阅读说明：本技术 一种光敏树脂及其制备方法和应用 (Photosensitive resin and preparation method and application thereof ) 是由 张丽娟 温广武 朱楠楠 侯永昭 仲诚 杨国威 刘芸 于 2021-03-15 设计创作，主要内容包括：本发明公开了一种光敏树脂,包括有机硅先驱体、活性稀释剂、光引发剂和硅烷偶联剂；其中,所述有机硅先驱体含有乙烯基、烯丙基、巯基和环氧基中的一种或多种；所述活性稀释剂为自由基型活性稀释剂和/或阳离子型活性稀释剂；所述硅烷偶联剂为乙烯基硅烷偶联剂、氨基硅烷偶联剂、环氧基硅烷偶联剂、巯基硅烷偶联剂和甲基丙烯酰氧基硅烷偶联剂中的一种或多种。本发明的光敏树脂固化收缩率低,陶瓷产率高,用于3D打印时打印精度高,而且成本低。(The invention discloses photosensitive resin, which comprises an organic silicon precursor, an active diluent, a photoinitiator and a silane coupling agent; wherein the organic silicon precursor contains one or more of vinyl, allyl, sulfydryl and epoxy; the active diluent is a free radical type active diluent and/or a cationic type active diluent; the silane coupling agent is one or more of vinyl silane coupling agent, amino silane coupling agent, epoxy silane coupling agent, mercapto silane coupling agent and methacryloxy silane coupling agent. The photosensitive resin disclosed by the invention is low in curing shrinkage rate, high in ceramic yield, high in printing precision when used for 3D printing and low in cost.)

1. A photosensitive resin is characterized by comprising an organic silicon precursor, a reactive diluent, a photoinitiator and a silane coupling agent;

wherein the organic silicon precursor contains one or more of vinyl, allyl, sulfydryl and epoxy;

the active diluent is a free radical type active diluent and/or a cationic type active diluent; the silane coupling agent is one or more of vinyl silane coupling agent, amino silane coupling agent, epoxy silane coupling agent, mercapto silane coupling agent and methacryloxy silane coupling agent.

2. The photosensitive resin according to claim 1, wherein the parts by mass of the organosilicon precursor, the reactive diluent, the photoinitiator and the silane coupling agent are 50 to 80 parts, 5 to 50 parts, 0.5 to 5 parts and 5 to 50 parts, respectively.

3. The photosensitive resin of claim 1, wherein the organosilicon precursor is one or more of polycarbosilane, polysilacetylene, polysiloxane, and polyazosilane.

4. The photosensitive resin of claim 1, wherein the free radical type reactive diluent is one or more of a monofunctional acrylate reactive diluent, a difunctional acrylate reactive diluent, a trifunctional acrylate reactive diluent, and a hexafunctional acrylate reactive diluent.

5. The photosensitive resin of claim 1, wherein the cationic reactive diluent is one or more of diethylene glycol vinyl ether, allyl glycidyl ether, and 3-ethyl-3-allylmethoxyoxetane.

6. The photosensitive resin of claim 1, wherein the photoinitiator is one or more of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, triphenylhexafluoroantimonate, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl) butanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzophenone, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, triarylsulfonium hexafluoroantimonate, and 2-hydroxy-2-methyl-1-phenylpropanone.

7. The photosensitive resin according to claim 1, further comprising other auxiliary agents, wherein the other auxiliary agents are one or more of antifoaming agents, polymerization inhibitors and sensitizers.

8. A method for preparing the photosensitive resin according to any one of claims 1 to 6, comprising the steps of: and uniformly mixing the organic silicon precursor, the active diluent, the photoinitiator and the silane coupling agent under the condition of keeping out of the sun to prepare the photosensitive resin.

9. A method for preparing the photosensitive resin of claim 7, comprising the steps of: and uniformly mixing the organic silicon precursor, the active diluent, the photoinitiator, the silane coupling agent and other auxiliaries under the condition of keeping out of the sun to obtain the photosensitive resin.

10. Use of the photosensitive resin of any one of claims 1-7 in the preparation of ceramics by photocuring 3D printing.

Technical Field

The invention belongs to the technical field of 3D printing materials, and particularly relates to photosensitive resin and a preparation method and application thereof.

Background

The traditional forming method is difficult to manufacture ceramic products with complex structures and high precision, the 3D printing technology is applied to the manufacturing of ceramic parts, brand new and brand new possibilities are provided for solving the problem, in various 3D printing technologies, the precision of photocuring printing is high, the speed is high, and the method has great potential in the aspect of manufacturing ceramic parts with complex shapes and high precision and quality.

The photosensitive ceramic slurry for preparing ceramic parts by the existing light curing technology mainly comprises ceramic powder and light curing resin, but when preparing dark ceramic materials such as silicon carbide, silicon nitride and the like, the curing depth is greatly reduced due to the fact that the refractive index of the ceramic powder is seriously mismatched with the refractive index of the light curing resin, the curing resolution is lowered, and even the slurry is difficult to form.

In recent years, the method for preparing the ceramic piece by combining the organosilicon precursor conversion method with the photocuring forming can solve the problems, but the non-oxide ceramic prepared by 3D printing of the organosilicon precursor has low yield, low forming precision and high cost.

Disclosure of Invention

Aiming at the problems, the invention provides a photosensitive resin and a preparation method and application thereof.

The photosensitive resin comprises an organic silicon precursor, an active diluent, a photoinitiator and a silane coupling agent;

wherein the organic silicon precursor contains one or more of vinyl, allyl, sulfydryl and epoxy;

the active diluent is a free radical type active diluent and/or a cationic type active diluent;

the silane coupling agent is one or more of vinyl silane coupling agent, amino silane coupling agent, epoxy silane coupling agent, mercapto silane coupling agent and methacryloxy silane coupling agent.

Compared with the prior art, the invention has the following beneficial effects:

the photosensitive resin disclosed by the invention is low in curing shrinkage rate, high in ceramic yield, high in printing precision when used for 3D printing, and low in raw material price.

The main components of the active diluent are carbon and oxygen, and the active diluent is converted into gas to escape after high-temperature treatment and cannot be remained in a matrix, so that the ceramic yield of the photosensitive resin is reduced;

if the yield of the ceramic is to be improved, the proportion of the polymer in the photosensitive resin system needs to be improved, and the proportion of the reactive diluent needs to be reduced, but the reduction of the proportion of the reactive diluent can influence the viscosity, the flowability and the photocuring efficiency of the photosensitive resin, and further influence the forming performance of the photosensitive resin;

firstly, the silane coupling agent in the system can reduce the dosage of the reactive diluent without influencing the fluidity of the system;

secondly, a silane coupling agent containing vinyl, amino, epoxy, methacryloxy or mercapto is selected, and a polymer containing vinyl, allyl, mercapto or epoxy photocuring groups is selected as the organosilicon precursor, so that the curing process is not influenced on the basis of reducing the dosage of the reactive diluent;

the silane coupling agent can participate in the polymerization and crosslinking of the organic silicon precursor and the active diluent, so that on one hand, the large-amplitude shrinkage of the photosensitive resin caused by the rapid polymerization of the active diluent can be relieved, and on the other hand, the ceramic yield is greatly improved, the curing shrinkage is small, the ceramic yield is high, and the printing precision is also improved due to the reduction of the proportion of the active diluent.

In addition, the silane coupling agent is low in price, and the method for improving the yield of the ceramic by adding the silane coupling agent is low in cost.

The organosilicon precursor refers to a silicon-containing ceramic precursor.

Preferably, the mass parts of the organosilicon precursor, the reactive diluent, the photoinitiator and the silane coupling agent are respectively 50-80 parts, 5-50 parts, 0.5-5 parts and 5-50 parts.

The beneficial effect of this preferred scheme does: the quality of each component is controlled, so that the photosensitive resin has good fluidity, the curing efficiency is high in the photocuring process, the curing shrinkage rate is effective, the 3D printing precision is high, and the ceramic yield is higher during later-stage sintering.

Preferably, the organosilicon precursor is one or more of polycarbosilane, polysilacetylene, polysiloxane and polynitrosilane.

The beneficial effect of this preferred scheme does: the polycarbosilane, the polysilacetylene, the polysiloxane and the polynitrosilane are used as organic silicon precursors, so that the photocuring 3D printing forming of silicon nitride or silicon carbide ceramic is realized conveniently.

Preferably, the free radical type reactive diluent is one or more of a monofunctional acrylate reactive diluent, a difunctional acrylate reactive diluent, a trifunctional acrylate reactive diluent and a hexafunctional acrylate reactive diluent.

Preferably, the cationic reactive diluent is one or more of diethylene glycol vinyl ether, allyl glycidyl ether and 3-ethyl-3-allylmethoxyoxetane.

Preferably, the photoinitiator is one or more of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, triphenylhexafluoroantimonate, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinebenzylphenyl) butanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzophenone, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, triarylsulfonium hexafluoroantimonate and 2-hydroxy-2-methyl-1-phenylpropanone.

Preferably, the coating also comprises other auxiliary agents, and the other auxiliary agents are one or more of defoaming agents, polymerization inhibitors and sensitizers.

The beneficial effect of this preferred scheme does: the defoaming agent can eliminate foam, the polymerization inhibitor can prevent the photosensitive resin from spontaneously polymerizing before the ultraviolet light is incident, and the sensitizer can increase the photocuring efficiency.

The present invention also provides a method for preparing the above photosensitive resin, comprising the steps of: and uniformly mixing the organic silicon precursor, the active diluent, the photoinitiator and the silane coupling agent under the condition of keeping out of the sun to prepare the photosensitive resin.

The present invention also provides a method for preparing the above photosensitive resin, comprising the steps of: uniformly mixing the organic silicon precursor, the active diluent, the photoinitiator, the silane coupling agent and other auxiliaries under the condition of keeping out of the sun to prepare photosensitive resin; other auxiliary agents include one or more of defoaming agents, polymerization inhibitors and sensitizers.

The invention also provides an application of the photosensitive resin in preparation of ceramics through photocuring 3D printing.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.

Example 1

The embodiment provides photosensitive resin which comprises 50-80 parts by weight of an organic silicon precursor, 5-50 parts by weight of an active diluent, 0.5-5 parts by weight of a photoinitiator, 5-50 parts by weight of a silane coupling agent and 0-5 parts by weight of other auxiliaries;

wherein the organic silicon precursor contains one or more of vinyl, allyl, sulfydryl and epoxy; the organosilicon precursor is preferably an oligomer;

the active diluent is a free radical type active diluent and/or a cationic type active diluent;

the free radical type reactive diluent is one or more of a monofunctional acrylate reactive diluent, a difunctional acrylate reactive diluent, a trifunctional acrylate reactive diluent and a hexafunctional acrylate reactive diluent;

the cationic reactive diluent is one or more of diethylene glycol vinyl ether, allyl glycidyl ether and 3-ethyl-3-allyl methoxy oxetane;

the silane coupling agent is one or more of vinyl silane coupling agent, amino silane coupling agent, epoxy silane coupling agent, mercapto silane coupling agent and methacryloxy silane coupling agent;

the photoinitiator is one or more of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, triphenyl hexafluoroantimonate, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzophenone, ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate, triarylsulfonium hexafluoroantimonate and 2-hydroxy-2-methyl-1-phenyl acetone;

the other auxiliary agents are one or more of defoaming agents, polymerization inhibitors and sensitizers.

Preferably, the organosilicon precursor is one or more of polycarbosilane, polysilacetylene, polysiloxane and polyazetasilane containing vinyl, allyl, mercapto or epoxy groups.

Preferably, the mass parts of the organosilicon precursor, the reactive diluent, the photoinitiator and the silane coupling agent are respectively 50-80 parts, 10-50 parts, 0.5-5 parts and 5-50 parts.

Preferably, the mass parts of the organosilicon precursor, the reactive diluent, the photoinitiator and the silane coupling agent are respectively 50-80 parts, 10-50 parts, 0.5-5 parts and 10-50 parts.

Preferably, the difunctional acrylate reactive diluent is 1, 6-hexanediol diacrylate, the trifunctional acrylate reactive diluent is trimethylol triacrylate, and the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane.

The embodiment also provides a preparation method of the photosensitive resin, which comprises the following steps: the method comprises the following steps: and uniformly mixing the organic silicon precursor, the active diluent, the photoinitiator, the silane coupling agent and other auxiliaries under the condition of keeping out of the sun to obtain the photosensitive resin.

The embodiment also provides an application of the photosensitive resin in preparation of ceramics through photocuring 3D printing.

Example 2

This example provides a photosensitive resin, which comprises, by weight, 50 parts of vinyl polyacetylene, 20 parts of 1, 6-hexanediol diacrylate, 10 parts of trimethylol triacrylate, 20 parts of γ -methacryloxypropyl trimethoxysilane, and 3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.

Example 3

This example provides a photosensitive resin, which comprises, by weight, 50 parts of vinyl polyacetylene, 10 parts of 1, 6-hexanediol diacrylate, 10 parts of trimethylolpropane triacrylate, 30 parts of gamma-methacryloxypropyl trimethoxysilane, and 3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.

Example 4

This example provides a photosensitive resin, which comprises, by weight, 50 parts of vinyl polyacetylene, 5 parts of 1, 6-hexanediol diacrylate, 5 parts of trimethylolpropane triacrylate, 40 parts of gamma-methacryloxypropyl trimethoxysilane, and 3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.

Example 5

This example provides a photosensitive resin, which comprises, by weight, 67 parts of vinyl polyacetylene, 10 parts of 1, 6-hexanediol diacrylate, 10 parts of trimethylolpropane triacrylate, 30 parts of gamma-methacryloxypropyl trimethoxysilane, and 3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.

Comparative example

Preparing 5 parts of photosensitive resin with the following mixture ratio, wherein the photosensitive resin is respectively numbered as X1, X2, Y1, Y2, Y3 and Y4;

x1: according to the weight parts, 50 parts of vinyl poly-silicon acetylene, 50 parts of 1, 6-hexanediol diacrylate and 3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide are stirred for 6 hours under the condition of avoiding light and are uniformly mixed to obtain photosensitive resin X1;

x2: according to the weight parts, 50 parts of vinyl poly-silicon acetylene, 30 parts of 1, 6-hexanediol diacrylate, 20 parts of trihydroxymethyl triacrylate and 3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide are stirred for 6 hours under the condition of keeping out of the sun and are uniformly mixed to obtain photosensitive resin X2;

y1: according to the weight parts, 50 parts of vinyl poly-silicon acetylene, 20 parts of 1, 6-hexanediol diacrylate, 10 parts of trihydroxymethyl triacrylate, 20 parts of gamma-methacryloxypropyl trimethoxy silane and 3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide are stirred for 6 hours under the condition of keeping out of the sun and are uniformly mixed to obtain photosensitive resin Y1;

y2: according to the weight parts, 50 parts of vinyl poly-silicon acetylene, 10 parts of 1, 6-hexanediol diacrylate, 10 parts of trihydroxymethyl triacrylate, 30 parts of gamma-methacryloxypropyl trimethoxy silane and 3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide are stirred for 6 hours under the condition of keeping out of the sun and are uniformly mixed to obtain photosensitive resin Y2;

y3: according to the weight parts, 50 parts of vinyl poly-silicon acetylene, 5 parts of 1, 6-hexanediol diacrylate, 5 parts of trihydroxymethyl triacrylate, 40 parts of gamma-methacryloxypropyl trimethoxy silane and 3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide are stirred for 6 hours under the condition of keeping out of the sun and are uniformly mixed to obtain photosensitive resin Y3;

y4: according to the weight parts, 67 parts of vinyl poly-silicon acetylene, 10 parts of 1, 6-hexanediol diacrylate, 10 parts of trihydroxymethyl triacrylate, 30 parts of gamma-methacryloxypropyl trimethoxy silane and 3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide are stirred for 6 hours under the condition of keeping out of the sun and are uniformly mixed to obtain photosensitive resin Y4;

respectively coating the photosensitive resin on a glass slide, curing for 60s, carrying out TG test, measuring the density of 5 parts of photosensitive resin before and after curing by a pycnometer method to obtain the curing shrinkage rate of the photosensitive resin, and pyrolyzing at 1000 ℃ to obtain the ceramic yield, wherein the table is as follows:

as can be seen from the table, Y1, Y2, Y3, and Y4 showed smaller curing shrinkage and higher ceramic yield.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; all other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.