CN105068378B - A kind of flame retardant type SLA photosensitive resin for 3D printing - Google Patents
A kind of flame retardant type SLA photosensitive resin for 3D printing Download PDFInfo
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Abstract
The invention discloses a kind of flame retardant type SLA photosensitive resins for 3D printing, it is characterized in that, consist of the following components in percentage by weight: phosphoric acrylic ester prepolymer 15-75%, acrylate 15-75%, radical initiator 1-5%, auxiliary agent 0.5-2%, reactive diluent 5-15%, the sum of the above components weight percent are 100%；The phosphoric acrylic ester prepolymer structure general formula isWherein, R1=H2C=CH- orR2=-CH2- CH2,Or-CH2- CH2- CH2- CH2One of.
Description
Technical field
The present invention relates to 3D printing technique fields, in particular to a kind of fire-retardant type photosensitive resin of the SLA for 3D printing.
Background technique
Photocuring solid forming is using stereosopic printing (Stereo Lithography Apparatus, SLA) principle
A kind of technique, and occur earliest, the most mature and most widely used rapid prototyping technology of technology, by U.S. 3D Systems
Company releases in the late 1980s.The manufacturing process of SLA is to fill with liquid photosensitive resin in resin liquid bath, make its
Rapid curing under the irradiation of laser beam, when forming process starts, liftable workbench is in the next section thickness of liquid level
Highly, the laser beam after focusing according to the requirement of cross section profile, is scanned under control of the computer along liquid level, makes to be swept
The resin solidification in region is retouched, to obtain the plastic tab of the cross section profile.Then, workbench declines the height of one layer of thin slice,
Cured plastic tab is just by one layer of new liquid resin institute top cover, new to solidify to carry out second layer laser scanning solidification
One layer securely it is withered knot in preceding layer, so repeat endlessly, until entire product shaping finishes.Since SLA technology solidifies
The advantages that speed is fast, high production efficiency and suitable industrial flow-line produce, SLA photosensitive resin is increasingly widely applied quick
It forms in manufacturing industry.The characteristic that SLA photosensitive resin needs to have has: viscosity is low, good fluidity, is conducive to resin levelling；Solidification
Speed is fast, and curing rate directly affects shaping efficiency, influences economic benefit indirectly；Cure shrinkage is small, liquid resin solidification process
In can generate contraction, cause to solidify part warpage, deformation etc., influence formed precision.
Though the photosensitive resin currently used for SLA technology is able to satisfy above-mentioned characteristic, the overwhelming majority is inflammable, and with
The fast development and large-scale application of SLA technology, this disadvantage will limit its application range, hinder the development of entire industry.
It is added in SLA photopolymer system using phosphorus oxychloride as fire retardant derived from raw material according to conventional means, though it can partially solve
Certainly fire-retardant problem, but phosphorus oxychloride has high toxicity in production, can decomposite HCl, pollute the environment, and as additional
There are some problems for the compatibility of type fire retardant and SLA photosensitive resin.Therefore, the SLA light with ingrain fireproofing performance is developed
Quick resin has great importance.
Summary of the invention
The purpose of the present invention is to solve the deficiency of the above background technology, provides a kind of nontoxic, environmentally friendly use
In the flame retardant type SLA photosensitive resin of 3D printing.
The technical solution of the present invention is as follows: a kind of flame retardant type SLA photosensitive resin for 3D printing, which is characterized in that by with
The group of lower weight percent is grouped as: phosphoric acrylic ester prepolymer 15-75%, acrylate 15-75%, radical initiator
1-5%, auxiliary agent 0.5-2%, reactive diluent 5-15%, the sum of the above components weight percent are 100%；Described phosphorous third
Olefin(e) acid ester prepolymer structure general formula is
Wherein,
R1=H2C=CH- or
R2=-CH2-CH2-、Or-CH2-CH2-CH2-CH2One of.
Preferably, the phosphoric acrylic ester prepolymer is by 2- methyl -2,5- dioxy -1,2- oxygen phospholane (abbreviation
OP it) is mixed with hydroxy acrylic acid esters compound with the ratio of molar ratio 1:1, catalyst and polymerization inhibitor is added at 110-130 DEG C
It is obtained after lower reaction 5-6h；
The hydroxy acrylic acid esters compound is hydroxy-ethyl acrylate, senecioate-hydroxypropyl acrylate, acrylic acid -4- hydroxyl
One of butyl ester, hydroxyethyl methacrylate, methacrylic acid-β-hydroxypropyl acrylate.
Further, the polymerization inhibitor be hydroquinone, p-hydroxyanisole, 1,4-benzoquinone, N- phenyl-2-naphthylamine, to uncle
The combination of one or more of butyl-catechol, the polymerization inhibitor dosage are 2- methyl -2,5- dioxy -1,2- oxygen phosphorus heterocycle penta
The 0.1-5.0% of alkane OP and hydroxy acrylic acid esters compound quality sum.
Further, the catalyst be storng-acid cation exchange resin PK208LH, PK212LH, RCP106M,
One or more of D001, NKC-9 combination, the catalyst amount are 2- methyl -2,5- dioxy -1,2- oxygen phospholane
The 5-8% of OP and hydroxy acrylic acid esters compound quality sum.PK208LH, PK212LH, RCP106M are Mitsubishi Chemical's production
Storng-acid cation exchange resin, D001, NKC-9 are the storng-acid cation exchange resin of resin processing plant, University Of Tianjin production.
Preferably, the acrylate is aliphatic urethane acrylate, aromatic urethane acrylate, epoxy third
The combination of one or more of olefin(e) acid ester or polyester acrylate.The acrylate can choose the fat of Taiwan Changxing company
Adoption urethane acrylate: 6141H-80,6148J-75,615-100,6151,6153-3,6157B-80,6168,6170, DR-
U356,DR-U390；The aromatic urethane acrylate of Changxing company: 6146-100；The epoxy acrylate of Changxing company:
6202,622A-80,623-100,624A-45,625C-45；The polyester acrylate of Changxing company: 6315,6320,6351,
6371、6390F。
Preferably, the radical initiator include photoinitiator 1173,184,907,369,651,819, in ITX
One or more combination.Photoinitiator 1173,184,907,369,651,819, ITX are initiation common in the art
Agent.
Preferably, the reactive diluent is acrylate-functional monomer 2- (1,2- hexamethylene -1,2- dicarboxyl acyl
Imines) ethyl propylene acid esters, ring trimethylolpropane dimethoxym ethane acrylate, 2- phenoxyethyl acrylate, isobornyl
One of acrylate, cyclohexyl methacrylate, dipropylene glycol diacrylate, 1,9- nonanediol diacrylate are several
Kind combination.The reactive diluent can select the acrylate-functional monomer of Taiwan Changxing company: EM2140 2- (1,2-
Hexamethylene -1,2- dicarboximide) ethyl propylene acid esters, EM212 ring trimethylolpropane dimethoxym ethane acrylate CTFA,
EM210 2- phenoxyethyl acrylate PHEA, EM70 iso-bornyl acrylate IBOA, EM71-E methacrylic acid hexamethylene
Ester CHMA, EM222 dipropylene glycol diacrylate DPGDA, EM2203 1,9- nonanediol diacrylate NDDA.
Preferably, the auxiliary agent includes levelling agent and defoaming agent, and the levelling agent quality and defoaming agent mass ratio are 1-
3:1.
Further, the levelling agent is dimethyl silicone polymer, polymethylphenylsiloxane, organic-silicon-modified poly- silicon oxygen
One of alkane.
Further, the defoaming agent is Polyether Modified Polysiloxanes Defoaming Agent.
In the present invention, in the present invention, 2- methyl -2,5- dioxy -1,2- oxygen phospholane OP and hydroxy acrylic acid esters
Compound prepares the reaction process of phosphoric acrylic ester prepolymer are as follows:
Wherein, hydroxy acrylic acid esters compound formula is
R1=H2C=CH- or
R2=-CH2-CH2-、Or-CH2-CH2-CH2-CH2One of.
The invention has the benefit that
1. using the phosphoric acrylic ester prepolymer containing fire-retardant group, there is the prepolymer for being made into photosensitive resin itself
Good flame retardant property.
2. prepolymer itself has flame retarding construction, photosensitive resin is cooperatively formed with urethane acrylate, catalyst, auxiliary agent
Afterwards, photosensitive resin is solidifying or not will form in use process later the substance for polluting environment or impairing human body health, peace
Loopful is protected, and is avoided when in order to which the anti-flammability of photosensitive resin adds the inorganic matter containing brominated flame retardant or the class containing antimony pentoxide
When, it threatens to environment, people's health is damaged.
3. existing oil-soluble ester structure in phosphoric acrylic ester prepolymer, and have water-soluble hydroxyl structure, make pre-polymerization
Object not only can be used for oil-soluble photopolymer system but also can be used for Water-soluble product system.
4. photosensitive resin made from has preferable while meeting that original viscosity is low, curing rate is fast, shrinking percentage is small
Flame retardant property, safety and environmental protection.
Detailed description of the invention
Fig. 1 is the FTIR map of phosphorous hydroxy-ethyl acrylate prepolymer
Fig. 2 is phosphorous hydroxy-ethyl acrylate prepolymer NMR-H1Map
Specific embodiment
The present invention is described in further detail combined with specific embodiments below.
Embodiment 1
It takes 13.40g (0.1mol) OP and 11.60g (0.1mol) hydroxy-ethyl acrylate in three-necked flask, 2.00g is added
Catalyst storng-acid cation exchange resin PK208LH (catalyst quality be OP and hydroxy-ethyl acrylate quality and 8%) and
0.0250g hydroquinone of polymerization retarder (polymerization inhibitor quality be OP and hydroxy-ethyl acrylate quality and 0.1%), at 110 DEG C, instead
Stop reaction after answering 5h.Product phosphoric acrylic ester prepolymer in system is separated: 100mL ethyl acetate is added, is continued
30min is stirred, after system temperature is reduced to room, is filtered with cloth funnel and separates PK208LH resin cation with reaction solution
(the PK208LH resin isolated immersion is washed away into phosphoric acrylic ester prepolymer in ethanol to reuse), by filtrate
It is added in the pyriform funnel of 250mL, addition saturated salt solution 50ML two-phase, which is vigorously mixed, washes away polymerization inhibitor and unreacted OP, satisfies
It is larger in lower layer with salt water layer specific gravity, lower layer is released for use, each 50mL of saturated salt solution is continuously washed three times.Lower layer's salt
It is extracted twice after being hydrated simultaneously with ethyl acetate 200mL, ethyl acetate phase extract mutually merges with the oil that upper layer obtains with anhydrous sulphur
After sour sodium is dry, vacuum distillation removes ethyl acetate and hydroxy-ethyl acrylate obtains phosphoric acrylic ester prepolymer 18g, mole receipts
Rate is 72%.
By phosphoric acrylic ester prepolymer 61.33g, aliphatic urethane acrylate 6170 made from the above method
26.67g, it reactive diluent EM212 ring trimethylolpropane dimethoxym ethane acrylate 5g, 1173 5g of free radical photo-initiation, helps
Agent 2g (is made of) 1g dimethyl silicone polymer levelling agent and 1g Polyether Modified Polysiloxanes Defoaming Agent, is mixed evenly, is obtained
Flame retardant type SLA photosensitive resin.Polyether Modified Polysiloxanes Defoaming Agent is that the ZK-203 of Tianjin Zhong Ke Chemical Co., Ltd. production is organic
Silicon defoaming agent.
Embodiment 2
It takes 13.40g (0.1mol) OP and 13.00g (0.1mol) senecioate-hydroxypropyl acrylate in three-necked flask, is added
2.00g catalyst storng-acid cation exchange resin PK208LH (catalyst quality be OP and senecioate-hydroxypropyl acrylate quality and
7.58%) and 0.0264g hydroquinone of polymerization retarder (polymerization inhibitor quality be OP and senecioate-hydroxypropyl acrylate quality and
0.1%), at 110 DEG C, reaction 5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), and molar yield is
68%.
By phosphoric acrylic ester prepolymer 63.33g obtained above, 6170 21.67g of aliphatic urethane acrylate,
Reactive diluent EM210 2- phenoxyethyl acrylate 10g, 1173 3g of free radical photo-initiation, auxiliary agent 2g are (by 1g poly- two
Methylsiloxane levelling agent and 1g Polyether Modified Polysiloxanes Defoaming Agent composition), it is mixed evenly, it is photosensitive to obtain flame retardant type SLA
Resin.
Embodiment 3
It takes 13.40g (0.1mol) OP and 14.40g (0.1mol) acrylic acid -4- hydroxy butyl ester in three-necked flask, is added
2.00g catalyst storng-acid cation exchange resin PK208LH (catalyst quality be OP and acrylic acid -4- hydroxy butyl ester quality and
7.18%) and 0.0278g hydroquinone of polymerization retarder (polymerization inhibitor quality be OP and acrylic acid -4- hydroxy butyl ester quality and
0.1%), at 110 DEG C, reaction 5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), and molar yield is
79%.
Phosphoric acrylic ester prepolymer 40g obtained above, 6170 43g of aliphatic urethane acrylate, activity is dilute
Agent EM70 iso-bornyl acrylate 15g, 1173 1g of free radical photo-initiation, auxiliary agent 1g are released (by 0.5g dimethyl silicone polymer
Levelling agent and 0.5g Polyether Modified Polysiloxanes Defoaming Agent composition), it is mixed evenly, obtains flame retardant type SLA photosensitive resin.
Embodiment 4
It takes 13.40g (0.1mol) OP and 13g (0.1mol) hydroxyethyl methacrylate in three-necked flask, 2.11g is added
Catalyst storng-acid cation exchange resin PK212LH (catalyst quality be OP and hydroxyethyl methacrylate quality and
8%) and 0.132g polymerization inhibitor p-hydroxyanisole (polymerization inhibitor quality be OP and hydroxyethyl methacrylate quality and
0.5%), at 110 DEG C, reaction 5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), and molar yield is
65%.
By phosphoric acrylic ester prepolymer 15g obtained above, aromatic urethane acrylate 6146-100 73g, work
Property diluent EM222 dipropylene glycol diacrylate 7g, 907 4.5g of free radical photo-initiation, auxiliary agent 0.5g are (by 0.25g levelling
Agent polymethylphenylsiloxane and 0.25g Polyether Modified Polysiloxanes Defoaming Agent composition), it is mixed evenly, obtains flame retardant type SLA
Photosensitive resin.
Embodiment 5
It takes 13.40g (0.1mol) OP and 14.40g (0.1mol) methacrylic acid-β-hydroxypropyl acrylate in three-necked flask, adds
Entering 1.39g catalyst storng-acid cation exchange resin PK212LH, (catalyst quality is OP and methacrylic acid-β-hydroxypropyl acrylate
Quality and 5%) and 0.278g polymerization inhibitor 1,4-benzoquinone (polymerization inhibitor quality be OP and methacrylic acid-β-hydroxypropyl acrylate quality and
1%), at 120 DEG C, reaction 6h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), and molar yield is
70%.
By phosphoric acrylic ester prepolymer 50g obtained above, 6202 34.5g of epoxy acrylate, reactive diluent
12g is (by 6g EM212 ring trimethylolpropane dimethoxym ethane acrylate and 6g EM210 2- phenoxyethyl acrylate group
At), 369 2g of free radical photo-initiation, auxiliary agent 1.5g (have by 1g levelling agent polymethylphenylsiloxane and 0.5g are polyether-modified
Machine silicon defoaming agent composition), it is mixed evenly, obtains flame retardant type SLA photosensitive resin.
Embodiment 6
It takes 13.40g (0.1mol) OP and 11.6g (0.1mol) hydroxy-ethyl acrylate in three-necked flask, 1.5g is added and urges
Agent storng-acid cation exchange resin RCP106M (catalyst quality be OP and hydroxy-ethyl acrylate quality and 6%) and
0.5g polymerization inhibitor N- phenyl-2-naphthylamine (polymerization inhibitor quality be OP and hydroxy-ethyl acrylate quality and 2%), at 120 DEG C, instead
5.5h is answered to obtain phosphoric acrylic ester prepolymer (separation method is with embodiment 1), molar yield 75%.
By phosphoric acrylic ester prepolymer 75g obtained above, 6315 15.5g of polyester acrylate, reactive diluent
EM210 2- phenoxyethyl acrylate 5g, 184 3g of free radical photo-initiation, auxiliary agent 1.5g (are changed by 1g levelling agent organosilicon
Property polysiloxanes and 0.5g Polyether Modified Polysiloxanes Defoaming Agent composition), be mixed evenly, obtain flame retardant type SLA photosensitive resin.
Embodiment 7
It takes 13.40g (0.1mol) OP and 13g (0.1mol) senecioate-hydroxypropyl acrylate in three-necked flask, 1.85g is added
Catalyst storng-acid cation exchange resin D001 (catalyst quality be OP and senecioate-hydroxypropyl acrylate quality and 7%) and
1.32g polymerization inhibitor p-tert-Butylcatechol (polymerization inhibitor quality be OP and senecioate-hydroxypropyl acrylate quality and 5%), 110
At DEG C, reaction 5.5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), molar yield 78%.
By phosphoric acrylic ester prepolymer 63.6g obtained above, 6320 15g of polyester acrylate, reactive diluent
15g (being made of 5g EM70 iso-bornyl acrylate and 10g EM222 dipropylene glycol diacrylate), free radical are light-initiated
651 5g of agent, auxiliary agent 1.4g are (by the organic-silicon-modified polysiloxanes of 0.7g levelling agent and 0.7g Polyether Modified Polysiloxanes Defoaming Agent group
At), it is mixed evenly, obtains flame retardant type SLA photosensitive resin.
Embodiment 8
It takes 13.40g (0.1mol) OP and 14.4g (0.1mol) acrylic acid -4- hydroxy butyl ester in three-necked flask, is added
2.22g catalyst storng-acid cation exchange resin D001 (catalyst quality be OP and acrylic acid -4- hydroxy butyl ester quality and
8%) and 1.112g polymerization inhibitor p-hydroxyanisole (polymerization inhibitor quality be OP and acrylic acid -4- hydroxy butyl ester quality and 4%),
At 120 DEG C, reaction 6h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), molar yield 80%.
By phosphoric acrylic ester prepolymer 35.2g obtained above, acrylate 50g (by 25g aliphatic polyurethane propylene
Acid esters 6170 and 25g epoxy acrylate 6202 form), reactive diluent EM70 iso-bornyl acrylate 10g, free radical light
819 3g of initiator, auxiliary agent 1.8g are (by the organic-silicon-modified polysiloxanes of 1g levelling agent and 0.8g Polyether Modified Polysiloxanes Defoaming Agent
Composition), it is mixed evenly, obtains flame retardant type SLA photosensitive resin.
Embodiment 9
It takes 13.40g (0.1mol) OP and 13g (0.1mol) hydroxyethyl methacrylate in three-necked flask, 1.45g is added
Catalyst (catalyst quality be OP and hydroxyethyl methacrylate quality and 5.5%), catalyst is handed over by highly acidic cation
Resin PK212LH and NKC-9 1:1 in mass ratio composition are changed, 0.66g polymerization inhibitor is added, and (polymerization inhibitor quality is OP and metering system
The 2.5% of sour hydroxyl ethyl ester quality sum), polymerization inhibitor is that 1,4-benzoquinone and N- phenyl-2-naphthylamine 1:1 in mass ratio are formed, at 130 DEG C
Under, reaction 5h obtains phosphoric acrylic ester prepolymer (separation method is with embodiment 1), molar yield 74%.
By phosphoric acrylic ester prepolymer 16.4g obtained above, acrylate 75g (by 25g aliphatic polyurethane propylene
Acid esters 6170 and 50g polyester acrylate 6315 form), reactive diluent EM222 dipropylene glycol diacrylate 6g, free radical
Photoinitiator ITX 1g, auxiliary agent 1.6g are (by 1.2g levelling agent dimethyl silicone polymer and 0.4g Polyether Modified Polysiloxanes Defoaming Agent
Composition), it is mixed evenly, obtains flame retardant type SLA photosensitive resin.
Embodiment 10
It takes 13.40g (0.1mol) OP and 14.4g (0.1mol) methacrylic acid-β-hydroxypropyl acrylate in three-necked flask, is added
1.81g catalyst (catalyst quality be OP and methacrylic acid-β-hydroxypropyl acrylate quality and 6.5%), catalyst is by highly acid
Cation exchange resin PK212LH, RCP106M, D001, NKC-9 1:1:1:1 in mass ratio composition, are added 1.39g polymerization inhibitor
(polymerization inhibitor quality be OP and methacrylic acid-β-hydroxypropyl acrylate quality and 5%), polymerization inhibitor is benzenediol, 1,4-benzoquinone and to hydroxyl
Base methyl phenyl ethers anisole 1:1:1 in mass ratio composition, at 130 DEG C, reaction 5h obtains phosphoric acrylic ester prepolymer, and (separation method is the same as real
Apply example 1), molar yield 69%.
By phosphoric acrylic ester prepolymer 20.2g obtained above, acrylate 60g (by 30g epoxy acrylate 6202
Formed with 30g polyester acrylate 6315), reactive diluent 14g is (by 4g EM70 iso-bornyl acrylate, 5g EM212 ring
Trimethylolpropane dimethoxym ethane acrylate and 5g EM210 2- phenoxyethyl acrylate composition), free radical photo-initiation
5g (being made of 1173 2.5g and 907 2.5g), auxiliary agent 0.8g (are gathered by the organic-silicon-modified polysiloxanes of 0.4g levelling agent and 0.4g
Ether modified organic silicon defoaming agent composition), it is mixed evenly, obtains flame retardant type SLA photosensitive resin.
Performance test:
The infared spectrum that phosphorous hydroxy-ethyl acrylate prepolymer, hydroxy-ethyl acrylate and OP are made in embodiment 1 is shown in Fig. 1,
Phosphorous hydroxy-ethyl acrylate prepolymer is made in embodiment 11H-NMR (DMSO-D6) map is shown in Fig. 2.
B curve can be seen that in 1709cm from Fig. 1 infared spectrum-1Place is C=O stretching vibration, in 1637cm-1Place is C
The characteristic absorption peak of=C, in 1130cm-1Place is the characteristic absorption peak of P=O, in 979cm-1Corresponding is that C-P stretching vibration is inhaled
Peak is received, illustrates the characteristic group in target molecule there are acrylic acid groups and phosphorus.In addition, comparison b spectrogram can be seen with a, c spectrogram
The characteristic absorption peaks such as C=O, C=C, P=O, C-P all generate red shift out, illustrate that hydroxy-ethyl acrylate and OP react.From Fig. 21H-NMR (DMSO-D6) pattern analysis results:
δ/ppm:1.28-1.44 (3H ,-CH3, a), 1.76-2.43 (4H ,-CH2, c, d), 3.59-4.29 (4H ,-CH2,
E, f), 5.93-6.39 (3H ,-CH=CH2, g, h, i).From FT-IR analysis and1H-NMR analysis can prove that synthetic product is to contain
Phosphorus hydroxy-ethyl acrylate.
SLA photosensitive resin obtained in embodiment 1-10 is tested for the property, as a result as shown in the table:
As can be seen from the above table, the resulting SLA photosensitive resin of embodiment 1-10 is in curing time, gel fraction, viscosity, volume
Shrinking percentage keeps excellent flame retardancy in good situation.
Claims (6)
1. a kind of flame retardant type SLA photosensitive resin for 3D printing, which is characterized in that by following components in percentage by weight group
At: phosphoric acrylic ester prepolymer 15-75%, acrylate 15-75%, radical initiator 1-5%, auxiliary agent 0.5-2%, work
Property diluent 5-15%, the sum of the above components weight percent be 100%；The phosphoric acrylic ester prepolymer structure general formula
For
Wherein,
R1=H2C=CH- or
R2=-CH2-CH2-、Or CH2CH2CH2CH2One of；
The auxiliary agent is made of levelling agent and defoaming agent 1-3:1 in mass ratio；
The phosphoric acrylic ester prepolymer is by 2- methyl -2,5- dioxy -1,2- oxygen phospholane OP and hydroxy acrylate
Class compound is mixed with the ratio of molar ratio 1:1, be added catalyst and polymerization inhibitor react 5-6h at 110-130 DEG C after obtain；
The hydroxy acrylic acid esters compound be hydroxy-ethyl acrylate, senecioate-hydroxypropyl acrylate, acrylic acid -4- hydroxybutyl,
One of hydroxyethyl methacrylate, methacrylic acid-β-hydroxypropyl acrylate；
The polymerization inhibitor is hydroquinone, in p-hydroxyanisole, 1,4-benzoquinone, N- phenyl-2-naphthylamine, p-tert-Butylcatechol
One or more combination, the polymerization inhibitor dosage be 2- methyl -2,5- dioxy -1,2- oxygen phospholane OP and hydroxy
The 0.1-5.0% of acid esters compound quality sum；
The catalyst is one in storng-acid cation exchange resin PK208LH, PK212LH, RCP106M, D001, NKC-9
Kind or several combinations, the catalyst amount are 2- methyl -2,5- dioxy -1,2- oxygen phospholane OP and hydroxy acrylate
The 5-8% of class compound quality sum.
2. photosensitive resin as described in claim 1, which is characterized in that the acrylate is aliphatic polyurethane acrylic acid
The combination of one or more of ester, aromatic urethane acrylate, epoxy acrylate or polyester acrylate.
3. photosensitive resin as described in claim 1, which is characterized in that the radical initiator be photoinitiator 1173,
184,907,369,651,819, one or more of ITX combination.
4. photosensitive resin as described in claim 1, which is characterized in that the reactive diluent is acrylate-functional monomer
2- (1,2- hexamethylene -1,2- dicarboximide) ethyl propylene acid esters, ring trimethylolpropane dimethoxym ethane acrylate, 2- benzene
Oxygroup ethyl propylene acid esters, iso-bornyl acrylate, cyclohexyl methacrylate, dipropylene glycol diacrylate, 1,9- nonyl
The combination of one or more of omega-diol diacrylate.
5. photosensitive resin as described in claim 1, which is characterized in that the levelling agent is dimethyl silicone polymer, poly- methyl
One of phenyl siloxane, organic-silicon-modified polysiloxanes.
6. photosensitive resin as described in claim 1, which is characterized in that the defoaming agent is Polyether Modified Polysiloxanes Defoaming Agent.
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| CN106814537B (en) * | 2015-11-30 | 2020-02-21 | 乐凯华光印刷科技有限公司 | Photosensitive imaging composition containing cyclohexane amide monofunctional acrylate copolymer |
| CN107300828B (en) * | 2016-04-15 | 2021-01-15 | 常州强力电子新材料股份有限公司 | Photosensitive resin for 3D printing |
| CN108727550A (en) * | 2018-04-23 | 2018-11-02 | 浙江锐胜新材料有限公司 | A kind of photosensitive resin and its application |
| CN108587100A (en) * | 2018-05-18 | 2018-09-28 | 深圳永昌和科技有限公司 | Environment and human body friendly vegetable oil base ultraviolet light cure 3D printing resin |
| CN111154211B (en) * | 2019-12-26 | 2021-11-19 | 诺思贝瑞新材料科技（苏州）有限公司 | Photocuring composition for 3D printing and photocuring part |
| CN112080183A (en) * | 2020-09-01 | 2020-12-15 | 徐振东 | Environment-friendly acrylic pressure-sensitive adhesive for paper and preparation method thereof |
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| EP4369098A1 (en) | 2022-11-14 | 2024-05-15 | Cubicure GmbH | Resin composition |
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| CN103502313A (en) * | 2012-05-03 | 2014-01-08 | 株式会社Lg化学 | Novel polyamic acid, photosensitive resin composition, dry film and circuit board |
| CN104109328A (en) * | 2014-06-23 | 2014-10-22 | 东莞智维立体成型股份有限公司 | Photocuring wax material used for 3D printing |
| CN104570603A (en) * | 2013-10-22 | 2015-04-29 | 青岛中科新材料有限公司 | Preparation method and application of photosensitive resin for ultrasonic curing 3D printing |
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| DE102006012878A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Limited | Phosphorus-containing mixtures, a process for their preparation and their use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103502313A (en) * | 2012-05-03 | 2014-01-08 | 株式会社Lg化学 | Novel polyamic acid, photosensitive resin composition, dry film and circuit board |
| CN104570603A (en) * | 2013-10-22 | 2015-04-29 | 青岛中科新材料有限公司 | Preparation method and application of photosensitive resin for ultrasonic curing 3D printing |
| CN104109328A (en) * | 2014-06-23 | 2014-10-22 | 东莞智维立体成型股份有限公司 | Photocuring wax material used for 3D printing |
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