CN103450414B - Compositions of a kind of photosensitive resin and preparation method thereof and photosensitive resin - Google Patents
Compositions of a kind of photosensitive resin and preparation method thereof and photosensitive resin Download PDFInfo
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- CN103450414B CN103450414B CN201210167639.XA CN201210167639A CN103450414B CN 103450414 B CN103450414 B CN 103450414B CN 201210167639 A CN201210167639 A CN 201210167639A CN 103450414 B CN103450414 B CN 103450414B
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- 229920005989 resin Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 40
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 40
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 26
- 239000003085 diluting agent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 12
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 8
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- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 4
- 229920006305 unsaturated polyester Polymers 0.000 claims description 4
- LELKUNFWANHDPG-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane;prop-2-enoic acid Chemical compound OC(=O)C=C.C1OC1COCC1CO1 LELKUNFWANHDPG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000016 photochemical curing Methods 0.000 claims description 3
- 241000522215 Dipteryx odorata Species 0.000 claims description 2
- 150000008062 acetophenones Chemical class 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000013530 defoamer Substances 0.000 description 7
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
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- 229930195729 fatty acid Natural products 0.000 description 3
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- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
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- HNBDQABBWNOTRU-UHFFFAOYSA-N thalline Chemical compound C1=CC=[Tl]C=C1 HNBDQABBWNOTRU-UHFFFAOYSA-N 0.000 description 2
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical group OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- OURRXQUGYQRVML-AREMUKBSSA-N [4-[(2s)-3-amino-1-(isoquinolin-6-ylamino)-1-oxopropan-2-yl]phenyl]methyl 2,4-dimethylbenzoate Chemical group CC1=CC(C)=CC=C1C(=O)OCC1=CC=C([C@@H](CN)C(=O)NC=2C=C3C=CN=CC3=CC=2)C=C1 OURRXQUGYQRVML-AREMUKBSSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
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- 238000007654 immersion Methods 0.000 description 1
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- 238000001746 injection moulding Methods 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
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- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
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Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides the compositions of a kind of photosensitive resin, described compositions includes UV-Curable Prepolymer, reactive diluent, photosensitizer and polyhydroxyalkanoate.The invention also discloses the preparation method of this photosensitive resin composition.The water absorption rate of the photosensitive resin composition of the present invention is less than 2.4%, and the photosensitive resin composition of the present invention has good piezoelectricity simultaneously.
Description
Technical field
Compositions that the present invention relates to a kind of photosensitive resin and preparation method thereof and photosensitive resin.
Background technology
Photosensitive resin material is a kind of special resin with many-sided superiority, is typically made up of UV-Curable Prepolymer, reactive diluent and photosensitizer.Photosensitive resin material can produce biologically active fragment under the action of uv light, causes polymerization, cross-linking reaction, realizes solidification in moment.During photosensitive resin is used in rapid laser-shaping technique (RapidPrototyping is called for short RP) in a large number at present, its ultimate principle is: be contained in resin storage tank by photosensitive resin, has one by the computer-controlled platform that can lift in resin storage tank.Add man-hour from the beginning of bottom, carry out laser scanning according to designed model.Light-cured resin crosslinks polymerization and produces a cross-sectional layers (thickness is generally 0.11-0.13mm) of part after being irradiated by ultraviolet light.Then platform moves down a height, is coated on previous cured layer by resin, solidifies new one layer, the most repeatedly, ultimately forms a complete part.Can produce with the time of traditional moulds manufacture 1/10 and manufacturing cost due to rapid laser-shaping technique and be used directly for the manufactured part of small lot injection molding.The advantages such as its curing rate is fast, production efficiency is high, Suitable commercial production line balance, photosensitive resin is increasingly widely applied in laser fast shaping manufacturing industry.
But the resistance to water of existing photosensitive resin and piezoelectricity are the most very poor, it is impossible to meet demand.Such as the Chinese patent of Publication No. CN102385250, disclose a kind of ultraviolet laser solidification rapid shaping photosensitive resin, it is characterized in that, by quality proportioning, being made up of following raw material:
Epoxy resin 5-80%
Oxetane compound 0-65%
Cationic initiators 1-12%
Hydroxyl organic compound 1-40%
Unsaturated oligomer 0-55% containing carbon-to-carbon double bond
Unsaturated monomer 0-35% containing carbon-to-carbon double bond
Low-molecular-weight glycidyl ether or title epoxide diluent 0-20%
Free radical type Photoepolymerizationinitiater initiater 0-10%.
Although the heliosensitivity of this photosensitive resin is fine, but its resistance to water and piezoelectricity are poor.
Summary of the invention
The present invention solves the resistance to water of existing photosensitive resin composition and the technical problem of piezoelectricity difference, it is provided that a kind of resistance to water and the good photosensitive resin composition of piezoelectricity and preparation method thereof.
The invention provides the compositions of a kind of photosensitive resin, described compositions includes UV-Curable Prepolymer, reactive diluent, photosensitizer and polyhydroxyalkanoate.
Present invention also offers the preparation method of this photosensitive resin composition, the method includes being mixed and stirred for performed polymer and diluent uniformly, adding polyhydroxyalkanoate, photosensitizer and additive, heated and stirred in 40-50 DEG C of water-bath, and evacuation.
Present invention also offers a kind of photosensitive resin, described photosensitive resin is formed by photosensitive resin photocuring of the present invention.
Polyhydroxyalkanoate (Polyhydroxyalkanoates is called for short PHA) joins in photosensitive resin, with photosensitive resin generation synergism, improves resistance to water and the piezoelectricity of photosensitive resin composition.And polyhydroxyalkanoate has degradability and its raw material all is from crops and plant, its product completes going back to nature of its use week after date 100%, and institute is so that photosensitive resin composition is more environmentally-friendly.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides the compositions of a kind of photosensitive resin, described compositions includes UV-Curable Prepolymer, reactive diluent, photosensitizer and polyhydroxyalkanoate.
According to compositions provided by the present invention, it is preferable that the structural formula of described polyhydroxyalkanoate is as follows:
,
Wherein, R be H, CH3-, CH3CH2-, CH3CH2CH2-, at least one in (CH3) 2CH-and CH2=CH-；M is the integer of 1-3, and n is the integer of 400-5000.
According to compositions provided by the present invention, it is preferable that described polyhydroxyalkanoate is poly butyric ester.Poly butyric ester is the Typical Representative product of polyhydroxyalkanoate, not only has the molecular structure similar to traditional chemical synthesis macromolecular material, also has similar physical property, such as similar molal weight, softening point, degree of crystallinity, hot strength etc.；And there is the performances such as density big, biological degradability, biocompatibility, piezoelectricity, optical activity, the insulating of its product and water and moisture-proof and printability are similar to polyethylene terephthalate (PET), and its physical and chemical performance is close with PP.
According to compositions provided by the present invention, it is preferable that the molecular weight of described polyhydroxyalkanoate is 1 × 105-1×107。
According to compositions provided by the present invention, it is preferable that the fusing point of described polyhydroxyalkanoate is 170 DEG C-190 DEG C.
According to compositions provided by the present invention, it is preferable that the mean diameter of described polyhydroxyalkanoate is 40-300 mesh.
According to compositions provided by the present invention, it is preferable that the weight portion of described performed polymer is 30-80 part；The weight portion of photosensitizer is 2-8 part；The weight portion of diluent is 20-60 part；The weight portion of polyhydroxyalkanoate is 10-50 part；The weight portion of additive is 1.5-5 weight portion.
According to compositions provided by the present invention, it is preferable that described performed polymer is at least one in epoxy acrylate, urethane acrylate, unsaturated polyester (UP), water-and acrylate and polyether acrylate.More preferably epoxy acrylate, owing to its cementability is high, curing rate is fast, completion of cure, heat stability is high, to substrate wetting good, good with other resin miscible, light solidifying coating glossiness is high, chemical resistance is excellent, and raw material is cheap and easy to get, especially by adjusting its consumption and kind, can adapt to the needs of varying strength, thus preferentially select.
According to compositions provided by the present invention, it is preferable that described diluent is at least one in trimethylolpropane trimethacrylate, NVP and aliphatic glycidyl ether acrylic acid ester.More preferably trimethylolpropane trimethacrylate (TMPTA), has the features such as double bond content high, curing rate is fast, viscosity is low, high boiling point, low volatility, thus the present invention preferentially selects due to TMPTA.
According to compositions provided by the present invention, preferably, at least one during described photosensitizer is Benzoinum class photosensitizer, acetophenones photosensitizer, willow miscellaneous anthrone class photosensitizer, tonkabean ketone photosensitizer, benzophenone class photosensitizer, aromatic diazo salt photosensitizer and iron arene complexes class photosensitizer.More preferably benzoin dimethylether, owing to its curing rate is fast, good stability, thus the present invention preferentially selects.
According to compositions provided by the present invention, it is preferable that described compositions also includes additive.It is highly preferred that described additive includes defoamer and pigment.Described defoamer is at least one in amide-type, fatty acid, phosphoric acid ester, polyethers and silicone.Described pigment is at least one in organic pigment and inorganic pigment.
Present invention also offers the preparation method of a kind of compositions of the present invention, the method includes being mixed and stirred for performed polymer and diluent uniformly, adding polyhydroxyalkanoate, photosensitizer and additive, heated and stirred in 40-50 DEG C of water-bath, and evacuation.
According to preparation method provided by the present invention, it is preferable that described preparation method comprises the following steps:
A. fermentation the centrifugal vickers nitrogen-fixing bacteria thalline obtained containing polyhydroxyalkanoate are first passed through；
B. make antibacterial breaking cellular wall with the anion surfactant alkaline solution agitator treating microorganism that pH value is 9-13 and its cell wall is degraded to fractionlet, discharging cell Dissolve things inside simultaneously；
C. the polyhydroxyalkanoate granule of separation and Extraction solid phase；Remove the major part non-polyhydroxyalkanoate composition produced in fermentation；
The most again with the enzymatic solution further agitator treating granule of the alkaline protein that temperature is 40-80 DEG C, remove the protein impurities of residual；Improve its purity further and be substantially reduced its protein impurities content so that it is meeting the requirement being processed further；
E. separating-purifying solid polycondensation hydroxy fatty acid granule；
F. drying and grinding obtains polyhydroxyalkanoate particle powder.
Present invention also offers a kind of photosensitive resin, described photosensitive resin is formed by photosensitive resin composition photocuring of the present invention.
The present invention is described in further detail by application specific embodiment below.
Embodiment 1
1, polyhydroxyalkanoate granule is prepared
A. fermentation the centrifugal vickers nitrogen-fixing bacteria thalline obtained containing polyhydroxyalkanoate are first passed through；
B. make antibacterial breaking cellular wall with the anion surfactant alkaline solution agitator treating microorganism that pH value is 10 and its cell wall is degraded to fractionlet, discharging cell Dissolve things inside simultaneously；
C. the polyhydroxyalkanoate granule of separation and Extraction solid phase；Remove the major part non-polyhydroxyalkanoate composition produced in fermentation；
The most again with the enzymatic solution further agitator treating granule of the alkaline protein that temperature is 60 DEG C, remove the protein impurities of residual；Improve its purity further and be substantially reduced its protein impurities content so that it is meeting the requirement being processed further；
E. separating-purifying solid polycondensation hydroxy fatty acid granule；
F. drying and grinding obtain particle diameter be 100 mesh, molecular weight be 1 × 105, fusing point be the polyhydroxyalkanoate particle powder of 178 DEG C.
2, photosensitive resin composition is prepared
Epoxy acrylate and trimethylolpropane trimethacrylate are mixed and stirred for uniformly, add the polyhydroxyalkanoate of above-mentioned preparation, benzoin dimethylether, defoamer and pigment, heated and stirred in 40 DEG C of water-baths, and evacuation i.e. obtains photosensitive resin composition A1.The weight portion of the most each material is as follows:
Epoxy acrylic resin 50 parts
Polyhydroxyalkanoate 30 parts
Benzoin dimethylether 5 parts
Trimethylolpropane trimethacrylate 40 parts
Pigment 1 part
Defoamer 2 parts.
Embodiment 2
1, the poly butyric ester being purchased, particle diameter be 200 mesh, molecular weight be 1 × 107, fusing point be 180 DEG C.
2, preparing photosensitive resin composition A2 according to the method for embodiment 1, difference is:
The weight portion of the most each material is as follows:
Urethane acrylate 30 parts
Polyhydroxyalkanoate 40 parts
Benzophenone 8 parts
NVP 20 parts
Pigment 2 parts
Defoamer 1 part.
Embodiment 3
1, the poly butyric ester being purchased, difference is: the particle diameter of polyhydroxyalkanoate be 40 mesh, molecular weight be 8.6 × 105, fusing point be 170 DEG C.
2, preparing photosensitive resin composition A3 according to the method for embodiment 1, difference is:
The weight portion of the most each material is as follows:
Water-and acrylate 80 parts
Polyhydroxyalkanoate 10 parts
1-Phenylethanone. 2 parts
Aliphatic glycidyl ether acrylic acid ester 60 parts
Pigment 0.5 part
Defoamer 3 parts.
Embodiment 4
1, the poly butyric ester being purchased, difference is: the particle diameter of polyhydroxyalkanoate be 300 mesh, molecular weight be 1.2 × 106, fusing point be 190 DEG C.
2, preparing photosensitive resin composition A4 according to the method for embodiment 1, difference is:
The weight portion of the most each material is as follows:
Polyether acrylate 60 parts
Polyhydroxyalkanoate 50 parts
Coumarone 4 parts
Trimethylolpropane trimethacrylate 50 parts
Pigment 1.5 parts
Defoamer 2.5 parts.
Comparative example 1
Prepare the photosensitive resin composition B1 disclosed in CN102385250.
Method of testing and result
1, resistance to water
Photosensitive resin composition A1-A4 and B1 prepared is respectively coated on sheet glass, thickness is 1～2mm, is placed under the ultraviolet high-pressure mercury lamps of 500W irradiation, sample distance uviol lamp 10cm, hardening time with finger touch resin surface tack-free till, obtain sample film.Thin film is placed in drying baker and dries to constant weight, then put it in the water bath with thermostatic control of 20-30 DEG C immersion 1d, quickly dry surface after taking-up and weigh, by be calculated sample water absorption rate.The results are shown in Table 1.
2, piezoelectricity
First cured film is inserted in high pressure chest and be passed through the N2 of certain pressure, after at room temperature depositing certain time, high pressure chest is warming up to specified temp and stores and open high pressure chest after certain time and exit rapidly, and store for future use after naturally cooling to room temperature.The thickness of sample is measured by the micrometer of a band spring contact.Using normal pressure negative some corona discharge and contact method polarized sample, charging interval tp=15s, corona pin and sample distance 4cm during corona charging, the regulation and control of corona voltage should avoid causing the spark discharge of air.Measure its surface potential by penalty method immediately after sample polarization, and store two-sided electrode evaporation after a period of time at normal temperatures and pressures, contact method polarized sample then before polarization to two-sided electrode evaporation.Dynamic method is utilized to measure piezoelectric coefficient d33.The results are shown in Table 1.
Table 1
| Resistance to water/(water absorption rate %) | Piezoelectricity/(piezoelectric coefficient d33) | |
| A1 | 1.5 | 11 |
| A2 | 1.2 | 13 |
| A3 | 2.4 | 9 |
| A4 | 0.8 | 14 |
| B1 | 16 | / |
From table 1 it follows that the water absorption rate of the photosensitive resin composition of the present invention is less than 2.4%, and the water absorption rate of the photosensitive resin composition of comparative example is 16%, is far longer than the water absorption rate of the photosensitive resin composition of the present invention.The photosensitive resin composition of the present invention has good piezoelectricity simultaneously, but the photosensitive resin composition of comparative example does not have piezoelectricity.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, should be included within the scope of the present invention.
Claims (11)
1. the compositions of a photosensitive resin, it is characterised in that described compositions includes UV-Curable Prepolymer, reactive diluent, photosensitizer and polyhydroxyalkanoate；The weight portion of described performed polymer is 30-80 part；The weight portion of photosensitizer is 2-8 part；The weight portion of diluent is 20-60 part；The weight portion of polyhydroxyalkanoate is 10-50 part；The weight portion of additive is 1.5-5 weight portion.
Compositions the most according to claim 1, it is characterised in that the structural formula of described polyhydroxyalkanoate is as follows:
,
Wherein, R is H, CH3-、CH3CH2-、CH3CH2CH2-, (CH3)2CH-and CH2At least one in=CH-；M is the integer of 1-3, and n is the integer of 400-5000.
Compositions the most according to claim 1, it is characterised in that described polyhydroxyalkanoate is poly butyric ester.
Compositions the most according to claim 1, it is characterised in that the molecular weight of described polyhydroxyalkanoate is 1 × 105-1×107。
Compositions the most according to claim 1, it is characterised in that the fusing point of described polyhydroxyalkanoate is 170 DEG C-190 DEG C.
Compositions the most according to claim 1, it is characterised in that the mean diameter of described polyhydroxyalkanoate is 40-300 mesh.
Compositions the most according to claim 1, it is characterised in that described performed polymer is at least one in epoxy acrylate, urethane acrylate, unsaturated polyester (UP), water-and acrylate and polyether acrylate.
Compositions the most according to claim 1, it is characterised in that described diluent is at least one in trimethylolpropane trimethacrylate, NVP and aliphatic glycidyl ether acrylic acid ester.
Compositions the most according to claim 1, it is characterized in that, described photosensitizer is at least one in Benzoinum class photosensitizer, acetophenones photosensitizer, thioxanthones photosensitizer, tonkabean ketone photosensitizer, benzophenone class photosensitizer, aromatic diazo salt photosensitizer and iron arene complexes class photosensitizer.
10. the preparation method of the compositions described in a claim 1, it is characterized in that, the method includes being mixed and stirred for performed polymer and diluent uniformly, adding polyhydroxyalkanoate, photosensitizer and additive, heated and stirred in 40-50 DEG C of water-bath, and evacuation.
11. 1 kinds of photosensitive resins, it is characterised in that this photosensitive resin is formed by the compositions photocuring described in claim 1-9 any one.
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| CN201210167639.XA CN103450414B (en) | 2012-05-28 | 2012-05-28 | Compositions of a kind of photosensitive resin and preparation method thereof and photosensitive resin |
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| CN201210167639.XA CN103450414B (en) | 2012-05-28 | 2012-05-28 | Compositions of a kind of photosensitive resin and preparation method thereof and photosensitive resin |
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| Publication Number | Publication Date |
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| CN103450414B true CN103450414B (en) | 2016-08-03 |
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|---|---|---|---|---|
| CN104710548B (en) * | 2014-01-03 | 2017-09-29 | 南京波斯塔新材料科技有限公司 | A kind of 3D printing core material |
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| CN109796853A (en) * | 2018-11-28 | 2019-05-24 | 湖南阳光新材料有限公司 | A kind of ultraviolet light solidification heat conduction and heat radiation vehicle reflector coating and preparation method thereof |
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| CN101815698A (en) * | 2007-08-02 | 2010-08-25 | 巴斯夫欧洲公司 | Degradation accelerator for polymers and polymer article comprising it |
| CN101963757A (en) * | 2009-07-25 | 2011-02-02 | 比亚迪股份有限公司 | Organic silicon modified alkali soluble photosensitive resin, preparation method thereof and printing ink composition |
| CN102375336A (en) * | 2010-08-05 | 2012-03-14 | 旭化成电子材料株式会社 | Manufacturing Method Of Photosensitive Resin Composition And Solidified Embossing Pattern, And Semiconductor Device |
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