CN108485183A - One kind can be used for transparent photosensitive resin of clinical medical high tenacity and preparation method thereof - Google Patents
One kind can be used for transparent photosensitive resin of clinical medical high tenacity and preparation method thereof Download PDFInfo
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- CN108485183A CN108485183A CN201810140501.8A CN201810140501A CN108485183A CN 108485183 A CN108485183 A CN 108485183A CN 201810140501 A CN201810140501 A CN 201810140501A CN 108485183 A CN108485183 A CN 108485183A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses one kind can be used for transparent photosensitive resin of clinical medical high tenacity and preparation method thereof, counts in parts by weight, including following components：10 50 parts of hydrogenated bisphenol A epoxy resin, 10 60 parts of cycloaliphatic epoxy resin, 10 50 parts of bisphenol A epoxide resin, 1 10 parts of cation light initiator, 5 20 parts of polyalcohol.Resin transparent degree height, moderate viscosity, the low smell of the present invention, forming part high tenacity, high-precision are suitable for clinical medicine, have no toxic and side effect to human body, non-stimulated, rejection, organism good compatibility.
Description
Technical field
The invention belongs to medical composite material technical fields, are related to RP technique field, and in particular to a kind of
It can be used for transparent photosensitive resin of clinical medical high tenacity and preparation method thereof.
Background technology
Rapid prototyping manufacturing (RPM：Rapid Prototyping Manufacturing) technology, it is called rapid shaping skill
Art, abbreviation RP technologies can rapidly and accurately produce the part according to the three-dimensional modeling data of part.It is in 20 generation
Record emerging technology that the eighties, Later development got up, it is considered to be nearly two manufacturing technology fields during the last ten years it is primary great prominent
It is broken, it is one of the hot spot of currently advanced manufacturing field research.Introduction To Stereolithography (SLA) is that first input business is answered
RPM technologies, and technology the most ripe, are what the principle based on liquid photocurable resin photopolymerization worked, specific work
It is as follows to make principle：Using light-cured resin as raw material, UV laser beam is respectively layered section under the control of the computer, with predetermined part
Profile is track, to liquid resin point by point scanning, so that the thin resin layer in scanned area is generated polymerisation to line to face by putting,
To form a thin layer section of part.Molding start when, workbench the next determination of liquid level depth, after focusing
Hot spot is cured on liquid level by computer instruction point by point scanning.When one layer of solidification finishes, self-powered platform moves a synusia thickness
The distance of degree covers one layer of new liquid fat to carry out new one layer of scanning solidification again in the resin surface being originally cured.Newly
Cured one layer is firmly bonded in preceding layer, so repeats to finish until entire part raw basin, forms a three-dimensional
Model, the precision of the model processed is high, surface quality is good, utilization rate of raw materials nearly 100%, and it is special can to manufacture shape
Part complicated, appearance is especially fine.
In laser formation SLA resin industries, most of photosensitive resin is all white, and the photosensitive resin of water white transparency
It is fewer.At abroad, developed country maintains the leading position to the research and development of SLA photosensitive resins, transparent SLA photosensitive resins are always
By a small number of 3D printing material producer institutes ridges such as 3D Systems companies of the U.S., Huntsman companies, German EOS Corp.
It is disconnected.Since the price of external transparent photosensitive resin is somewhat expensive, the import shipping period is long and domestic equipment quotient and external raw material quotient
Mutual cooperation response, the reasons such as poor in timeliness, therefore there is an urgent need for develop the transparent photosensitive tree with comprehensive performances such as high tenacity
Fat.
China has begun to study photosensitive resin in the 1970s, in recent years many universities and R＆D institution
Certain progress is also being obtained to the research of SLA photosensitive resins.Wei Yanyan such as Qingdao University of Science and Technology et al. proposed " one in 2015
Kind high tenacity 3D printing photosensitive resin and preparation method thereof ", the number of applying for a patent are 201410620653.X.Section in the Fujian of Qingdao
The Lin Runxiong et al. of great achievement Chemical Industry Science Co., Ltd proposes a kind of " preparation side of ultraviolet light solidification 3D printing photosensitive resin
Method and application ", the number of applying for a patent are 2013104981948.Yingying Zhang of Shaanxi Heng Tong intelligence machine Co., Ltd et al. proposes
" a kind of high temperature resistant high tenacity light-cured resin for photocuring 3D printing ", the number of applying for a patent are 2016108544031.But
It is in the patent of these papers delivered and application, to be not involved with completely for can be used in clinical medical high tenacity
Transparent photosensitive resin.Traditional medical model production method time is long, and handling process is easily damaged, can be with using 3D printing technique
Production Time is greatly reduced, reduces the risk for carrying damage, and can at any time be made according to various required shapes
Make, histoorgan substitute is made, face modifies and greatly facilitates effect with the application of the medical domains such as beauty.Cause
This needs the flexibility for further increasing transparent photosensitive resin to improve 3D printing technique in clinical medical application level.
In addition, in view of medical instrument for having harsh quality requirement, above-mentioned and existing many 3D for the material of life entity
Printed material does not meet the stringent standard of medical instrument substantially.
Invention content
In view of the problems of the existing technology, the present invention provides one kind, to can be used for clinical medical high tenacity transparent photosensitive
Resin and preparation method thereof.
The present invention uses following technical scheme：
One kind can be used for the transparent photosensitive resin of clinical medical high tenacity, counts in parts by weight, including following components：
In some embodiments, hydrogenated bisphenol A epoxy resin is 10-20 parts, and cycloaliphatic epoxy resin is 10-30 parts, double
Phenol A epoxy resin is 10-20 parts, and cation light initiator is 1-5 parts, and polyalcohol is 5-10 parts.In some embodiments, it hydrogenates
Bisphenol A epoxide resin is 30-50 parts, and cycloaliphatic epoxy resin is 30-60 parts, and bisphenol A epoxide resin is 30-50 parts, cation
Photoinitiator is 5-10 parts, and polyalcohol is 10-20 parts.
It is further preferred that the transparent photosensitive resin of high tenacity, counts, is made of following components in parts by weight：Hydrogenation
10-50 parts of bisphenol A epoxide resin, 10-60 parts of cycloaliphatic epoxy resin, 10-50 parts of bisphenol A epoxide resin, cationic photopolymerization cause
1-10 parts of agent, 5-20 parts of polyalcohol.
Further, the hydrogenated bisphenol A epoxy resin is selected to the type of Jia Dida Chemical Co., Ltd.s of Shenzhen offer
Model EP-4080E, the Yantai Ao Lifu chemical industry that number Epalloy 5000, Ai Dike (Shanghai) trade Co., Ltd provide are limited
It is one or more in model AL-3040 or HAL-3040 that company provides.
Further, the cycloaliphatic epoxy resin is selected to the model of Daicel (China) Investment Co., Ltd offer
Celoxide 2021P, the model TTA21 (JR-HS-21) of Jiangsu Tai Teer new materials Science and Technology Ltd. offer, Hensel advanced in yearsization
The model of model C Y179, Hensel Chemical trade (Shanghai) Co., Ltd. offer advanced in years that the easy (Shanghai) Co., Ltd. of industry and trade provides
It is one or more in CY184.
Further, the bisphenol A epoxide resin is selected to the model Epon that Dutch Hexion Chemical Co., Ltd. provides
828, the model E- of Dow Chemical (China) Company Limited provides model DER 331, the offer of Jinan Yi Sheng resins Co., Ltd
It is one or more in the model E-44 (6101) that 51 (618), Jinan Yi Sheng resins Co., Ltd provide.
Further, the cation light initiator is selected to the model that the strange titanizing Science and Technology Ltd. in Shanghai provides1190, the model Easepi 6976 of the easy Chemical Co., Ltd.'s offer of upper sea light, BASF China
One kind in the model Uyracure-160 that the model Irgacure 250 of offer, You Yang Science and Technology Ltd.s of Shenzhen provide or
It is a variety of.
Further, the polyalcohol is selected to the model of the offer of SANYO GS chemical conversion (Shanghai) trade Co., Ltd
Sunnix GP-400, the model Voranol of Dow Chemical's offer, win wound Degussa (China) investment have
It is one or more in the model Oxyester that limit company provides.
It is further preferred that the hydrogenated bisphenol A epoxy resin selects Jia Dida Chemical Co., Ltd.s of Shenzhen to provide
Model Epalloy 5000；The cycloaliphatic epoxy resin selects the model that Daicel (China) Investment Co., Ltd provides
Celoxide 2021P；The bisphenol A epoxide resin select the model Epon 828 that Dutch Hexion Chemical Co., Ltd. provides or
The model DER 331 that Dow Chemical (China) Company Limited provides；The cation light initiator selects the strange titanizing subject in Shanghai
The model that skill Co., Ltd provides1190；The polyalcohol selects chemical conversion (Shanghai) trade Co., Ltd of Sanyo to carry
The model Sunnix GP-400 of confession.
The hydrogenated bisphenol A epoxy resin for the model Epalloy 5000 that Jia Dida Chemical Co., Ltd.s of Shenzhen provide：
Viscosity (25 DEG C of cps@)：1300-2500；Epoxide equivalent (g/eq.)：210-230；Hydrolyzable chlorine content (max, %)：0.2；Color
Damp (max)：100(APHA)；Purposes：Good compared with standard bisphenol a resin uv-resistance, viscosity is low, can be used for substituting polyurethane coating and uses
In weatherability coating, there is excellent adhesive force to metal.
The alicyclic epoxy tree for the model Celoxide 2021P that Japanese Daicel (China) Investment Co., Ltd provides
Fat is a kind of Halogen cycloaliphatic epoxy resin of low-viscosity, has excellent UV resistant, radiation resistance, and water-fast well
Property, alkali resistance：Color and luster (APHA)：80MAX；Refractive index (n20/D)：1.498(lit.)；Flash-point：118℃；Molecular weight：252；It is viscous
It spends (cps)：200-350；Functional group's number：2；Density (g/cc)：1.2；Epoxide equivalent：128-140；Acid value：5MAX；CAS：
2386-87-0。
The bisphenol A epoxide resin for the model Epon 828 that Dutch Hexion Chemical Co., Ltd. provides is clearly bifunctional
Undiluted bisphenol-A/epichlorohydrin derived the liquid epoxies of group：Epoxide number (mmol/kg, test method：SMS 2026)：
5260-5420；Viscosity (25 DEG C, Pas, test method：ASTM D445)：12-14；Color (Pt/Co scale, test side
Method：ASTM D1209)：<100；Refractive index (25 DEG C)：1.573.
The bisphenol A epoxide resin for the model DER 331 that DOW Chemical Co., Ltd provides：Solid content：99%；Viscosity
(cps@25℃)：11000-14000；Epoxide equivalent (g/eq.)：182-192.
The model that the strange titanizing Science and Technology Ltd. in Shanghai provides1190 cation light initiator：
CAS：74227-35-3；Boiling point：232℃；Viscosity (cps)：100.
The polyalcohol that Sanyo is melted into the model Sunnix GP-400 that (Shanghai) trade Co., Ltd provides is polyether polyols
Alcohol is further three alcohol type, PH=6.5 (14% water/aqueous isopropanol), solidification point：- 31 DEG C (- 23.8 °F), flash-point：218℃
(424.4 °F), proportion：1.06 (20 DEG C), viscosity (25 DEG C, mPas) 365, hydroxyl value：400.
A kind of preparation method can be used for the transparent photosensitive resin of clinical medical high tenacity, includes the following steps：By each original
Expect that component is matched according to parts by weight to mix, then be stirred 60~150 minutes at 20 DEG C~70 DEG C of temperature, is obtained transparent equal
Even liquid.
The transparent photosensitive resin of high tenacity is 500- with the viscosity that NOJ-79 types rotational viscometer is measured at 25 DEG C
1000cps, preferably 700-800cps.
As a whole, each component is mutually coordinated, and suitable viscosity, good machinery may be implemented for the formula of the present invention
Performance, chemical-resistance have preferable base material adhesive force, weatherability and heat resistance, improve flexibility, the reactivity of base material
And impact resistance, while weatherability is promoted, there is compatibility well between each component, be the transparent photosensitive resin of high tenacity.
The transparent photosensitive transparent resin of high tenacity, moderate viscosity, the low smell of the present invention, the resin pass through stereolithography
Afterwards, forming part high tenacity, surface drying it is good, high-precision.Low warpage, high-precision can directly be produced using the resin for preparing of the present invention
The part of degree, arbitrarily complicated shape.There is transparent, moderate viscosity, low smell, forming part high-ductility in view of prepared resin
Property, surface drying be good, high-precision feature, is suitable as the transparent photosensitive resin of high tenacity needed for clinical medicine, or as doctor
Treat instrument, surgical guide (such as：Joint type guide plate, backbone guide plate, mouth cavity planting body guide plate, inside tumor irradiation source particle are planted
Guide-localization guide plate entered etc.), 3D printing implantation material, hearing aid, such as artificial limb, facing, blood vessel, cartilage, tracheae, bone (example
Such as cervical vertebra, cranium) or other artificial tissues, organ.
Beneficial effects of the present invention：
(1) resin of the invention is suitable in clinical medicine domain, as medical instrument, has no toxic and side effect to human body,
Non-stimulated, rejection, organism good compatibility；
(2) resin transparent degree height of the invention, moderate viscosity, low smell, forming part high tenacity, high-precision；
(3) preparation method of the invention is simple, and step is easy, and production efficiency is high, and security risk is few, is suitable for extensive steady
Determine metaplasia production.
Specific implementation mode
In order to preferably explain the present invention, it is described further in conjunction with following specific examples, but the present invention is unlimited
In specific embodiment.
Table 1：Component, each component dosage and the model of embodiment 1-5.
Embodiment 1-5 in table 1 is each added to the special capacity equipped with blender and condenser pipe by component and dosage
In 200 milliliters of stainless steel cauldrons, to be heated to 60 DEG C, stirs 120 minutes, make the liquid of clear homogeneous, gained
Liquid is the transparent photosensitive resin of high tenacity.The resin of embodiment 1 is measured at 25 DEG C using NOJ-79 types rotational viscometer
Viscosity 878cps, the viscosity 843cps of the resin of embodiment 2, the viscosity 821cps of the resin of embodiment 3, the tree of embodiment 4
The viscosity 802cps of fat, the viscosity 786cps of the resin of embodiment 5.
Join the SLA-600 type ultraviolet laser solidification rapid forming equipment systems of safe three-dimensional Science and Technology Ltd.'s manufacture using Shanghai
Make some test blocks, cures 90 minutes in 480W ultra-violet curing casees, data measured is listed in table 2.The fracture of embodiment 1-5 extends
Rate and impact strength are higher, show that resin of the present invention has good toughness.
Table 2：The test result of embodiment 1-5.
The group of comparative example 1 is divided into：What hydrogenated bisphenol A epoxy resin (10g) was selected is that Shanghai complexing Chemical Co., Ltd. carries
The model ST-3000 of confession, what cycloaliphatic epoxy resin (30g) was selected is the model that Wuhan Senmao Fine Chemical Co., Ltd. provides
CER-170, what bisphenol A type epoxy resin (50g) was selected is the model E-44 that Yueyang petrochemical industry Co., Ltd of Ba Ling Huaxing provides, sun
What ionic photoinitiator (5g) was selected is the model UVI6976 that good inhibition and generation (China) Co., Ltd of Germany provides, polyalcohol
What (5g) was selected is the model PPG400 that 100,000 Chemical Co., Ltd. of Shandong provides, the use of comparative example 1 and each component of embodiment 1
Measure identical, but producer and model are all different.
The group of comparative example 2 is divided into：What hydrogenated bisphenol A epoxy resin (30g) was selected is that Shanghai complexing Chemical Co., Ltd. carries
The model ST-3000 of confession, what cycloaliphatic epoxy resin (30g) was selected is the model that Wuhan Senmao Fine Chemical Co., Ltd. provides
CER-170, what bisphenol A type epoxy resin (15g) was selected is the model E-44 that Yueyang petrochemical industry Co., Ltd of Ba Ling Huaxing provides, sun
What ionic photoinitiator (5g) was selected is the model UVI6976 that good inhibition and generation (China) Co., Ltd of Germany provides, polyalcohol
What (20g) was selected is the model PPG400 that 100,000 Chemical Co., Ltd. of Shandong provides, comparative example 2 and each component of embodiment 5
Dosage is identical, but producer and model are all different.
Comparative example 3 is identical as the dosage of each component of embodiment 1, but the hydrogenated bisphenol A epoxy resin of comparative example 3 is selected
Be Shanghai complexing Chemical Co., Ltd. provide model ST-3000, the producer of other components and model are all identical.
Comparative example 4 is identical as the dosage of each component of embodiment 5, but what the cycloaliphatic epoxy resin of comparative example 4 was selected
It is the model C ER-170 that Wuhan Senmao Fine Chemical Co., Ltd. provides, the producer of other components and model are all identical.
Comparative example 5 is identical as the dosage of each component of embodiment 3, but what the bisphenol A type epoxy resin of comparative example 5 was selected
It is the model E-44 that Yueyang petrochemical industry Co., Ltd of Ba Ling Huaxing provides, the producer of other components and model are all identical.
Comparative example 6 is identical as the dosage of each component of embodiment 3, but what the cation light initiator of comparative example 6 was selected
It is the model UVI6976 that good inhibition and generation (China) Co., Ltd of Germany provides, the producer of other components and model are all identical.
The producer of each component of comparative example 7 and embodiment 1-5 and model are all identical, but match different, the group of comparative example 7
It is divided into：Hydrogenated bisphenol A epoxy resin Epalloy 5000 (5g)；Cycloaliphatic epoxy resin Celoxide 2021P (65g)；Bis-phenol
A epoxy resin Epon 828 or DER 331 (5g)；Cation light initiator1190(5g)；Polyalcohol Sunnix
GP-400(20g)。
The producer of each component of comparative example 8 and embodiment 1-5 and model are all identical, but match different, the group of comparative example 8
It is divided into：Hydrogenated bisphenol A epoxy resin Epalloy 5000 (55g)；Cycloaliphatic epoxy resin Celoxide 2021P (5g)；Bis-phenol
A epoxy resin Epon 828 or DER 331 (15g)；Cation light initiator1190(5g)；Polyalcohol Sunnix
GP-400(20g)。
Table 3：The test result of comparative example 1-8.
Test：Medical instrument quality examination.
1, delayed allergy is tested
According to standard GB/T/T16886.10-2005《The 10th part of BiologicalEvaluationofMedicalDevice：Stimulation and delayed
Hypersensitivity is tested》The maximum dose method of middle recommendation is tested.
Method：The sample of naval stores of the present invention is prepared into leaching liquor with extraction medium.Leaching liquor passes through cavy intradermal
Injection carries out intradermal induction and sticks the induction of progress part by closing to generate sensitization, and control animals are given in the same way
Blank extracts medium.Test group and control animals are carried out sticking excitation with respective sample leaching liquor and comparison liquid after induction.
Remove applicator after for 24 hours, 48h to all animals excitation area skin reaction be classified.
Extract medium：0.9% sodium chloride injection.It is prepared by leaching liquor：The sample 4.0g for taking naval stores of the present invention, is filled with
Medium 20.0mL is extracted, placing 72h at 37 DEG C prepares sample leaching liquor as test sample.Negative controls：Same lot number is taken to extract
It is prepared by medium, the same terms.Experimental animal：15 regular grade Harlty cavys (experimental animal is qualified and permits).
As a result：All animal excitation area skins do not occur erythema and oedema.
Conclusion：Under the experimental condition, sample does not cause cavy delayed allergy.
Intradermal induction：In the pairs of intracutaneous injection 0.1mL of the plucked shoulder blade inside line of every animal.
Part induction：7d after intradermal induction, with area 8cm2Sterile gauze be impregnated with leaching liquor, be locally pasted on every globefish
On the inside of the shoulder blade of mouse, covering induction injection point is fixed with closed binder, binder and gauze piece is removed after 48h.Same method
Media operation control animals are extracted with blank.
Excitation：14d after the induction of part, filter paper or absorbent yarn cloth are respectively placed in test specimen leaching liquor and comparison liquid
It is impregnated with, hair-fields (induction period not test (N.T.) position) is gone at the abdomen back for being pasted on every animal respectively.Closed binder is taken to fix,
And binder and applying patch are removed after ± 2h in for 24 hours.
Observation：Test group is observed with 48h for 24 hours after removing applying patch and control animals excite area skin response situation,
Erythema and oedema reaction are described and are classified by Magnusson and Kligman grade scales.
Table 4：Magnusson and Kligman grade scales
| Percutaneous test reacts | Grade |
| Nothing is substantially change | 0 |
| Sporadic or mottled erythema | 1 |
| Moderate amalgamation erythema | 2 |
| Severe amalgamation erythema | 3 |
Table 5：Dermoreaction result after excitation
Test result：The weight of all animals and the performance of clinical observation result no abnormality seen during experiment.Test group (this
Invention naval stores) animal excitation area skin have no erythema and oedema, do not observe apparent sensitivity response symptom (0 grade, without bright
It is aobvious to change), show naval stores of the present invention without guinea pig skin sensitivity response.
2, Skin Irritation Test
According to standard GB/T/T16886.10-2005《The 10th part of BiologicalEvaluationofMedicalDevice：Stimulation and delayed
Hypersensitivity is tested》The method of middle recommendation carries out rabbit Skin Irritation Test.
Method：There is the gauze piece of appropriate amount of sample leaching liquor to contact at least 4h with rabbit skin of back experiment position drop, it will
Drop has the gauze piece of blank control extraction medium to be operated as a contrast with method.1h after contact, for 24 hours, 48h and 72h observations it is dynamic
The dermoreaction of object contact site.
Extract medium：0.9% sodium chloride injection.It is prepared by leaching liquor：The sample 2.0g for taking naval stores of the present invention, is pressed
The ratio of 0.2g/mL is filled with extraction medium 10.0mL, and placing 72h at 37 DEG C prepares sample leaching liquor.Experimental animal：3 common
Grade New Zealand White Rabbit (experimental animal is qualified and permits).
Prepare before experiment：4-24h before experiment, is identified animal and weighs, back part of animal backbone both sides hair is removed
(about 10cm × 15cm) is removed, as experiment and look-out station.
Test method：Sample leaching liquor 0.5mL is dripped on the hospital gauze of 2.5cm × 2.5cm sizes, animal is applied to
Back backbone both sides, by blank extraction medium with method operation application at control position.It is fixed with the semiclosed property of bandage or closure
Applying patch at least 4h.Contact removes applying patch after the phase, is marked to contact site with persistence ink, warm water is used in combination to remove
Remove residue test material.And after contact for 24 hours, 48h and 72h observe and record the erythema of contact point, oedema reaction.
As a result：Rabbit primary stimulus index (PII) is 0.
Conclusion：Under the experimental condition, the skin wound repair type of naval stores (test sample, test group) of the present invention
It is extremely slight.
Table 6：Rabbit stimulate the reaction type
| Mean score | Reaction type |
| 0~0.4 | It is extremely slight |
| 0.5~1.9 | Slightly |
| 2~4.9 | Moderate |
| 5~8 | Severe |
Table 7：Rabbit skin stimulate the reaction result
Rabbit primary stimulus index (PII)=0 illustrates under the experimental condition, naval stores of the present invention is complete to skin
There is no stimulate the reaction.
3, vitro cytotoxicity test
According to the 5th part of GB/T16886.5-2003 BiologicalEvaluationofMedicalDevices：Recommend in vitro cytotoxicity test
Method carry out vitro cytotoxicity test.
Method：It is added in cultured cell monolayer after the sample of naval stores of the present invention is extracted, sets carbon dioxide training
It supports 37 DEG C of culture 48h of case and observes result.
Culture medium：RPMI1640；Cell strain：(the Chinese Academy of Sciences Shanghai l cell ATCC CCL1 (L-929)
Life science institute provides)；Extract medium：MEM；It is prepared by leaching liquor：In the ratio of 0.2g/mL, 2.0g test specimens is taken to fill
Enter 10.0mL extraction media, is placed at 37 DEG C and prepare sample leaching liquor for 24 hours.
Positive control：The pvc material (confirmed reproducible cytotoxicity) of the additive containing organotin, uses ultra-pure water
It cleans and dries, ultraviolet light irradiation overnight, extraction medium is filled in the ratio of 0.2g/mL, is extracted at 37 DEG C for 24 hours, as positive right
According to liquid.
As a result：After culture, culture dish is set into microscopically observation, wherein the cellular morphology of naval stores of the present invention is just
Often, adherent production is good, there is discrete particle, acellular dissolving in endochylema.The cellular layer of positive controls almost destroys.
Conclusion：Naval stores of the present invention meets the toxicity criterion of medical instrument quality.Positive controls are severe cell toxicant
Property.
Above is only a specific embodiment of the present invention, it is not intended to limit the scope of the invention, every utilization
The equivalent transformation that the present invention makees is applied directly or indirectly in other relevant technical fields, is similarly included in the present invention's
Among scope of patent protection.
Claims (9)
1. one kind can be used for the transparent photosensitive resin of clinical medical high tenacity, which is characterized in that count in parts by weight, including following
Component：
2. the transparent photosensitive resin of high tenacity according to claim 1, which is characterized in that the hydrogenated bisphenol A epoxy resin
It is difficult to understand for the Epalloy 5000 of Jia Dida Chemical Co., Ltd.s of Shenzhen, the EP-4080E of Ai Dike trade Co., Ltds, Yantai
The AL-3040 of Li Fu Chemical Co., Ltd.s or one or more in HAL-3040.
3. the transparent photosensitive resin of high tenacity according to claim 1, which is characterized in that the cycloaliphatic epoxy resin is big
Celoxide 2021P of Sai Lu Investment Co., Ltd, the TTA21 of Jiangsu Tai Teer new materials Science and Technology Ltd., Hensel advanced in yearsization
CY179, the Hensel of work trade Co., Ltd step one or more in the CY184 of Chemical trade Co., Ltd.
4. the transparent photosensitive resin of high tenacity according to claim 1, which is characterized in that the bisphenol A epoxide resin is lotus
The Epon 828 of blue Hexion Chemical Co., Ltd., the DER 331 of DOW Chemical Co., Ltd, Jinan Yi Sheng resins Co., Ltd
E-51, Jinan Yi Sheng resins Co., Ltd E-44 in it is one or more.
5. the transparent photosensitive resin of high tenacity according to claim 1, which is characterized in that the cation light initiator is upper
Extra large strange titanizing Science and Technology Ltd.1190, Easepi 6976, the Bath of the easy Chemical Co., Ltd. of upper sea light
It is one or more in the Irgacure 250 of husband Co., Ltd, the Uyracure-160 of You Yang Science and Technology Ltd.s of Shenzhen.
6. the transparent photosensitive resin of high tenacity according to claim 1, which is characterized in that the polyalcohol is that Sanyo is melted into trade
Sunnix GP-400 of easy Co., Ltd, Voranol, Ying Chuan Degussa Investment Co., Ltd of DOW Chemical Co., Ltd
It is one or more in Oxyester.
7. the transparent photosensitive resin of high tenacity according to claim 1, which is characterized in that the hydrogenated bisphenol A epoxy resin
For the Epalloy 5000 of Jia Dida Chemical Co., Ltd.s of Shenzhen；The cycloaliphatic epoxy resin is that Daicel limited investment is public
The Celoxide 2021P of department；The bisphenol A epoxide resin is the Epon 828 or Tao Shiization of Dutch Hexion Chemical Co., Ltd.
Learn the DER 331 of Co., Ltd；The cation light initiator is the strange titanizing Science and Technology Ltd. in Shanghai
1190；The polyalcohol is the Sunnix GP-400 that Sanyo is melted into trade Co., Ltd.
8. a kind of preparation method of the transparent photosensitive resin of high tenacity according to any one of claim 1-7, feature exist
In including the following steps：Each raw material component is matched according to parts by weight and is mixed, then stirs 60 at 20 DEG C~70 DEG C of temperature
~150 minutes, obtain the transparent photosensitive resin of the high tenacity.
9. a kind of application of the transparent photosensitive resin of high tenacity according to any one of claim 1-7, which is characterized in that will
The transparent photosensitive resin of high tenacity is used as medical instrument.
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