CN101786021B - Catalyst for accelerating ultraviolet curing and preparation method thereof - Google Patents
Catalyst for accelerating ultraviolet curing and preparation method thereof Download PDFInfo
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- CN101786021B CN101786021B CN2010101219709A CN201010121970A CN101786021B CN 101786021 B CN101786021 B CN 101786021B CN 2010101219709 A CN2010101219709 A CN 2010101219709A CN 201010121970 A CN201010121970 A CN 201010121970A CN 101786021 B CN101786021 B CN 101786021B
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- salt
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- ultraviolet curing
- acrylate
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Abstract
The invention provides a catalyst for accelerating ultraviolet curing and a preparation method thereof. The catalyst comprises the following components in parts by weight: 2-55 parts of Sn<> salt, 2-28 parts of Co<> salt and 2-70 parts of Zn<> salt, mixture of three salts. The preparation method comprises the following steps: stirring the mixture of Sn<>, Co<> and Zn<> salts, which are proportionally weighed, for 20 minutes. Single functional group acrylate monomers can also be added to the catalyst to promote the dissolution of the components; and then, the preparation method comprises the following steps: adding the solid or liquid of the three salts proportionally weighed into the single functional group acrylate monomers; stirring at 40-55 DEG C for 2 hours until the mixture becomes transparent and uniform; and packaging for use. The catalyst can increase the curing speed by 5-20 m/min when being used in the formula of the ultraviolet curing system. Both the hardness and the wearability of the film are enhanced after being cured.
Description
Technical field
The invention belongs to ultraviolet light polymerization system preparation field, particularly accelerate the preparation method of the auxiliary agent of ultraviolet light polymerization speed.
Background technology
UV-curing technology is to belong to a kind of most important curing in the radiation curing technology, because technical characterstics such as UV-curing technology has efficiently, environmental protection, excellent performance, in recent years rapidly in China's development, particularly all there is the speed that is exceedingly fast increasing in coating, printing ink, adhesive field, owing to use so as not to popularizing, more and more higher to the curing technology requirement, also be more important so improve the importance of curing technology.
Though ultraviolet light polymerization is a kind of curing more fast, but because oligomer, the monomer classification of system are different, functional group is different, in polymerization process, be difficult to reach the quick curing of unanimity, at present only way is to use the way that increases light trigger, and the residual initator of this way has the weakness of two aspects: the one, and initator residual quickened the aging of film forming, and weatherability is poor; The 2nd, the toxicity of initator is bigger, should not be used for the relevant process of food, has limited the application of ultraviolet light polymerization.So improving curing rate is an important and complicated problems, prepare a kind of can curing by quick catalysis, the application that reduces initator is very important.
Summary of the invention
Big in order to solve in the existing ultraviolet light polymerization system light trigger consumption, the shortcoming that curing rate is not high enough, the catalyst that the invention provides a kind of like this preparation method can quicken the speed of raising ultraviolet light polymerization and the consumption of minimizing light trigger.
Technical scheme of the present invention is: a kind of catalyst of accelerating ultraviolet curing in weight portion, consists of:
Sn
2+Salt 2～55;
Co
2+Salt 2～28;
Zn
2+The mixture of salt 2～70 3 kind of salt.
Described Sn
2+Salt, Co
2+Salt, Zn
2+Salt be in hydrochloride, sulfate, naphthenate, chlorate, nitrate, the stearate (octadecane hydrochlorate) any one.Described Sn
2+Co
2+, Zn
2+The mixture of salt is meant that several salt mix by above-mentioned.
The preparation method is with load weighted Sn
2+Salt, Co
2+Salt, Zn
2+The mixture of salt stir the 20min system and evenly get final product.
In order to obtain better effect, in the catalyst of above-mentioned accelerating ultraviolet curing, can also add the simple function group acrylate monomer again to promote the dissolving of each composition, in weight portion, consist of:
Sn
2+Salt 2～55;
Co
2+Salt 2～28;
Zn
2+Salt 2～70;
Simple function group acrylate monomer 1～40.
The acrylate monomer of described simple function group is any one in methyl acrylate, butyl acrylate, Isooctyl acrylate monomer, hydroxy-ethyl acrylate, hydroxypropyl acrylate, propylene halide acid hydroxypropyl acrylate, methyl methacrylate, butyl methacrylate, EHMA, hydroxyethyl methacrylate, hydroxy propyl methacrylate, the halogenated methyl hydroxypropyl acrylate.
At this moment, the preparation method is: with the solid or the liquid of load weighted three kinds of salt, add the acrylate monomer of simple function group, stirred 2 hours at 40～55 ℃, extremely transparent uniform state can be packed use.
Beneficial effect
In the ultraviolet light polymerization system, use catalyst of the present invention in prescription, to reach 0.5～3%wt, just can improve curing rate 5～20m/min.Reach identical curing rate, can will reduce the light trigger use amount of 1～2%wt, in a lot of systems even can cut the aided initiating of 50%wt amount than the situation that does not add catalyst of the present invention.The hardness and the wearability of the film after the curing all increase.
The specific embodiment
Following percentage is all mass percent.
A kind of catalyst of accelerating ultraviolet curing in weight portion, consists of:
Sn
2+Salt 2～55: such as getting numerical value such as 2,10,20,55;
Co
2+Salt 2～28: can be numerical value such as 2,10,20,28;
Zn
2+Salt 2～70; Can be numerical value such as 2,10,30,70;
Simple function group acrylate monomer 0～40: can be the numerical value between 0,10,20,40 etc. 0～40, described Sn
2+, Co
2+, Zn
2+Any component of salt be present in the ultraviolet light polymerization system.
Described Sn
2+Salt, Co
2+Salt, Zn
2+Salt be in hydrochloride, sulfate, naphthenate, chlorate, nitrate, the stearate any one.
The acrylate monomer of described simple function group is any one in methyl acrylate, butyl acrylate, Isooctyl acrylate monomer, hydroxy-ethyl acrylate, hydroxypropyl acrylate, propylene halide acid hydroxypropyl acrylate, methyl methacrylate, butyl methacrylate, EHMA, hydroxyethyl methacrylate, hydroxy propyl methacrylate, the halogenated methyl hydroxypropyl acrylate.
When adding the simple function group acrylate monomer, with described Sn
2+, Co
2+, Zn
2+Salt mixes in the acrylate monomer that is dissolved in simple function group by a certain percentage, stirs 2 hours at 40～55 ℃, presents transparent uniform state and can pack use.
When not adding the simple function group acrylate monomer, each component is stirred 20min make evenly, presenting translucent can use.
Embodiment 1
Can be configured by following step:
Stannic chloride (SnCl
2) 20%, cobalt chloride (CoCl
2) 28%, zinc stearate: 15%, Isooctyl acrylate monomer 37%.Several materials are added in the Isooctyl acrylate monomer successively,, present transparent uniform state and can pack use stirring 2 hours at 40-55 ℃.
In as the prescription of following table 1, disperse to make, on pine, press 80g/m
2Coating weight, through 120mj/cm
2Film-forming.Detect by relevant criterion again and can contrast relevant curing performance in the table two.Curing rate improves as can be seen, and hardness has also increased.
Table 1 cured coating film prescription
TMPTA trimethylolpropane tris acrylic acid Trimethylolpropane Triacrylate; 1173 light trigger 2-hydroxyls-aminomethyl phenyl propane-1-ketone 2-Hydroxy-2-methyl-1-phenyl-1-propanone; HDDA 1, the 6-hexanediyl ester; EO-NPGDA ethoxyquin neopentylglycol diacrylate EthOxylated NeoPentylGlycol DiAcrylate.
Table two Performance Detection of being correlated with
Embodiment 2
Can be configured by following step:
Stannic chloride (SnCl
2) 35%, cobalt naphthenate 10%, zinc stearate: 15%, Isooctyl acrylate monomer 40%.Several materials are added in the Isooctyl acrylate monomer successively,, present transparent uniform state and can pack use stirring 2 hours at 40-55 ℃.
In as the prescription of following table 3, disperse to be formed on the pine by 80g/m
2Coating weight, through 120mj/cm
2Film-forming.Detect by relevant criterion again and can contrast relevant curing performance in the table 4.Curing rate improves as can be seen, and hardness has also increased.
Table 3 cured coating film prescription
Table 4 correlated performance detects
Embodiment 3
Can be configured by following step:
Stannic chloride (SnCl
2) 10%, cobalt chloride (CoCl
2) 28%, zinc stearate: 32%, Isooctyl acrylate monomer 30%.Several materials are added in the Isooctyl acrylate monomer successively,, present transparent uniform state and can pack use stirring 2 hours at 40-55 ℃.
In as the prescription of following table 5, disperse to make, on pine, press 80g/m
2Coating weight, through 120mj/cm
2Film-forming.Detect by relevant criterion again and can contrast relevant curing performance in the table 6.Curing rate improves as can be seen, and hardness has also increased.
Table 5 cured coating film prescription
Table 6 correlated performance detects
Embodiment 4
Can be configured by following step:
Stannic chloride (SnCl
2) 55%, cobalt naphthenate 28%, zinc stearate: 2%, Isooctyl acrylate monomer 15%.Several materials are added in the Isooctyl acrylate monomer successively,, present transparent uniform state and can pack use stirring 2 hours at 40-55 ℃.
In as the prescription of following table 7, disperse to make, on pine, press 80g/m
2Coating weight, through 120mj/cm
2Film-forming.Can contrast relevant curing performance in the table 4 by the relevant criterion detection.Curing rate improves as can be seen, and hardness has also increased.
Table 7 cured coating film prescription
Table 8 correlated performance detects
Embodiment 5
Can be configured by following step:
Stannic chloride (SnCl in proportion
2) 26%, cobalt naphthenate 14%, zinc stearate: 10%, different hot 50% ester of acrylic acid.Several materials are added in the Isooctyl acrylate monomer successively, stirred 2 hours, present transparent uniform state and can pack use at 40-55 ℃.
In as the prescription of following table 9, disperse to make, on pine, press 80g/m
2Coating weight, through 120mj/cm
2Film-forming.Detect by relevant criterion again and can contrast relevant curing performance in the table 10.Curing rate improves as can be seen, and hardness has also increased.
Table 9 cured coating film prescription
Table 10 correlated performance detects
Embodiment 6
Can be configured by following step:
STANNOUS SULPHATE CRYSTALLINE (SnSO
4) 35%, cobaltous chlorate 25%, zinc nitrate: 40%.The mixture of several materials was stirred 20 minutes, present translucent uniform state and can pack use.
In as the prescription of following table 11, disperse to make, on pine, press 80g/m
2Coating weight, through 120mj/cm
2Film-forming.Detect by relevant criterion again and can contrast relevant curing performance in the table 12.Curing rate improves as can be seen, and hardness has also increased.
Table 11 cured coating film prescription
Table 12 correlated performance detects
Embodiment 7
Can be configured by following step:
Stannic chloride (SnCl
2) 10%, cobaltous octadecanate 28%, zinc chloride: 32%, chloroacrylic acid hydroxypropyl acrylate 30%.Several materials are added in the chloroacrylic acid hydroxypropyl acrylate successively,, present transparent uniform state and can pack use stirring 2 hours at 40-55 ℃.
In as the prescription of following table 13, disperse to be formed on the pine by 80g/m
2Coating weight, through 120mj/cm
2Film-forming.Can contrast relevant curing performance in the table 6 by the relevant criterion detection.Curing rate improves as can be seen, and hardness has also increased.
Table 13 cured coating film prescription
Table 14 correlated performance detects
Embodiment 8
Can be configured by following step:
Nitric acid tin 10%, cobaltous sulfate 28%, zinc chloride: 32%, fluoro hydroxy propyl methacrylate 30%.Several materials are added in the fluoro hydroxy propyl methacrylate successively,, present transparent uniform state and can pack use stirring 2 hours at 40-55 ℃.
In as the prescription of following table 15, disperse to be formed on the pine by 80g/m
2Coating weight, through 120mj/cm
2Film-forming.Can contrast relevant curing performance in the table 6 by the relevant criterion detection.Curing rate improves as can be seen, and hardness has also increased.
Table 15 cured coating film prescription
Table 16 correlated performance detects
Embodiment 9
Can be configured by following step:
Chloric acid tin 10%, cobalt nitrate 28%, zinc naphthenate: 32%, hydroxyethyl methacrylate 30%.Several materials are added in the hydroxyethyl methacrylate successively,, present transparent uniform state and can pack use stirring 2 hours at 40-55 ℃.
In as the prescription of following table 17, disperse to be formed on the pine by 80g/m
2Coating weight, through 120mj/cm
2Film-forming.Can contrast relevant curing performance in the table 6 by the relevant criterion detection.Curing rate improves as can be seen, and hardness has also increased.
Table 17 cured coating film prescription
Table 18 correlated performance detects
Embodiment 10
Can be configured by following step:
Chloric acid tin 10%, cobalt nitrate 28%, zinc naphthenate: 32%, hydroxyethyl methacrylate 30% stirred after 20 minutes, presented translucent uniform state and can pack use.Owing to do not add the simple function group acrylate monomer, so dissolubility does not have the good of adding, for translucent, but because the emphasis of catalysis is a metal ion.So for catalytic effect is not very big influence.
Claims (6)
1. the catalyst of an accelerating ultraviolet curing is characterized in that, in weight portion, consists of:
Sn
2+Salt 2～55;
Co
2+Salt 2～28;
Zn
2+Salt 2～70;
The mixture of three kinds of salt.
2. the catalyst of accelerating ultraviolet curing as claimed in claim 1 is characterized in that, described Sn
2+Salt, Co
2+Salt, Zn
2+Salt be in hydrochloride, sulfate, naphthenate, chlorate, nitrate, the stearate any one.
3. the Preparation of catalysts method based on the described accelerating ultraviolet curing of claim 1 is characterized in that, with load weighted Sn
2+Salt, Co
2+Salt, Zn
2+The mixture of salt stir the 20min system and evenly get final product.
4. the catalyst of accelerating ultraviolet curing as claimed in claim 1 or 2 is characterized in that, in weight portion, has added 1～40 part simple function group acrylate monomer in the composition.
5. the catalyst of accelerating ultraviolet curing as claimed in claim 4, it is characterized in that described simple function group acrylate monomer is any one in methyl acrylate, butyl acrylate, Isooctyl acrylate monomer, hydroxy-ethyl acrylate, hydroxypropyl acrylate, propylene halide acid hydroxypropyl acrylate, methyl methacrylate, butyl methacrylate, EHMA, hydroxyethyl methacrylate, hydroxy propyl methacrylate, the halogenated methyl hydroxypropyl acrylate.
6. Preparation of catalysts method based on the described accelerating ultraviolet curing of claim 4, it is characterized in that,, add the acrylate monomer of simple function group the solid or the liquid of load weighted three kinds of salt, stirred 2 hours at 40～55 ℃, extremely transparent uniform state can be packed use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101219709A CN101786021B (en) | 2010-03-11 | 2010-03-11 | Catalyst for accelerating ultraviolet curing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101219709A CN101786021B (en) | 2010-03-11 | 2010-03-11 | Catalyst for accelerating ultraviolet curing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101786021A CN101786021A (en) | 2010-07-28 |
| CN101786021B true CN101786021B (en) | 2011-11-09 |
Family
ID=42529482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101219709A Expired - Fee Related CN101786021B (en) | 2010-03-11 | 2010-03-11 | Catalyst for accelerating ultraviolet curing and preparation method thereof |
Country Status (1)
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654090A (en) * | 1994-04-08 | 1997-08-05 | Nippon Arc Co., Ltd. | Coating composition capable of yielding a cured product having a high refractive index and coated articles obtained therefrom |
| JP2004162021A (en) * | 2002-07-26 | 2004-06-10 | Sanyo Chem Ind Ltd | Powder coating and slurry coating |
| CN101173033B (en) * | 2007-10-12 | 2010-04-21 | 广东天银化工实业有限公司 | Method for producing expediting setting type aquosity ultraviolet light solidifying composition |
| CN101423677B (en) * | 2008-12-18 | 2011-01-26 | 江南大学 | Method for preparing transparent and heat insulating water ultraviolet curing coating |
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2010
- 2010-03-11 CN CN2010101219709A patent/CN101786021B/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN101786021A (en) | 2010-07-28 |
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Address after: 225499, No. 88 East Daqing Road, Taizhou, Jiangsu, Taixing Patentee after: SUZHOU MINDA POLYMER SCI-TECH MATERIAL CO.,LTD. Address before: 215234 seven Town, Wujiang City, Jiangsu Province, No. 18 Ming Road, Zhejiang Economic Zone Patentee before: SUZHOU MINDA POLYMER SCI-TECH MATERIAL CO.,LTD. |
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Address after: 215234, Zhejiang Province, Wujiang City, Suzhou, seven towns, Zhejiang economic zone is located in Jiangsu Patentee after: SUZHOU MINDA POLYMER SCI-TECH MATERIAL CO.,LTD. Address before: 225499, No. 88 East Daqing Road, Taizhou, Jiangsu, Taixing Patentee before: SUZHOU MINDA POLYMER SCI-TECH MATERIAL CO.,LTD. |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111109 |