CN103205146B - A kind of ultraviolet curing type PET film surface treatment silane coupling agent and its preparation method and application - Google Patents
A kind of ultraviolet curing type PET film surface treatment silane coupling agent and its preparation method and application Download PDFInfo
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- CN103205146B CN103205146B CN201310102539.3A CN201310102539A CN103205146B CN 103205146 B CN103205146 B CN 103205146B CN 201310102539 A CN201310102539 A CN 201310102539A CN 103205146 B CN103205146 B CN 103205146B
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Abstract
The invention discloses a kind of ultraviolet curing type PET film surface treatment silane coupling agent and its preparation method and application.Ultraviolet curing type PET film surface treatment silane coupling agent, is characterized in that, by massfraction 100%, comprising: two functionality aliphatic carbamate-acrylate type oligopolymer 45% ~ 55%; Trifunctional reactive thinner Viscoat 295 15% ~ 20%; Di-functional reactive's thinner tripropylene glycol diacrylate 15% ~ 20%; Light trigger 2-hydroxy-2-methyl-1-phenyl-acetone 1.5% ~ 2.5%; Light trigger 1-hydroxy cyclohexyl phenylketone 1.5% ~ 2.5%; Ethyl acetate 5% ~ 15%.Ultraviolet curing type PET film surface treatment silane coupling agent of the present invention can be applicable to PET finishing material, label material, PET protection film surface treatment, for improving UV ink, paint adhesion.
Description
Technical field
The invention belongs to environmentally friendly coated material technical field, be specifically related to a kind of ultraviolet curing type PET film surface treatment silane coupling agent and its preparation method and application.
Background technology
PET film good heat resistance, transparency and intensity are high, are not easy to stretch, and tension control requires lower than other films, more and more extensive in field application such as label, thin film switch, protective membranes.Because PET macromolecular chain structure is regular, degree of crystallinity is higher, therefore its surperficial affinity, printing and ink attachment fastness are poor.UV coating, the general weather resistance of UV ink, solvent resistance are good, there is environmental protection and energy saving feature, share of market improves constantly in recent years, but this kind of there is good durability ink, sticking power is generally undesirable on a pet film for coating, be often difficult to reach application requiring.Raising UV coating and ink on a pet film sticking power are difficult problems of covering with paint, lacquer, colour wash, etc. or encountering in printing practice.
Conventional PET film surface treatment method has corona method and coating.Corona method has ageing, and treatment effect can with storage environment humiture and the difference of shelf-time generation decay in various degree, and in addition to UV ink, coating, even if through corona, attachment fastness is usual or not ideal enough.The advantage of coating is that film surface tension force can not be decayed along with storage environment temperature and shelf-time.Pet sheet face process coating, first needs there is powerful sticking power with PET film itself, and simultaneously have good ply adhesion with the gloss oil of surface printing, ink, undercoat itself also answers good durability, solvent resistance in addition.Current existing PET film surface treatment silane coupling agent, mainly contain solvent borne polyurethane, solvent-borne type saturated polyester resin class two class, be generally two component thermoset silane coupling agent, it is no problem to the sticking power of PET material own, the deficiency existed mainly contains: one is to part UV ink, UV coating, especially to larger still very poor with UV ink, the paint adhesion of high functionality epoxy-modified acrylic acid oligopolymer or high-functionality polyurethane modified acrylic oligomer preparation of hardness; Two is that the existing silane coupling agent heated drying time is long, and energy consumption is large, and general coating machinery is difficult to adapt to; Three is that existing silane coupling agent constructing operation discharges a large amount of volatile organic matter (VOC).
For overcoming currently available products deficiency, need further exploitation to improve UV coating, ink adhesion better effects if, suitability is wider, dry solidification PET film surface treatment easily silane coupling agent.
Summary of the invention
The object of this invention is to provide a kind of ultraviolet curing type, adaptability ultraviolet curing type PET film surface treatment silane coupling agent and its preparation method and application widely.Ultraviolet curing type PET film surface treatment silane coupling agent of the present invention can be applicable to PET finishing material, label material, PET protection film surface treatment, for improving UV ink, paint adhesion.
Ultraviolet curing type PET film surface treatment silane coupling agent of the present invention, is characterized in that, by massfraction 100%, comprising:
A) two functionality aliphatic carbamate-acrylate type oligopolymer 45% ~ 55%;
B) trifunctional reactive thinner Viscoat 295 (TMPTA) 15% ~ 20%
C) di-functional reactive's thinner tripropylene glycol diacrylate (TPGDA) 15% ~ 20%;
D) light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Switzerland Ciba Dorocure-1173) 1.5% ~ 2.5%;
F) light trigger 1-hydroxy cyclohexyl phenylketone (Switzerland Ciba Irgacure-184) 1.5% ~ 2.5%
G) ethyl acetate 5% ~ 15%.
Preferably, described ultraviolet curing type PET film surface treatment silane coupling agent, by massfraction 100%, comprising:
Two functionality aliphatic carbamate-acrylate type oligopolymer 45%;
Trifunctional reactive thinner Viscoat 295 20%;
Di-functional reactive's thinner tripropylene glycol diacrylate 20%;
Light trigger 2-hydroxy-2-methyl-1-phenyl-acetone 1.5%;
Light trigger 1-hydroxy cyclohexyl phenylketone 2.5%;
Ethyl acetate 11%.
The preparation method of ultraviolet curing type PET film surface treatment silane coupling agent of the present invention is: by two functionality aliphatic carbamate-acrylate type oligopolymer, trifunctional reactive thinner Viscoat 295, di-functional reactive's thinner tripropylene glycol diacrylate, light trigger 2-hydroxy-2-methyl-1-phenyl-acetone and light trigger 1-hydroxy cyclohexyl phenylketone, mix according to proportioning, as added feeding cylinder, 3min is disperseed under 800rpm, and then add ethyl acetate adjusting viscosity 20-25 second/painting-4 glasss, stir, as stirred 1min, ultraviolet curing type PET film surface treatment silane coupling agent is after filtration.
The using method of ultraviolet curing type PET film surface treatment silane coupling agent of the present invention is: adopt line rod spreader, ultraviolet curing type PET film surface treatment silane coupling agent is evenly applied on a pet film, 20-30 second is dried at 80 DEG C, then under UV cure lamp, UV solidification is carried out, condition of cure 1500-2000mJ/cm
2, obtained PET photocuring undercoat.After ultraviolet curing type PET film surface treatment silane coupling agent process solidification, place 7 days, then apply UV gloss oil, coating or UV ink.
Two functionality aliphatic carbamate-acrylate type oligopolymer of the present invention are aliphatic urethane-modified, and origoester acrylate, has two functionality, belong to material of the prior art.
Ultraviolet curing type PET film surface treatment silane coupling agent of the present invention is compared to silane coupling agent of the prior art, and it has following beneficial effect:
A () ultraviolet curing type PET film of the present invention surface treatment silane coupling agent, can be used for PET label material, finishing material, protective membrane surface treatment, can effectively improve UV ink, paint adhesion.
B () ultraviolet curing type PET film of the present invention surface treatment silane coupling agent, its dry solidification time is short, energy efficient.Ultraviolet curing type PET film surface treatment silane coupling agent of the present invention, it is only containing a small amount of ethyl acetate solvent, and compared with solvent-borne type silane coupling agent, the quantity of solvent of coating process volatilization is little, is environment-friendly type coating.
Embodiment:
Following examples further illustrate of the present invention, instead of limitation of the present invention.
Two functionality aliphatic carbamate-acrylate type oligopolymer in following examples, purchased from Li Qin Industry Co., Ltd, name of product: two functionality aliphatic carbamate-acrylate type oligopolymer, model: UA1239.
Embodiment 1
A) ultraviolet curing type PET film surface treatment silane coupling agent formula (weight ratio)
Two functionality aliphatic carbamate-acrylate type oligopolymer: 500 grams;
Trifunctional reactive thinner Viscoat 295 (TMPTA): 200 grams;
Di-functional reactive's thinner tripropylene glycol diacrylate (TPGDA): 150 grams;
Light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Switzerland Ciba Dorocure-1173): 25 grams;
Light trigger 1-hydroxy cyclohexyl phenylketone (Switzerland Ciba Irgacure-184): 15 grams;
Ethyl acetate: 110 grams;
Add up to 1000 grams.
B) the preparations and applicatio method of ultraviolet curing type PET film surface treatment silane coupling agent:
By two functionality aliphatic carbamate-acrylate type oligopolymer, reactive thinner (TMPTA, TPGDA), light trigger (Dorocure-1173, Irgacure-184), weigh by above proportioning, add feeding cylinder, 3min is disperseed under 800rpm, add ethyl acetate adjusting viscosity again, stir 1min, after filtration, be ultraviolet curing type PET film surface treatment silane coupling agent.21 seconds/the painting-4 glasss of ultraviolet curing type PET film surface treatment silane coupling agent viscosity.Adopt line rod spreader, ultraviolet curing type PET film surface treatment silane coupling agent is evenly coated in the PET film of corona treatment, dries 30 seconds at 80 DEG C, then under UV cure lamp, carry out UV solidification, condition of cure 2000mJ/cm
2, obtained PET photocuring undercoat.After the solidification of PET photocuring undercoat, place after 7 days, coating UV gloss oil (i.e. varnish, the good good omen Chemical Co., Ltd. in Shenzhen provides, model HCT902, and modified acrylic oligomer prepares by high-functionality polyurethane).
C) effect of ultraviolet curing type PET film surface treatment silane coupling agent
The effect of embodiment 1 is in table 1.
Table 1: the implementation result of embodiment 1
(contrast of table empty is PET corona film; In table, sticking power is tested by GB9286-1998 standard; Hardness is tested by GB/T6739-2006 standard; Solvent resistant wiping is tested by GB/T23989-2009 standard.）
As seen from Table 1, PET film, after ultraviolet curing type PET film surface treatment silane coupling agent of the present invention process, is brought up to 95% to the sticking power of HCT902 gloss oil from 60%, can be met application request.
Embodiment 2
A) ultraviolet curing type PET film surface treatment silane coupling agent formula (weight ratio)
Two functionality aliphatic carbamate-acrylate type oligopolymer: 450 grams;
Trifunctional reactive thinner (Viscoat 295 (TMPTA): 200 grams;
Di-functional reactive's thinner tripropylene glycol diacrylate (TPGDA): 200 grams;
Light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Switzerland Ciba Dorocure-1173): 15 grams;
Light trigger 1-hydroxy cyclohexyl phenylketone (Switzerland Ciba Irgacure-184): 25 grams;
Ethyl acetate: 110 grams;
Add up to 1000 grams.
B) the preparations and applicatio method of ultraviolet curing type PET film surface treatment silane coupling agent:
By two functionality aliphatic carbamate-acrylate type oligopolymer, reactive thinner (TMPTA, TPGDA), light trigger (Dorocure-1173, Irgacure-184), weigh by above proportioning, add feeding cylinder, 3min is disperseed under 800rpm, add ethyl acetate adjusting viscosity again, stir 1min, after filtration, be ultraviolet curing type PET film surface treatment silane coupling agent.20 seconds/the painting-4 glasss of ultraviolet curing type PET film surface treatment silane coupling agent viscosity.Adopt line rod spreader, ultraviolet curing type PET film surface treatment silane coupling agent is evenly coated in the PET film of corona treatment, dries 30 seconds at 80 DEG C, then under UV cure lamp, carry out UV solidification, condition of cure 2000mJ/cm
2, obtained PET photocuring undercoat.After the solidification of PET photocuring undercoat, place after 7 days, coating UV gloss oil (i.e. varnish, by Shenzhen, good good omen Chemical Co., Ltd. provides model HCT903, prepares UV gloss oil by high-functionality polyurethane modified acrylic oligomer).
C) effect of ultraviolet curing type PET film surface treatment silane coupling agent
The effect of embodiment 2 is in table 2.
Table 2: the implementation result of embodiment 2
(contrast of table empty is PET corona film; In table, sticking power is tested by GB9286-1998 standard; Hardness is tested by GB/T6739-2006 standard; Solvent resistant wiping is tested by GB/T23989-2009 standard.）
As seen from Table 2, PET film, after the ultraviolet curing type PET film surface treatment silane coupling agent process of the present embodiment, is brought up to 100% to the sticking power of HCT903 gloss oil from 50%, can be met application request.
Embodiment 3
A) ultraviolet curing type PET film surface treatment silane coupling agent formula (weight ratio)
Two functionality aliphatic carbamate-acrylate type oligopolymer: 550 grams;
Trifunctional reactive thinner (Viscoat 295 (TMPTA): 150 grams;
Di-functional reactive's thinner tripropylene glycol diacrylate (TPGDA): 200 grams;
Light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Switzerland Ciba Dorocure-1173): 20 grams;
Light trigger 1-hydroxy cyclohexyl phenylketone (Switzerland Ciba Irgacure-184): 15 grams;
Ethyl acetate: 65 grams;
Add up to 1000 grams.
B) the preparations and applicatio method of ultraviolet curing type PET film surface treatment silane coupling agent:
By two functionality aliphatic carbamate-acrylate type oligopolymer, reactive thinner (TMPTA, TPGDA), light trigger (Dorocure-1173, Irgacure-184), weigh by above proportioning, add feeding cylinder, 3min is disperseed under 800rpm, add ethyl acetate adjusting viscosity again, stir 1min, after filtration, be ultraviolet curing type PET film surface treatment silane coupling agent.25 seconds/the painting-4 glasss of ultraviolet curing type PET film surface treatment silane coupling agent viscosity.Adopt line rod spreader, ultraviolet curing type PET film surface treatment silane coupling agent is evenly coated in the PET film of corona treatment, dries 30 seconds at 80 DEG C, then under UV cure lamp, carry out UV solidification, condition of cure 2000mJ/cm
2, obtained PET photocuring undercoat.After the solidification of PET photocuring undercoat, place after 7 days, printing UV ink (UV ink types UB-2 is provided by Japanese Jujo Chemical Co, Ltd.).
C) effect of ultraviolet curing type PET film surface treatment silane coupling agent
The effect of embodiment 3 is in table 3.
Table 3: the implementation result of embodiment 3
(contrast of table empty is PET corona film; In table, sticking power is tested by GB9286-1998 standard; Hardness is tested by GB/T6739-2006 standard; Solvent resistant wiping is tested by GB/T23989-2009 standard.）
As seen from Table 3, PET film, after the ultraviolet curing type PET film surface treatment silane coupling agent process of the present embodiment, is brought up to 98% to the sticking power of UB-2 ink from 30%, can be met application request.
Embodiment 4
A) ultraviolet curing type PET film surface treatment silane coupling agent formula (weight ratio)
Two functionality aliphatic carbamate-acrylate type oligopolymer: 500 grams;
Trifunctional reactive thinner Viscoat 295 (TMPTA): 160 grams;
Di-functional reactive's thinner tripropylene glycol diacrylate (TPGDA): 150 grams;
Light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Switzerland Ciba Dorocure-1173): 25 grams;
Light trigger 1-hydroxy cyclohexyl phenylketone (Switzerland Ciba Irgacure-184): 15 grams;
Ethyl acetate: 150 grams;
Add up to 1000 grams.
B) the preparations and applicatio method of ultraviolet curing type PET film surface treatment silane coupling agent:
By two functionality aliphatic carbamate-acrylate type oligopolymer, reactive thinner (TMPTA, TPGDA), light trigger (Dorocure-1173, Irgacure-184), weigh by above proportioning, add feeding cylinder, 3min is disperseed under 800rpm, add ethyl acetate adjusting viscosity again, stir 1min, after filtration, be ultraviolet curing type PET film surface treatment silane coupling agent.21 seconds/the painting-4 glasss of ultraviolet curing type PET film surface treatment silane coupling agent viscosity.Adopt line rod spreader, ultraviolet curing type PET film surface treatment silane coupling agent is evenly coated in the PET film of corona treatment, dries 20 seconds at 80 DEG C, then under UV cure lamp, carry out UV solidification, condition of cure 1500mJ/cm
2, obtained PET photocuring undercoat.After the solidification of PET photocuring undercoat, place after 7 days, coating UV gloss oil (i.e. varnish, the good good omen Chemical Co., Ltd. in Shenzhen provides, model HCT902, and modified acrylic oligomer prepares by high-functionality polyurethane).
C) effect of ultraviolet curing type PET film surface treatment silane coupling agent
The effect of embodiment 4 is in table 4.
Table 4: the implementation result of embodiment 4
(contrast of table empty is PET corona film; In table, sticking power is tested by GB9286-1998 standard; Hardness is tested by GB/T6739-2006 standard; Solvent resistant wiping is tested by GB/T23989-2009 standard.）
As seen from Table 4, PET film, after ultraviolet curing type PET film surface treatment silane coupling agent of the present invention process, is brought up to 98% to the sticking power of HCT902 gloss oil from 50%, can be met application request.
Embodiment 5
A) ultraviolet curing type PET film surface treatment silane coupling agent formula (weight ratio)
Two functionality aliphatic carbamate-acrylate type oligopolymer: 550 grams;
Trifunctional reactive thinner Viscoat 295 (TMPTA): 160 grams;
Di-functional reactive's thinner tripropylene glycol diacrylate (TPGDA): 200 grams;
Light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Switzerland Ciba Dorocure-1173): 25 grams;
Light trigger 1-hydroxy cyclohexyl phenylketone (Switzerland Ciba Irgacure-184): 15 grams;
Ethyl acetate: 50 grams;
Add up to 1000 grams.
B) the preparations and applicatio method of ultraviolet curing type PET film surface treatment silane coupling agent:
By two functionality aliphatic carbamate-acrylate type oligopolymer, reactive thinner (TMPTA, TPGDA), light trigger (Dorocure-1173, Irgacure-184), weigh by above proportioning, add feeding cylinder, 3min is disperseed under 800rpm, add ethyl acetate adjusting viscosity again, stir 1min, after filtration, be ultraviolet curing type PET film surface treatment silane coupling agent.21 seconds/the painting-4 glasss of ultraviolet curing type PET film surface treatment silane coupling agent viscosity.Adopt line rod spreader, ultraviolet curing type PET film surface treatment silane coupling agent is evenly coated in the PET film of corona treatment, dries 20 seconds at 80 DEG C, then under UV cure lamp, carry out UV solidification, condition of cure 1500mJ/cm
2, obtained PET photocuring undercoat.After the solidification of PET photocuring undercoat, place after 7 days, coating UV gloss oil (i.e. varnish, the good good omen Chemical Co., Ltd. in Shenzhen provides, model HCT902,
By high-functionality polyurethane, modified acrylic oligomer prepares).
C) effect of ultraviolet curing type PET film surface treatment silane coupling agent
The effect of embodiment 5 is in table 5.
Table 5: the implementation result of embodiment 5
(contrast of table empty is PET corona film; In table, sticking power is tested by GB9286-1998 standard; Hardness is tested by GB/T6739-2006 standard; Solvent resistant wiping is tested by GB/T23989-2009 standard.）
As seen from Table 5, PET film, after ultraviolet curing type PET film surface treatment silane coupling agent of the present invention process, is brought up to 95% to the sticking power of HCT902 gloss oil from 60%, can be met application request.
Claims (4)
1. a ultraviolet curing type PET film surface treatment silane coupling agent, is characterized in that, by massfraction 100%, comprising:
A) two functionality aliphatic carbamate-acrylate type oligopolymer 45% ~ 55%;
B) trifunctional reactive thinner Viscoat 295 15% ~ 20%
C) di-functional reactive's thinner tripropylene glycol diacrylate 15% ~ 20%;
D) light trigger 2-hydroxy-2-methyl-1-phenyl-acetone 1.5% ~ 2.5%;
F) light trigger 1-hydroxy cyclohexyl phenylketone 1.5% ~ 2.5%;
G) ethyl acetate 5% ~ 15%.
2. ultraviolet curing type PET film surface treatment silane coupling agent according to claim 1, is characterized in that, by massfraction 100%, comprising:
Two functionality aliphatic carbamate-acrylate type oligopolymer 45%;
Trifunctional reactive thinner Viscoat 295 20%;
Di-functional reactive's thinner tripropylene glycol diacrylate 20%;
Light trigger 2-hydroxy-2-methyl-1-phenyl-acetone 1.5%;
Light trigger 1-hydroxy cyclohexyl phenylketone 2.5%;
Ethyl acetate 11%.
3. the preparation method of a ultraviolet curing type PET film surface treatment silane coupling agent according to claim 1, it is characterized in that, by two functionality aliphatic carbamate-acrylate type oligopolymer, trifunctional reactive thinner Viscoat 295, di-functional reactive's thinner tripropylene glycol diacrylate, light trigger 2-hydroxy-2-methyl-1-phenyl-acetone and light trigger 1-hydroxy cyclohexyl phenylketone, mix according to proportioning, and then add ethyl acetate adjusting viscosity 20-25 second/painting-4 glasss, stir, ultraviolet curing type PET film surface treatment silane coupling agent is after filtration.
4. the using method of a ultraviolet curing type PET film surface treatment silane coupling agent according to claim 1, it is characterized in that, adopt line rod spreader, ultraviolet curing type PET film surface treatment silane coupling agent according to claim 1 is evenly applied on a pet film, 20-30 second is dried at 80 DEG C, then under UV cure lamp, UV solidification is carried out, condition of cure 1500-2000mJ/cm
2, obtained PET photocuring undercoat.
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| CN105882172A (en) * | 2016-05-10 | 2016-08-24 | 深圳市睿同科技有限公司 | Novel flexographic printing method |
| CN108070299A (en) * | 2017-06-30 | 2018-05-25 | 施莹莺 | For the functional ink and preparation method and application of inkjet printing |
| CN107523207A (en) * | 2017-08-31 | 2017-12-29 | 安徽骏飞标识设计制作有限公司 | Suitable for feature primary coat, its preparation method and the application method of UV printings |
| WO2019095625A1 (en) * | 2017-11-15 | 2019-05-23 | 洛阳尖端技术研究院 | Ultraviolet curable ink and preparation method therefor |
| CN108250925B (en) * | 2017-12-20 | 2020-08-28 | 宁波激智科技股份有限公司 | Primer and preparation method thereof, polyester film and preparation method thereof |
| RU2718756C2 (en) * | 2018-09-28 | 2020-04-14 | Владислав Юрьевич Мирчев | Adhesive for jet printing and method for production thereof |
| CN109735221A (en) * | 2018-12-29 | 2019-05-10 | 中山市柏顿涂料有限公司 | A kind of priming paint and preparation method thereof with excellent UV ink adhesion |
| CN111423754B (en) * | 2020-04-29 | 2021-10-22 | 传美讯电子科技（珠海）有限公司 | Coating liquid for promoting UV ink adhesion and preparation method thereof |
| CN115477904A (en) * | 2022-09-02 | 2022-12-16 | 昆山乐凯锦富光电科技有限公司 | UV (ultraviolet) anti-adhesion film with surface layer capable of being photo-cured |
| CN116179071B (en) * | 2022-11-17 | 2024-03-08 | 武汉瑞普赛技术有限公司 | PET (polyethylene terephthalate) base film primer for flexographic printing plate and preparation method and use method thereof |
| CN115991959B (en) * | 2023-03-23 | 2023-06-16 | 富维薄膜（山东）有限公司 | Coating liquid and application thereof in holographic cat eye anti-counterfeiting polyester film |
| CN116804123A (en) * | 2023-06-26 | 2023-09-26 | 中国石油大学(华东) | PET film ultraviolet light curing (UV) hardening liquid for folding screen |
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