: the UV absorbent is one or a combination of UV326, UV327 and UV 328.

9. The preparation method of the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin, which adopts the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin as claimed in any one of claims 1 to 8, is characterized by comprising the following steps:

s1, sequentially adding the phosphate modified polyurethane acrylate oligomer, the tricyclodecane dimethanol diacrylate and the acryloyl morpholine into a stirring kettle according to the proportion, setting the stirring speed to be 150-350 r/min, continuously adding the tris (2-hydroxyethyl) isocyanurate triacrylate under the stirring state, increasing the stirring speed to be 400-600 r/min, and stirring for 30-60 minutes;

s2, adding a photoinitiator in a stirring state, and stirring for 20-40 minutes;

s3, adding a defoaming agent, a UV absorbent, a wetting leveling agent, a polymerization inhibitor and an anti-settling agent under a stirring state, and stirring for 20-40 minutes;

s4, adding the fire retardant under the stirring state, stirring for 30-60, and increasing the stirring speed to 800-

S5, filtering and packaging by using a 100-mesh filter screen to obtain the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin.

Technical Field

The invention relates to a 3D printing material technology, in particular to a high-temperature-resistant halogen-free flame-retardant 3D printing material and a production method thereof.

Background

The 3D printing technique is also called a three-dimensional printing technique, which is a technique for constructing an object by layer-by-layer printing on the basis of a digital model file. It can directly produce parts with any shape from computer graphic data without machining or any die, thus greatly shortening the development period of products, increasing productivity and reducing production cost

The photosensitive resin material is a special resin with various advantages, and generally consists of a photosensitive prepolymer, an active diluent and a photosensitizer. The photosensitive resin material can generate active fragments under the action of ultraviolet light, initiate polymerization and crosslinking reaction, and realize curing instantly.

At present, the general temperature resistance of photocuring 3D printing photosensitive resin on the market is less than 100 ℃; and the flame retardance is poor, although the resin mentioned in the patent has certain temperature resistance and flame retardance, the effect is not ideal.

Disclosure of Invention

In order to make up for the defects of temperature resistance and flame retardance of the conventional photosensitive resin, the invention provides the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin and the manufacturing method thereof, and the temperature resistance and the flame retardance of the photosensitive resin are greatly improved under the condition of ensuring printing and forming.

The technical scheme adopted by the invention is as follows:

the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin comprises the following components in percentage by mass:

the flame retardant is one or a combination of more than one of OP935, OP945, AP423 and AP 462.

The photoinitiator is one or a combination of more of 184, 1173, 369, ITX, TPO and 819.

The defoaming agent is one or a combination of several of BYK019, BYK1790, BYK535 and BYK065 KS 66.

The wetting and leveling agent is one or a combination of BYK333, BYK3570, BYK3720 and BYK 331.

The anti-settling agent is one or a combination of several of BYK410, BYK405, BYK420, BYK2009 and BYK 2013.

The polymerization inhibitor is one or a combination of HQ, PBQ, THQ, HQMME and MTBHQ.

The UV absorbent is one or a combination of UV326, UV327 and UV 328.

The preparation method of the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin comprises the following steps:

s1, sequentially adding the phosphate modified polyurethane acrylate oligomer, the tricyclodecane dimethanol diacrylate and the acryloyl morpholine into a stirring kettle according to the proportion, setting the stirring speed to be 150-350 r/min, continuously adding the tris (2-hydroxyethyl) isocyanurate triacrylate under the stirring state, increasing the stirring speed to be 400-600 r/min, and stirring for 30-60 minutes;

s2, adding a photoinitiator in a stirring state, and stirring for 20-40 minutes;

s3, adding a defoaming agent, a UV absorbent, a wetting leveling agent, a polymerization inhibitor and an anti-settling agent under a stirring state, and stirring for 20-40 minutes;

s4, adding the fire retardant under the stirring state, stirring for 30-60, and increasing the stirring speed to 800-

S5, filtering and packaging by using a 100-mesh filter screen to obtain the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin.

The sum of the mass percentages of the components in the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin is 100%.

At present, the general temperature resistance of photocuring 3D printing photosensitive resin on the market is less than 100 ℃; the flame-retardant resin has certain temperature resistance and flame retardance, but the method optimizes the printing and forming effects and the high-temperature-resistant flame-retardant effect by selecting a method of compounding the flame retardant with the flame retardant body.

The invention has the beneficial effects that: under the condition of ensuring printing and forming, the temperature resistance and the flame retardance of the photosensitive resin are greatly improved.

Drawings

FIG. 1 is a schematic flow chart of the steps of the present invention.

Detailed Description

As shown in fig. 1, the high temperature resistant halogen-free flame retardant 3D printing photosensitive resin comprises the following components in percentage by mass:

the flame retardant is one or a combination of more than one of OP935, OP945, AP423 and AP 462.

The photoinitiator is one or a combination of more of 184, 1173, 369, ITX, TPO and 819.

The defoaming agent is one or a combination of several of BYK019, BYK1790, BYK535 and BYK065 KS 66.

The wetting and leveling agent is one or a combination of BYK333, BYK3570, BYK3720 and BYK 331.

The anti-settling agent is one or a combination of several of BYK410, BYK405, BYK420, BYK2009 and BYK 2013.

The polymerization inhibitor is one or a combination of HQ, PBQ, THQ, HQMME and MTBHQ.

The UV absorbent is one or a combination of UV326, UV327 and UV 328.

The preparation method of the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin comprises the following steps:

s1, sequentially adding the phosphate modified polyurethane acrylate oligomer, the tricyclodecane dimethanol diacrylate and the acryloyl morpholine into a stirring kettle according to the proportion, setting the stirring speed to be 150-350 r/min, continuously adding the tris (2-hydroxyethyl) isocyanurate triacrylate under the stirring state, increasing the stirring speed to be 400-600 r/min, and stirring for 30-60 minutes;

s2, adding a photoinitiator in a stirring state, and stirring for 20-40 minutes;

s3, adding a defoaming agent, a UV absorbent, a wetting leveling agent, a polymerization inhibitor and an anti-settling agent under a stirring state, and stirring for 20-40 minutes;

s4, adding the fire retardant under the stirring state, stirring for 30-60, and increasing the stirring speed to 800-

S5, filtering and packaging by using a 100-mesh filter screen to obtain the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin.

The sum of the mass percentages of the components in the high-temperature-resistant halogen-free flame-retardant 3D printing photosensitive resin is 100%.

At present, the general temperature resistance of photocuring 3D printing photosensitive resin on the market is less than 100 ℃; the flame-retardant resin has certain temperature resistance and flame retardance, but the method optimizes the printing and forming effects and the high-temperature-resistant flame-retardant effect by selecting a method of compounding the flame retardant with the flame retardant body.

The following are test data:

the invention has the beneficial effects that: under the condition of ensuring printing and forming, the temperature resistance and the flame retardance of the photosensitive resin are greatly improved.