CN106632932A - UV-curable resin - Google Patents
UV-curable resin Download PDFInfo
- Publication number
- CN106632932A CN106632932A CN201611004617.6A CN201611004617A CN106632932A CN 106632932 A CN106632932 A CN 106632932A CN 201611004617 A CN201611004617 A CN 201611004617A CN 106632932 A CN106632932 A CN 106632932A
- Authority
- CN
- China
- Prior art keywords
- formaldehyde
- acid
- urea
- degree
- vacuumize
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09D161/14—Modified phenol-aldehyde condensates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention relates to a method for producing UV resin by taking urea and formaldehyde which are base materials in the field of coal chemical industry as main raw materials. The resin is small in smell and excellent in yellowing performance, thereby being capable of being taken as base resin to be widely used in bottom paint of UV woodenwares and UV paint of PVC buckle plates.
Description
Technical field
The present invention relates to one kind utilizes urea, the basestocks of formaldehyde --- coal chemical technology are the method that primary raw material manufactures UV resins,
The resin smell is little, xanthochromia excellent performance, can be widely used in UV woodenware bottom surface paint and PVC buckles UV paints as matrix resin.
Background technology
Traditional solvent wood coatings, it is positive due to containing substantial amounts of solvent VOC maximum discharges, larger pressure being caused to environment
Solvent-free environment-protection woodwork coating changes.Wherein there is prospect the most with UV coating, apply more than 80% in plane base material at present
Instead of traditional solvent based coating.But UV coatings industries have the defect of itself：One is that UV coating is not also accomplished very in isomery face
Good solidification, this part, traditional coating may develop towards water paint.Two is that the surface effect that UV coating is applied also does not reach biography
System solvent based coating applies effect, and this part, traditional solvent-borne coating still retains.Three is UV coating resins raw material sources ratio
Relatively narrower --- nearly all it is fine chemical product, price is high, and this causes portions of client it is contemplated that price factor is still selected
Select solvent based coating.For example show the maximum UV resins of consumption, epoxy acrylate is closed by 25% acrylic acid and 75% epoxy resin
Into.Epoxy resin belongs to fine chemistry industry, and synthesis technique is complicated, and price is high.
If the bulk raw material of UV resins is bypassed into fine chemistry industry and joint petrochemical industry, gas chemical industry or coal carbonization
Then UV resin raw materials price has a larger range of decrease to work.
In coal chemical industry, urea is cheap.Gone to produce UV resins, UV resin valencys as main raw material(s) with urea-formaldehyde
Lattice have the larger range of decrease.UV coating and traditional solvent based coating compare then without price inferior position, further promote traditional coating
To UV development.
Urea-formaldehyde UV resins, as other UV resins a performance requirement and index are had to comply with.Due to using
Formaldehyde is raw material, and paint film release formaldehyde naturally becomes the emphasis of control；Formaldehyde is added, and smell can be caused to increase, if not
Control free formaldehyde, then smell is pungent, and smell is control object.
1st, resin outward appearance：As clear as crystal mechanical impurity, the slightly yellow thick liquid of color
2nd, color：≤1#（Fe-Co colorimeters）
3rd, storage stability：80 DEG C, 72 hours（Sealing experiment）, increase s.mPa/25 DEG C of viscosity≤1000.
4th, free formaldehyde：≤ 0.5g/kg, quotes harmful substance limit in the solvent-based adhesive of GB18583-2001.3.1 tables 1
Value.
5th, dry film formaldehyde：≤ 40 mg/100g quote GB18585-2001《Harmful substance limit in indoor decorating and refurnishing materials
Amount》, solid wooden compound floor, B classes
6th, dry film smell：With net taste light trigger, separately made dry film is heard resin and is applied at 15-30 μm, directly in white ceramic tiles
Film has no irritating odor.
The content of the invention
It is contemplated that preparing a kind of urea-formaldehyde UV resins, it is made up of following portions by weight：
Urea 60；
Formaldehyde 60 ~ 90；
（Methyl）Crylic acid hydroxy ester 232 ~ 464；
Polymerization inhibitor polymerization inhibitor is the 0.03 ~ 0.1% of above-mentioned raw materials gross mass
The 0.25% of alkaline PH conditioning agents alkalescence PH conditioning agent total amounts
The 0.5% of acid PH conditioning agents acidity PH conditioning agent total amounts.
Formaldehyde catching agent
Described urea can be agricultural urea or industrial urea
It can also be liquid formalin that described formaldehyde can be solid formaldehyde, can be assumed that when raw material is solid formaldehyde and contain
Measure as 100%, when raw material is formalin, content of formaldehyde is defined according to actually detected value（Meet wanting for GB/T9009-2011
Ask, and detection method of content）.
Described（Methyl）Crylic acid hydroxy ester can be one or more following：2-Hydroxy ethyl acrylate
(HEA), methacrylic acid -2- hydroxy methacrylates (HEMA), acrylic acid -2- hydroxyl n-propyls (HPA), acrylic acid -2- hydroxyl isopropyls
Ester (HPA), methacrylic acid -2- hydroxyl n-propyls (HPMA), methacrylic acid -2- hydroxyl isopropyl esters (HPMA).
Described polymerization inhibitor using it is following one or more：MEHQ, TBHQ, 2- methoxyl groups pair
Benzenediol.
Described alkaline PH conditioning agents, using it is following one or more：Triethylamine, triethanolamine, triisopropanolamine, N, N
Dimethyl benzylamine, N, N diethyl benzylamine.
Described acid PH conditioning agents, using it is following one or more：Hydrochloric acid, phosphoric acid, p-methyl benzenesulfonic acid.
Described formaldehyde catching agent is：Dicyclohexylurea (DCU)（DCU）
The invention further relates to the preparation method of urea-formaldehyde UV resins.Comprise the following steps：
1st, urea, formalin（Or solid formaldehyde）、（Methyl）Dissolve in crylic acid hydroxy ester input reactor, plus alkalescence PH is adjusted
The 0.25% of section agent total amount, is warmed up to 60-65 degree, is incubated 45 minutes, then is warmed up to 90-92 degree insulation 2 hours.
2nd, cool to 65-68 to spend, the 0.5% of Plus acidic PH conditioning agents total amount.
3rd, sleeping cold, 65-68 degree are opened ,-80KPa vacuums vacuumize 1 hour.
4th, 85 degree are warmed up to, continue to vacuumize, till not water outlet, continue to vacuumize 1 hour.
5th, by GB18583-2008, appendix A 5.2.2 methods determine free formaldehyde content≤1700ppm, otherwise continue to take out true
Sky is until desired value.
6. less than 55 degree are cooled to, by free formaldehyde content formaldehyde catching agent is added, addition is 6 times of formaldehyde.
Specific embodiment
Following number is parts by weight.
Embodiment 1：The present invention is made up of following weight than raw material：
Urea 60；
Formalin（Or solid formaldehyde） 90；
Hydroxyethyl Acrylate（HEMA） 232~348；
MEHQ 0.3
Triethylamine 1.24
P-methyl benzenesulfonic acid 2.48
Dicyclohexylurea (DCU) 5.08
1st, stirring is opened, 60 parts of urea, 90 parts of solid formaldehydes, 232 parts of crylic acid hydroxy esters is put in reactors, plus alkalescence PH
1.24 parts of triethylamine, plus 0.3 part of polymerization inhibitor MEHQ are adjusted, 60-65 degree are heated to, 45 minutes are incubated, then is risen
Temperature was to 90-92 degree insulation 2 hours.
2nd, 65-68 degree, Plus acidic 2.48 parts of PH conditioning agents p-methyl benzenesulfonic acid are cooled to.
3rd, 65-68 degree, opens sleeping cold, and 1 hour is vacuumized under-80KPa vacuums.
4th, 85 degree are warmed up to, -80KPa continues to vacuumize, till not water outlet, continue to vacuumize 1 hour.
5th, by GB18583-2008, appendix A 5.2.2 methods determine free formaldehyde content, and≤1700ppm otherwise continues to take out
Vacuum is until desired value.
6. less than 55 degree are cooled to, adds 5.08 parts of formaldehyde catching agent dicyclohexylurea (DCU), stir discharging.
Embodiment 2：The present invention is made up of following weight than raw material：
Urea 60；
Formalin 90；
Hydroxyethyl methacrylate（HEMA） 260~390；
MEHQ 0.3
Triethylamine 1.24
P-methyl benzenesulfonic acid 2.48
Dicyclohexylurea (DCU) 5.51
1. the content of formaldehyde of formalin is detected according to the requirement of GB/T9009-2011.Formalin in above-mentioned or following
Weight is really the weight of the pure formaldehyde in the inside.
2nd, stirring is opened by 60 parts of urea, 90 parts of formalin, 260 parts of methacrylic acid hydroxy ester input reactors
Dissolving, plus 1.24 parts of alkalescence PH conditioning agent triethylamines, plus 0.3 part of polymerization inhibitor MEHQ, heat to 60-65 degree,
Insulation 45 minutes, then it is warmed up to 90-92 degree insulation 2 hours.
3rd, 65-68 degree are cooled to, Plus acidic PH adjusts 2.48 parts of p-methyl benzenesulfonic acid.
4th, sleeping cold, 65-68 degree are opened ,-80KPa vacuums vacuumize 1 hour.
5th, 85 degree are warmed up to, -80KPa continues to vacuumize, till not water outlet, continue to vacuumize 1 hour.
6th, by GB18583-2008, appendix A 5.2.2 methods determine free formaldehyde content, and free formaldehyde≤1700ppm is no
Then continue to vacuumize until desired value.
7. less than 55 degree are cooled to, adds 5.51 parts of formaldehyde catching agent dicyclohexylurea (DCU), stir discharging.
Embodiment 3：The present invention is made up of following weight than raw material：
Urea 60；
Formalin 90；
Hydroxypropyl acrylate（HPA） 260~390；
MEHQ 0.3
Triethylamine 1.24
P-methyl benzenesulfonic acid 2.48
Dicyclohexylurea (DCU) 5.51
1. the content of formaldehyde of formalin is detected according to the requirement of GB/T9009-2011.Formalin in above-mentioned or following
The weight of the actual pure formaldehyde of weight.
2nd, stirring is opened by 60 parts of urea, 90 parts of formalin, 390 parts of hydroxypropyl acrylates（HPA）In input reactor
Dissolving, plus 1.24 parts of alkalescence PH conditioning agent triethylamines, plus 0.3 part of polymerization inhibitor MEHQ, heat to 60-65 degree,
Insulation 45 minutes, then it is warmed up to 90-92 degree insulation 2 hours.
3rd, 65-68 degree are cooled to, Plus acidic PH adjusts 2.48 parts of p-methyl benzenesulfonic acid.
4th, sleeping cold, 65-68 degree are opened ,-80KPa vacuums vacuumize 1 hour.
5th, 85 degree are warmed up to, -80KPa continues to vacuumize, till not water outlet, continue to vacuumize 1 hour.
6th, by GB18583-2008, appendix A 5.2.2 methods determine free formaldehyde content, and free formaldehyde≤1700ppm is no
Then continue to vacuumize until desired value.
7. less than 55 degree are cooled to, adds 5.51 parts of formaldehyde catching agent dicyclohexylurea (DCU), stir discharging.
Embodiment 4：The present invention is made up of following weight than raw material：
Urea 60；
Formalin 90；
Hydroxy propyl methacrylate（HPMA） 288~432；
MEHQ 0.3
Triethylamine 1.24
P-methyl benzenesulfonic acid 2.48
Dicyclohexylurea (DCU) 5.94
1. the content of formaldehyde of formalin is detected according to the requirement of GB/T9009-2011.Formalin in above-mentioned or following
The weight of the actual pure formaldehyde of weight.
2nd, stirring is opened by 60 parts of urea, 90 parts of formalin, 288 parts of hydroxy propyl methacrylates（HPMA）Input is anti-
Answer in kettle and dissolve, plus 1.24 parts of alkalescence PH conditioning agent triethylamines, plus 0.3 part of polymerization inhibitor MEHQ, heat to
60-65 degree, are incubated 45 minutes, then are warmed up to 90-92 degree insulation 2 hours.
3rd, 65-68 degree are cooled to, Plus acidic PH adjusts 2.48 parts of p-methyl benzenesulfonic acid.
4th, sleeping cold, 65-68 degree are opened ,-80KPa vacuums vacuumize 1 hour.
5th, 85 degree are warmed up to, -80KPa continues to vacuumize, till not water outlet, continue to vacuumize 1 hour.
6th, by GB18583-2008, appendix A 5.2.2 methods determine free formaldehyde content, and free formaldehyde≤1700ppm is no
Then continue to vacuumize until desired value.
7. less than 55 degree are cooled to, adds 5.94 parts of formaldehyde catching agent dicyclohexylurea (DCU), stir discharging.
Claims (1)
1. the present invention is a kind of general UV-cured resin, is made up of following portions by weight：
Urea 60；
Formaldehyde 60 ~ 90；
（Methyl）Crylic acid hydroxy ester 232 ~ 464；
Polymerization inhibitor polymerization inhibitor is the 0.03 ~ 0.1% of above-mentioned raw materials gross mass
Alkaline PH conditioning agents
Acid PH conditioning agents
Formaldehyde catching agent
Described urea can be agricultural urea or industrial urea
It can also be liquid formalin that described formaldehyde can be solid formaldehyde, can be assumed that when raw material is solid formaldehyde and contain
Measure as 100%, when raw material is formalin, content of formaldehyde is defined according to actually detected value（Meet wanting for GB/T9009-2011
Ask, and detection method of content；
Described（Methyl）Crylic acid hydroxy ester can be one or more following：2-Hydroxy ethyl acrylate (HEA), first
Base 2-Hydroxy ethyl acrylate (HEMA), acrylic acid -2- hydroxyl n-propyls (HPA), acrylic acid -2- hydroxyl isopropyl esters (HPA),
Methacrylic acid -2- hydroxyl n-propyls (HPMA), methacrylic acid -2- hydroxyl isopropyl esters (HPMA)；
Described polymerization inhibitor using it is following one or more：MEHQ, TBHQ, 2- methoxyl groups are to benzene two
Phenol；
Described alkaline PH conditioning agents, using it is following one or more：Triethylamine, triethanolamine, triisopropanolamine, N, N diformazan
Base benzylamine, N, N diethyl benzylamine；
Described acid PH conditioning agents, using it is following one or more：Hydrochloric acid, phosphoric acid, p-methyl benzenesulfonic acid；
Described formaldehyde catching agent is：Dicyclohexylurea (DCU)（DCU）
The invention further relates to the preparation method of urea-formaldehyde UV resins；
Comprise the following steps：
S1, urea, formalin（Or solid formaldehyde）、（Methyl）Dissolve in crylic acid hydroxy ester input reactor, plus alkalescence PH
The 0.25% of conditioning agent total amount, is warmed up to 60-65 degree, is incubated 45 minutes, then is warmed up to 90-92 degree insulation 2 hours；
Cool to 65-68 to spend, the 0.5% of Plus acidic PH conditioning agents total amount；
S3, sleeping cold, 65-68 degree are opened ,-80KPa vacuums vacuumize 1 hour；
S4,85 degree are warmed up to, continue to vacuumize, till not water outlet, continue to vacuumize 1 hour；
S5, by GB18583-2008, appendix A 5.2.2 methods determine free formaldehyde content≤1700ppm, otherwise continue to vacuumize
Until desired value；
S6. less than 55 degree are cooled to, by free formaldehyde content formaldehyde catching agent is added, addition is 6 times of formaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611004617.6A CN106632932B (en) | 2016-11-15 | 2016-11-15 | UV-cured resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611004617.6A CN106632932B (en) | 2016-11-15 | 2016-11-15 | UV-cured resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106632932A true CN106632932A (en) | 2017-05-10 |
| CN106632932B CN106632932B (en) | 2019-03-05 |
Family
ID=58806904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611004617.6A Active CN106632932B (en) | 2016-11-15 | 2016-11-15 | UV-cured resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106632932B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177983A (en) * | 2014-08-28 | 2014-12-03 | 漳州鑫展旺化工有限公司 | Self-repairing anticorrosive coating and preparation method thereof |
| CN105061265A (en) * | 2015-07-30 | 2015-11-18 | 江门市广耀化工有限公司 | Preparation method of low formaldehyde urea solution used for urea |
| CN105218716A (en) * | 2015-10-21 | 2016-01-06 | 中山大桥化工集团有限公司 | A kind of UV-cured resin and preparation method thereof |
| CN105669962A (en) * | 2016-03-16 | 2016-06-15 | 无锡海特圣大光电材料科技有限公司 | Preparation method of novel ultraviolet light curing powder coating resin |
| CN105669446A (en) * | 2015-12-31 | 2016-06-15 | 上海美东生物材料股份有限公司 | Ultraviolet-curable resin and preparation method thereof |
-
2016
- 2016-11-15 CN CN201611004617.6A patent/CN106632932B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177983A (en) * | 2014-08-28 | 2014-12-03 | 漳州鑫展旺化工有限公司 | Self-repairing anticorrosive coating and preparation method thereof |
| CN105061265A (en) * | 2015-07-30 | 2015-11-18 | 江门市广耀化工有限公司 | Preparation method of low formaldehyde urea solution used for urea |
| CN105218716A (en) * | 2015-10-21 | 2016-01-06 | 中山大桥化工集团有限公司 | A kind of UV-cured resin and preparation method thereof |
| CN105669446A (en) * | 2015-12-31 | 2016-06-15 | 上海美东生物材料股份有限公司 | Ultraviolet-curable resin and preparation method thereof |
| CN105669962A (en) * | 2016-03-16 | 2016-06-15 | 无锡海特圣大光电材料科技有限公司 | Preparation method of novel ultraviolet light curing powder coating resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106632932B (en) | 2019-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101921357B (en) | High-solid low-viscosity hydroxy acrylic resin and preparation process thereof | |
| CN103756530A (en) | High-flexibility anti-cracking primer and preparation method thereof | |
| CN105504137B (en) | A kind of cold-resistant hot water soluble self-drying acrylic resin and preparation method thereof | |
| EP3224283B1 (en) | Polymer dispersions | |
| CN104371607B (en) | High-solid-content and low-viscosity acrylate emulsion stick and preparation method | |
| CN104114585B (en) | Vinylidene chloride based copolymer emulsion and Blister Package film | |
| EP2855579A1 (en) | Aqueous binder compositions | |
| CN104559698B (en) | A kind of color inhibition UV transparent primings for electrostatic spraying | |
| CN104497831B (en) | A kind of crystal coating | |
| CN105859951A (en) | Water-soluble acrylic resin and preparing method thereof | |
| CN102351979A (en) | Acrylic resin coating liquid for alumite coloring layer and preparation method thereof | |
| MX2015006182A (en) | Use of aqueous polymer dispersion in coating agents for improving colour retention. | |
| US20130303674A1 (en) | Powerfeed polymers having improved block resistance performance | |
| CN102167948A (en) | UV (ultraviolet) photo-cured acrylic resin composition | |
| CN107163256A (en) | Epoxy modified aqueous acrylic acid resin and the aqueous vacuum coating priming paint prepared with it | |
| KR100336528B1 (en) | Non-aqueous paints | |
| CN104479488B (en) | A kind of preparation method of corrosion resistant emulsion paint | |
| CA3189747A1 (en) | Aqueous polymer latex of film-forming copolymers suitable as binder in waterborne coating compositions | |
| CN108822285A (en) | The low thinning of the low hydroxyl of high-solid lower-viscosity is than alkyd resin and its preparation method and application | |
| CN102587203B (en) | High-gloss water-borne coating and preparation method as well as application thereof | |
| CN105219311B (en) | A kind of preparation and its application of water soluble acrylic acid ester pressure-sensitive | |
| CN105238199A (en) | Room-temperature self-crosslinkable polyacrylic wood varnish and preparation method thereof | |
| CN104693371A (en) | New acrylic acid modified resin for water-based two-component polyurethane coating | |
| CN106632932A (en) | UV-curable resin | |
| CN109880002B (en) | Solvent-free low-gloss hydroxyl acrylic acid dispersion and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 516221 No. 30 Xiayong Petrochemical Avenue, Daya Bay, Huizhou City, Guangdong Province Patentee after: Guangdong Libang Changrunfa Science and Technology Material Co., Ltd. Address before: 516083 L3 Block, Petrochemical Zone, No. 30 Xiayong Petrochemical Avenue, Daya Bay District, Huizhou City, Guangdong Province Patentee before: Huizhou Changrunfa Coating Co., Ltd. |
|
| CP03 | Change of name, title or address |