CN105278249B - A kind of stereolithography rapid prototyping cationic polysiloxane group photosensitive resin composition and its preparation method and application - Google Patents
A kind of stereolithography rapid prototyping cationic polysiloxane group photosensitive resin composition and its preparation method and application Download PDFInfo
- Publication number
- CN105278249B CN105278249B CN201410264129.3A CN201410264129A CN105278249B CN 105278249 B CN105278249 B CN 105278249B CN 201410264129 A CN201410264129 A CN 201410264129A CN 105278249 B CN105278249 B CN 105278249B
- Authority
- CN
- China
- Prior art keywords
- group
- polysiloxanes
- photosensitive resin
- rapid prototyping
- cationic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of photoetching Quick-forming cationic silicone base photosensitive resin compositions and its preparation method and application.It mainly includes the material component of following quality proportioning: polysiloxanes 10~85% of the both-end containing epoxy group；Polyepoxy polysiloxanes 3-21%；The diluent of based polysiloxane containing epoxy 10~60%；Cationic initiator 1.0~4.0% is mixed raw material by said ratio, and transparent liquid is heated under stirring to get stereolithography rapid prototyping polysiloxane group photosensitive resin.A kind of stereolithography rapid shaping polysiloxane group photosensitive resin of the present invention is after stereolithography, the characteristics of not only playing the rapid shaping of photosensitive resin, but also the characteristic of the high-low temperature resistant with polysiloxanes.The advantages that components shaped using the photosensitive resin have shrinking percentage small, and product accuracy is high, heat-resist.
Description
Technical field
The invention belongs to 3D printing Fast Forming Technique fields, and in particular to stereolithography rapid prototyping cation
Type polysiloxane group photosensitive resin composition and preparation method thereof.
Background technique
3D printing Fast Forming Technique is exactly computer design 3D figure, based on discrete-accumulation principle, is counted according to three-dimensional
Calculation machine mathematical model is suitable for personalization, small lot, complex-shaped, hollow etc. zero using the method formation of parts successively accumulated
Component manufacture, technique have unrivaled advantage with no model's point, in the small lot pilot stage of new product development.
Stereolithography rapid prototyping technology focuses on photo-curing material surface using the light of specific wavelength and intensity, be allowed to by
Point completes the drawing performance of a level by line to face consecutive solidification to line, and then lifting platform is in the mobile layer of vertical direction
The height of piece, another level of resolidification.It is layering in this way and constitutes a 3D solid.
Solidified using liquid photosensitive resin molded part with ultraviolet light as 3D printing of new generation, does not need valuableness
Laser system, therefore equipment price is cheap, and operation and maintenance cost are also very low, can be (minimum up to 50 in lower temperature
DEG C) under work；Moreover, also having, easy to operate, forming speed is fast, forming process is pollution-free, the precision of drip molding is high, can do
The advantages that public room environmental uses, therefore, application prospect is very good.
It is suitble to the photosensitive resin of stereolithography rapid prototyping to require the viscosity of glue system low, good fluidity, solidification rate
Fastly, cure shrinkage is low, and product is bent without sled, the requirement such as excellent heat resistance.Currently, domestic three-dimensional for high-precision, high-fire resistance
The preparation method report of photoetching fast shaping material is less.Specific to stereolithography rapid prototyping cationic polysiloxane group light
Quick resin and its preparation have not been reported.Polysiloxanes is with thermal stability is good, glass transition temperature is low, gas permeability is high, dielectricity is excellent
Many advantages, such as good and good biocompatibility and special surface property.
Summary of the invention
The purpose of the present invention is to provide a kind of high-precisions, high-fire resistance stereolithography rapid prototyping cationicPoly- silicon
Oxyalkyl photosensitive resin.The advantages of photosensitive glue using the preparation of this technology has system viscosity low, good fluidity, in ultraviolet light
Under irradiation, have glue curing rate fast, cure shrinkage is low, the product characteristic bent without sled, due to the main body of its polysiloxanes
Structure assigns the high-low temperature resistant characteristic that product is excellent after solidifying.The components shaped using the polysiloxane group photosensitive resin, tool
There is the advantages that precision is high, heat-resist, low temperature performance excellent, toughness enhances.
The object of the invention is also to provide the systems of stereolithography rapid prototyping cationic polysiloxane group photosensitive resin
Make method.
The present invention is achieved through the following technical solutions:
A kind of stereolithography rapid prototyping cationic photosensitive resin, the material component including following quality proportioning:
Polysiloxanes 10~85% of the both-end containing epoxy group；
Polyepoxy polysiloxanes 3-21%；
The diluent of based polysiloxane containing epoxy 10~60%；
Diluent 10-80%
Cationic initiator 1.0~4.0%.
Preferably, polysiloxanes of the both-end containing epoxy group is polysiloxane backbone, and epoxy group is contained at both ends
Polyorganosiloxane resin, molecular weight are made using the mixed with polymers of one or more kinds of molecular weight respectively between 2000-50000
With.
Preferably, the polyepoxy polysiloxanes is side group and (or) the polysiloxanes that end group contains epoxy group, is divided
Son amount is used using the mixed with polymers of one or more kinds of molecular weight respectively between 2000-50000.
Preferably, the diluent of based polysiloxane containing epoxy is side group and (or) the poly- silicon oxygen that end group contains epoxy group
Alkane, between molecular weight 300-2000；
It is highly preferred that the so-called diluent of based polysiloxane containing epoxy is two (epoxypropoxy) tetramethyl disiloxanes,
Two (epoxypropoxy) hexam ethylcyclotrisiloxanes, two (epoxypropoxy) octamethylcyclotetrasiloxanes, two (the third oxygen of epoxy third
Base) five siloxanes of decamethyl, four (epoxypropoxy) tetramethyl-ring tetrasiloxanes, four (epoxypropoxy) tetramethyl cyclotetrasiloxanes
Siloxanes, two (epoxy group hexyl propyl) tetramethyl disiloxanes, two (epoxy group hexyl propyl) hexam ethylcyclotrisiloxanes, two
(epoxy group hexyl propyl) octamethylcyclotetrasiloxane, two (epoxy group hexyl propyl) decamethyls, five siloxanes, four (the third oxygen of epoxy third
Base) tetramethyl-ring tetrasiloxane, four (epoxy group hexyl propyl) tetramethyl-ring tetrasiloxanes, two (glycidoxyethyl) tetramethyls
Disiloxane, two (glycidoxyethyl) hexam ethylcyclotrisiloxanes, two (glycidoxyethyl) octamethylcyclotetrasiloxanes, two (rings
The third oxygen of oxygen ethyl) five siloxanes of decamethyl, four (glycidoxyethyl) tetramethyl-ring tetrasiloxanes, four (glycidoxyethyls) four
Methyl cyclotetrasiloxane, two (epoxy group hexyl ethyl) tetramethyl disiloxanes, two (epoxy group hexyl ethyl) hexamethyls, three silicon
Oxygen alkane, two (epoxy group hexyl ethyl) octamethylcyclotetrasiloxanes, two (epoxy group hexyl ethyl) decamethyls, five siloxanes, four (rings
The third oxygen of oxygen ethyl) tetramethyl-ring tetrasiloxane, four (epoxy group hexyl ethyl) tetramethyl-ring tetrasiloxanes or the above substance it is mixed
Close object.
The diluent is the organic compound containing epoxy group, it is highly preferred that diluent is alkyl glycidyl ether, newly
Capric acid glycidol rouge, trihydroxymethylpropanyltri diglycidyl ether, toluene glycidol ether, castor oil polyglycidyl ether.
Preferably, so-called cationic initiator is the initiator for causing epoxy reaction.
It is highly preferred that so-called cationic initiators are the fluoro- 3- pyrroles's phenyl titanocenes of double 2,6- bis-, triaryl hexafluoro phosphorus
Sour sulfosalt, 4,4 '-dimethyl diphenyl iodine hexafluorophosphates, 10- (4- xenyl) -2-isopropylthioxanthone hexafluorophosphoric acid
Salt, -9 oxygen -9H- thioxanthones -10- sulphur hexafluorophosphate of the same 10- of polyalcohol [4- (2- carboxymethoxyl)-biphenyl] -2- isopropyl
Reaction product, bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of phenyl, 2,4,6- trimethylbenzoy-diphenies oxidation
Phosphine, 2,4,6- trimethylbenzoyl phosphinic acid ethyl esters or mixture two or more in them.Or in them two kinds or two kinds with
On mixture.
The present invention also provides a kind of preparation method of above-mentioned stereolithography rapid prototyping photosensitive resin, this method is by institute
It states material component to mix by the quality proportioning, mixed material is heated, stirring is until become transparent uniform liquid
Until, the product of acquisition is stereolithography rapid prototyping photosensitive resin.
Above-mentioned stereolithography rapid prototyping photosensitive resin is applied to stereolithography rapid prototyping skill as photo-curing material
Art field, curing light source preferably use wavelength for the ultraviolet light of 345nm~385nmnm.
Specific embodiment
Below with reference to embodiment, the present invention is done and is further described in detail, but implementation of the invention does not limit to
In this.
Embodiment 1
In 5000 milliliters of the glass there-necked flask equipped with blender and condenser pipe, the poly- silicon of both-end epoxypropoxy is added
Oxygen alkane (molecular weight 50000) 2210.0g, multi-epoxy the third oxygen propyl group polysiloxanes (molecular weight 2000) 546.0g, two (epoxies
Third oxygen propyl group) tetramethyl disiloxane 380.0g, neodecanoic acid glycidol rouge 450.g, triaryl hexafluorophosphoric acid sulfosalt
46.0g.Heating, until becoming transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin prepared for stirring.With
This photosensitive resin prepared can make 3D printing works using ultraviolet light 3D printer as material.
Embodiment 2
In 5000 milliliters of the glass there-necked flask equipped with blender and condenser pipe, the poly- silicon of both-end epoxypropoxy is added
Oxygen alkane (molecular weight 2000) 400.0g, multi-epoxy the third oxygen propyl group polysiloxanes (molecular weight 50000) 120.0g, four (epoxies
Third oxygen propyl group) tetramethyl-ring tetrasiloxane 2100.0g, toluene glycidol ether 560.0g, 10- (4- xenyl) -2- isopropyl
40.0 grams of thioxanthones hexafluorophosphate.Heating, stirring is until become transparent faint yellow uniform liquid, a kind of light as prepared
Quick resin.
Embodiment 3
In 5000 milliliters of the glass there-necked flask equipped with blender and condenser pipe, the poly- silicon of both-end epoxypropoxy is added
Oxygen alkane (molecular weight 20000) 1500.0g, multi-epoxy the third oxygen propyl group polysiloxanes (molecular weight 25000) 310.0g, two (rings
The third oxygen of oxygen ethyl) hexam ethylcyclotrisiloxane 930.0g, the fluoro- 3- of trihydroxymethylpropanyltri diglycidyl ether 450.0g, double 2,6- bis-
Pyrroles's phenyl titanocenes 60.0g.Heating, until becoming transparent faint yellow uniform liquid, the one kind as prepared is photosensitive for stirring
Resin.
Embodiment 4
In 5000 milliliters of the glass there-necked flask equipped with blender and condenser pipe, the poly- silicon of both-end epoxyhexyl propyl is added
Oxygen alkane (molecular weight 50000) 1275g, multi-epoxy hexyl propyl polysiloxanes (molecular weight 2000) 330.0g, two (epoxy oneself
Base propyl) hexam ethylcyclotrisiloxane 450.0g, castor oil polyglycidyl ether 1980.0g, 10- (4- xenyl) -2- isopropyl
Thioxanthones hexafluorophosphate 46g.Heating, until becoming transparent faint yellow uniform liquid, this liquid is to prepare for stirring
A kind of photosensitive resin.It uses this photosensitive resin of preparation as material, 3D printing can be made using ultraviolet light 3D printer and made
Product.
Embodiment 5
In 5000 milliliters of the glass there-necked flask equipped with blender and condenser pipe, the poly- silicon of both-end epoxyhexyl propyl is added
Oxygen alkane (molecular weight 2000) 1000g, multi-epoxy hexyl propyl polysiloxanes (molecular weight 50000) 300g, four (epoxyhexyls
Propyl) tetramethyl-ring tetrasiloxane 600g, neodecanoic acid glycidol rouge 1450.0g, 10- (4- xenyl) -2- isopropylthioxanthones
40 grams of ketone hexafluorophosphate.Heating, stirring is until become transparent faint yellow uniform liquid, a kind of photosensitive tree as prepared
Rouge.
Embodiment 6
In 5000 milliliters of the glass there-necked flask equipped with blender and condenser pipe, the poly- silicon of both-end epoxyhexyl propyl is added
Oxygen alkane (molecular weight 20000) 1500g, multi-epoxy hexyl propyl polysiloxanes (molecular weight 25000) 320g, two (epoxy oneself
Base ethyl) octamethylcyclotetrasiloxane 1050.0g, alkyl glycidyl ether 1050.0g, the same 10- of polyalcohol [4- (2- carboxylic methoxy
Base)-biphenyl] -2- isopropyl -9 56 grams of reaction product of oxygen -9H- thioxanthones -10- sulphur hexafluorophosphate.Heating, stirring are straight
Extremely become transparent faint yellow uniform liquid, a kind of photosensitive resin as prepared.
Embodiment 7
In 5000 milliliters of the glass there-necked flask equipped with blender and condenser pipe, the poly- silicon of both-end epoxyhexyl propyl is added
Oxygen alkane (molecular weight 20000) 1000g, oneself third oxygen propyl group polysiloxanes (molecular weight 25000) 210.0g of multi-epoxy, four (rings
Oxygroup hexyl ethyl) tetramethyl-ring tetrasiloxane 610g, trihydroxymethylpropanyltri diglycidyl ether 1420.0g, 2,4,6- front threes
Base benzoyl-diphenyl phosphine oxide 30.0g, 2,4,6- trimethylbenzoyl phosphinic acid ethyl ester 20.0g.Heating, stirring until
As transparent faint yellow uniform liquid, a kind of photosensitive resin for as preparing.
Embodiment 8
In 5000 milliliters of the glass there-necked flask equipped with blender and condenser pipe, the poly- silicon of both-end epoxyhexyl propyl is added
Oxygen alkane (molecular weight 20000) 1500g, oneself third oxygen propyl group polysiloxanes (molecular weight 25000) 360.0g of multi-epoxy, four (rings
Oxygroup hexyl propyl) tetramethyl-ring tetrasiloxane 450.0g, trihydroxy methyl ice alkane triglycidyl ether 450.0g, 2,4,6- front threes
Base benzoyl-diphenyl phosphine oxide 45.0g, 2,4,6- trimethylbenzoyl phosphinic acid ethyl ester 30.0g.Heating, stirring until
As transparent faint yellow uniform liquid, a kind of photosensitive resin for as preparing.
Claims (6)
1. a kind of stereolithography rapid prototyping cationic polysiloxane group photosensitive resin composition, it is characterised in that: including with
The material component of lower quality proportioning:
Polysiloxanes 10~85% of the both-end containing epoxy group, polysiloxanes of the both-end containing epoxy group are polysiloxanes master
The polyorganosiloxane resin of epoxy group is contained at chain, both ends, and molecular weight is between 2000-50000；
Polyepoxy polysiloxanes 3-21%, the polyepoxy polysiloxanes are that side group and/or end group contain epoxy group
Polysiloxanes, molecular weight is between 2000-50000；
The diluent of based polysiloxane containing epoxy 10~60%, the diluent of based polysiloxane containing epoxy are side group and/or end group
Polysiloxanes containing epoxy group, between molecular weight 300-2000；
Cationic initiator 1.0~4.0%.
2. a kind of stereolithography rapid prototyping cationic polysiloxane group lightsensitive resin composition according to claim 1
Object, it is characterised in that: the structure of the epoxy group be epoxypropoxy, glycidoxyethyl, epoxy cyclohexylethyl,
Expoxycyclohexyl propyl.
3. any a kind of photosensitive tree of stereolithography rapid prototyping cationic polysiloxane group in -2 according to claim 1
Oil/fat composition, it is characterised in that: the structure of the polysiloxanes, can also be by methyl, phenyl and trifluoro other than epoxy group
Propyl composition.
4. a kind of stereolithography rapid prototyping cationic polysiloxane group lightsensitive resin composition according to claim 1
Object, it is characterised in that: the cationic initiators are double 2, the fluoro- 3- pyrroles's phenyl titanocenes of 6- bis-, triaryl hexafluorophosphoric acid
Sulfosalt, 4,4 '-dimethyl diphenyl iodine hexafluorophosphates, 10- (4- xenyl) -2-isopropylthioxanthone hexafluorophosphoric acid
- 9 oxygen -9H- thioxanthones -10- sulphur hexafluorophosphate of the same 10- of salt, polyalcohol [4- (2- carboxymethoxyl)-biphenyl] -2- isopropyl
Reaction product, phenyl bis- (2,4,6- trimethylbenzoyl) phosphine oxides, 2,4,6- trimethylbenzoy-diphenies oxidation
Phosphine, 2,4,6- trimethylbenzoyl phosphinic acid ethyl esters or mixture two or more in them.
5. a kind of photosensitive tree of stereolithography rapid prototyping cationic polysiloxane group according to any one of claims 1-4
The preparation method of oil/fat composition, it is characterised in that: the material component is mixed by the quality proportioning, stirs lower heating,
Until becoming transparent uniform liquid.
6. a kind of stereolithography rapid prototyping cationic polysiloxane group photosensitive resin group as claimed in any one of claims 1 to 5
Close the application of object, it is characterised in that: curing light source uses wavelength for the ultraviolet light of 355nm~385nmnm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410264129.3A CN105278249B (en) | 2014-05-30 | 2014-05-30 | A kind of stereolithography rapid prototyping cationic polysiloxane group photosensitive resin composition and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410264129.3A CN105278249B (en) | 2014-05-30 | 2014-05-30 | A kind of stereolithography rapid prototyping cationic polysiloxane group photosensitive resin composition and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105278249A CN105278249A (en) | 2016-01-27 |
| CN105278249B true CN105278249B (en) | 2019-10-25 |
Family
ID=55147512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410264129.3A Expired - Fee Related CN105278249B (en) | 2014-05-30 | 2014-05-30 | A kind of stereolithography rapid prototyping cationic polysiloxane group photosensitive resin composition and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105278249B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102518495B1 (en) * | 2017-02-23 | 2023-04-05 | 동우 화인켐 주식회사 | A method of silicon compound, colored photosensitive resin composition, color filter and image display device comprising using the same |
| CN107357136A (en) * | 2017-08-23 | 2017-11-17 | 广西众昌树脂有限公司 | Photosensitive liquid resin |
| JP6904245B2 (en) * | 2017-12-27 | 2021-07-14 | 信越化学工業株式会社 | Photosensitive resin composition, pattern forming method, and manufacturing method of optical semiconductor device |
| CN111018764A (en) * | 2018-10-09 | 2020-04-17 | 常州强力先端电子材料有限公司 | Triphenylsulfonium salt compound and application thereof |
| EP3865473A4 (en) * | 2018-10-09 | 2022-11-23 | Changzhou Tronly Advanced Electronic Materials Co., Ltd. | Triphenylphosphonium salt compound, and uses thereof |
| CN113754441B (en) * | 2021-03-15 | 2023-02-17 | 山东理工大学 | Photosensitive resin and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007093801A (en) * | 2005-09-27 | 2007-04-12 | Fujifilm Corp | Photosensitive film, permanent pattern forming method and pattern |
| US20090004579A1 (en) * | 2007-06-27 | 2009-01-01 | Dsm Ip Assets B.V. | Clear and colorless three-dimensional articles made via stereolithography and method of making said articles |
| CN101848915B (en) * | 2007-11-07 | 2013-10-09 | 昭和电工株式会社 | Epoxy group-containing organosiloxane compound, curable composition for transfer material, and fine pattern forming method using the composition |
| TW201319170A (en) * | 2011-05-25 | 2013-05-16 | Dow Corning | Epoxy-functional radiation-curable composition containing an epoxy-functional siloxane oligomer for enhanced film retention and adhesion during solvent development |
-
2014
- 2014-05-30 CN CN201410264129.3A patent/CN105278249B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105278249A (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105278249B (en) | A kind of stereolithography rapid prototyping cationic polysiloxane group photosensitive resin composition and its preparation method and application | |
| CN100554315C (en) | Organopolysiloxane and contain the solidification compound of organopolysiloxane | |
| CN104755526B (en) | Epoxy curing agent | |
| CN104570603B (en) | A kind of ultraviolet light solidifies the preparation method and application of 3D printing photosensitive resin | |
| CN103937257B (en) | Organic silicone thixotropic agent and thixotropy addition type liquid silicone rubber | |
| CN108659471A (en) | A kind of light-cured resin and preparation method thereof that polyfunctionality POSS is modified | |
| CN104250422A (en) | Photosensitive resin used in 3D printing, and its preparation method | |
| CN108410162A (en) | Photocuring 3D printing material and its preparation method and application | |
| CN103755889A (en) | Light-emitting high precision three-dimensionally moulded photosensitive resin composition | |
| CN104558616B (en) | Silicone resin containing aryl and epoxy group, preparation method for silicone resin and epoxy resin adhesive containing silicone resin | |
| CN108192100A (en) | A kind of photo-curable silicone resin and preparation method thereof, photosensitive resin and application | |
| CN106928893A (en) | A kind of preparation method of cation type ultraviolet photo and hot dual deep cure adhesive | |
| CN105969301B (en) | A kind of organic silica gel for high-power LED encapsulation and preparation method thereof and application method | |
| CN107300828B (en) | Photosensitive resin for 3D printing | |
| CN105199058A (en) | 3D printing light-cured resin composition and modeling matter prepared from same | |
| CN104293116B (en) | A kind of photocuring 3 D-printing material and preparation method and application | |
| CN103246164A (en) | Photosensitive resin for stereo lithography forming and preparation method thereof | |
| CN106118584A (en) | Cold curing high transmission rate organosilicon adhesive and preparation method thereof | |
| CN107987474A (en) | A kind of light-cured resin and preparation method for rapid shaping | |
| CN107325770A (en) | A kind of 3D printing powder binding agent and its application | |
| CN103476764A (en) | Process for preparing episulfide compounds | |
| CN103897404A (en) | Application of modified polysiloxane in preparation of thixotropic addition type liquid silicone rubber | |
| CN105754052A (en) | Photocuring resin material for 3D printing as well as preparation method and application thereof | |
| CN103059268B (en) | A kind of electrical apparatus insulation part epoxide resin material | |
| CN104031392B (en) | A kind of add-on type silica gel and its production and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191025 Termination date: 20210530 |