Search

CN-122011288-A - Photosensitive resin composition and application thereof

CN122011288ACN 122011288 ACN122011288 ACN 122011288ACN-122011288-A

Abstract

The invention discloses a photosensitive resin composition, which comprises 20 to 60 parts by mass of olefinic compound monomers, 20 to 60 parts by mass of acrylic ester prepolymers and 1 to 5 parts by mass of photopolymerization initiator, wherein the acrylic ester prepolymers comprise rigid prepolymers with the functionality of 3 to 5 and flexible prepolymers with the functionality of 2, the rigid prepolymers with the functionality of 3 to 5 and the flexible prepolymers with the functionality of 2 comprise one or more combinations of epoxy acrylate, polyurethane acrylate and polyester acrylate, the mass ratio of the rigid prepolymers with the functionality of 3 to 5 to the flexible prepolymers with the functionality of 2 is 0:1 to 0.8:1, and the photopolymerization initiator comprises oxime ester compounds and ketene compounds, so that the photosensitive resin composition with wide spectrum response, high curing speed, low curing shrinkage and improved curing depth regulation precision, elongation at break and tensile strength is finally obtained.

Inventors

  • ZHANG CHENG
  • Hong Jinlang

Assignees

  • 武汉柔显科技股份有限公司
  • 柔显(仙桃)光电半导体材料有限公司
  • 湖北鼎龙控股股份有限公司

Dates

Publication Date
20260512
Application Date
20260227

Claims (10)

  1. 1. A photosensitive resin composition characterized by comprising the following components: 20 to 60 parts by mass of an olefinic compound monomer (A); 20 to 60 parts by mass of an acrylic prepolymer (B), and 1 To 5 parts by mass of a photopolymerization initiator (C); The acrylate prepolymer comprises a rigid prepolymer with the functionality of 3 to 5 and a flexible prepolymer with the functionality of 2, wherein the rigid prepolymer with the functionality of 3 to 5 and the flexible prepolymer with the functionality of 2 comprise one or more of Epoxy Acrylate (EA), polyurethane acrylate (PUA) and polyester acrylate (PEA) in combination, and the mass ratio of the rigid prepolymer with the functionality of 3 to 5 and the flexible prepolymer with the functionality of 2 is 0:1 to 0.8:1; the photopolymerization initiator (C) comprises an oxime ester compound represented by the following formula (C1) and an ketene compound represented by the following formula (C2): (C1) Wherein, R 1 is C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 –C 12 alkynyl, C 3 -C 12 cycloalkyl, C 3 -C 12 saturated heterocyclic group, aryl or heteroaryl, R 2 is hydrogen atom, C 1 -C 12 alkyl or C 3 -C 12 cycloalkyl, R 3 is hydrogen atom, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, alkyl substituted by nitrogen-containing functional group, R 4 is C 1 -C 12 alkyl; (C2) Wherein R 5 is a hydrogen atom, C 1 -C 12 alkyl, R 6 is a connecting bond, C 1 -C 10 alkylene, -CH 2 -N(-CH 2 -CH=CH 2 )-,R 7 is a connecting bond and carbonyl.
  2. 2. The photosensitive resin composition according to claim 1, wherein the mass ratio of the oxime ester compound to the ketene compound is 0.2:1 to 5:1.
  3. 3. The photosensitive resin composition of claim 1, wherein R 1 is C 3 -C 12 cycloalkyl, C 3 -C 12 saturated heterocyclyl, aryl or heteroaryl, R 2 is C 1 -C 12 alkyl, R 3 is C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, alkyl substituted with nitrogen-containing functional groups, R 4 is C 1 -C 8 alkyl, R 5 is a hydrogen atom, R 6 is C 1 -C 10 alkylene, -CH 2 -N(-CH 2 -CH=CH 2 )-,R 7 is carbonyl; Preferred R 1 is aryl, R 2 is C 1 -C 5 alkyl, R 3 is C 3 -C 12 cycloalkyl, alkyl substituted with nitrogen containing functionality, and R 4 is C 1 -C 5 alkyl.
  4. 4. The photosensitive resin composition according to claim 1, wherein the mass ratio of the rigid prepolymer having a functionality of 3 to 5 to the flexible prepolymer having a functionality of 2 is 0.1:1 to 0.8:1, and the mass ratio of the oxime ester compound to the ketene compound is 0.5:1 to 3:1.
  5. 5. The photosensitive resin composition according to claim 1, wherein the number average molecular weight of the acrylic prepolymer is 400 to 2000.
  6. 6. The photosensitive resin composition according to claim 1, wherein the olefinic compound monomer comprises one or a combination of an ester of an aliphatic polyhydroxy compound with an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound with an unsaturated carboxylic acid; The ester formed by the aliphatic polyhydroxy compound and the unsaturated carboxylic acid comprises one or a combination of more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate; the esters of the aromatic polyhydroxy compound and the unsaturated carboxylic acid comprise one or more of hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate and pyrogallol triacrylate.
  7. 7. The photosensitive resin composition according to claim 1, wherein the number of ethylenic unsaturated bonds in the ethylenic compound monomer is 1 to 5, preferably the number of ethylenic unsaturated bonds is 3 to 5.
  8. 8. The photosensitive resin composition according to claim 1, further comprising 20 to 50 parts by mass of a reactive diluent (D), 0.01 to 1.0 parts by mass of an antifoaming agent (E), 0.01 to 1.0 parts by mass of a leveling agent (F), and 0.01 to 1.0 parts by mass of an antioxidant (G).
  9. 9. The photosensitive resin composition according to claim 8, wherein said reactive diluent (D) comprises one or more combinations of glycerol triacrylate, pentaerythritol tetraacrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, isobornyl acrylate and cyclic trimethylolpropane methylacrylate; the defoaming agent (E) comprises one or a combination of more of organic silicon defoaming agents, mineral oil defoaming agents, polyether defoaming agents and fatty alcohol defoaming agents; The leveling agent (F) comprises one or a combination of a plurality of acrylic leveling agents, organic silicon leveling agents and fluorocarbon leveling agents; The antioxidant (G) comprises one or more of pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, phenyl tri (2, 4-di-tert-butyl) phosphite, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 2, 6-di-tert-butyl-4-methylphenol.
  10. 10. Use of the photosensitive resin composition according to any one of claims 1 to 9 in the field of photocuring.

Description

Photosensitive resin composition and application thereof Technical Field The present invention relates to a photosensitive resin composition, and more particularly, to a photocurable 3D printing resin composition having broad spectral response characteristics and low curing shrinkage. Background The photo-curing three-dimensional printing technology, in particular to the printing technology based on Stereo Lithography (SLA), digital Light Processing (DLP) and Liquid Crystal Display (LCD), has great potential in the fields of precision manufacturing, biological medical treatment, cultural originality and the like due to high precision and forming efficiency. The photocurable resin composition used in this technique generally contains an unsaturated monomer, a photoinitiator, and an unsaturated prepolymer. Under illumination, the initiator initiates the monomer and the prepolymer to generate polymerization crosslinking reaction, thereby realizing layer-by-layer curing molding. However, the existing photo-curable resin composition still has two significant technical difficulties in practical application, namely, firstly, the curing volume shrinkage rate of the existing resin system is high. Typical shrinkage is between 5% and 10% during photopolymerization. This defect causes a series of interlocking problems such as deterioration of dimensional accuracy, deviation of the actual dimensions of the molded part from the design values due to shrinkage, warpage, delamination and even cracking, and collapse when printing large-sized overhang structures due to shrinkage which may weaken the bonding force between the support structure and the part body. Secondly, the spectral response range of the existing photoinitiator system is not sufficiently matched with a practical light source. An ideal photoinitiator should possess broad spectrum absorption characteristics that are highly compatible with common uv-visible light sources (e.g., 365nm, 385nm, 405nm LEDs). However, conventional initiators such as TPO (absorption peak about 380 nm) tend to have a narrow absorption range and suffer from "spectral mismatch". This results in a large amount of light source energy not being absorbed efficiently, resulting in energy waste, and having to extend exposure time or increase light intensity to achieve sufficient curing depth, affecting printing speed, and the absorption mismatch may result in difficulty in precise control of light penetration depth in the resin, causing excessive curing (over-curing) of the sidewalls or insufficient interlayer bonding force (under-curing), and difficulty in meeting the stringent wavelength matching requirements of conventional initiator systems in applications requiring submicron precision or use of special wavelength light sources. In order to cope with the problem of curing shrinkage, various proposals have been made, such as adding an inorganic filler, using a cationic polymerization system or developing a low shrinkage monomer, but it is often difficult to balance between improvement in shrinkage, maintenance of mechanical properties and suitability for printing process. Meanwhile, in order to solve the spectrum matching problem, researchers develop novel initiators such as oxime esters, specific ketene and the like, and although the initiators are improved in absorption efficiency or wavelength range, the initiation efficiency of the initiators under the extremely low shrinkage requirement and the comprehensive performance of the initiators in the aspects of wide-spectrum response and high-precision curing are realized in cooperation with a resin system, and systematic optimization and promotion are still required. Disclosure of Invention The present invention addresses the problems of the prior art by providing in a first aspect a photosensitive resin composition comprising the following components: 20 to 60 parts by mass of an olefinic compound monomer (A); 20 to 60 parts by mass of an acrylic prepolymer (B), and 1 To 5 parts by mass of a photopolymerization initiator (C); The acrylate prepolymer comprises a rigid prepolymer with the functionality of 3 to 5 and a flexible prepolymer with the functionality of 2, wherein the rigid prepolymer with the functionality of 3 to 5 and the flexible prepolymer with the functionality of 2 comprise one or more of Epoxy Acrylate (EA), polyurethane acrylate (PUA) and polyester acrylate (PEA) in combination, and the mass ratio of the rigid prepolymer with the functionality of 3 to 5 and the flexible prepolymer with the functionality of 2 is 0:1 to 0.8:1; the photopolymerization initiator (C) comprises an oxime ester compound represented by the following formula (C1) and an ketene compound represented by the following formula (C2): (C1) Wherein, R 1 is C 1-C12 alkyl, C 2-C12 alkenyl, C 2–C12 alkynyl, C 3-C12 cycloalkyl, C 3-C12 saturated heterocyclic group, aryl or heteroaryl, R 2 is hydrogen atom, C 1-C12 alkyl or C 3-C12 cycloalkyl, R 3 is hydrogen a