阅读说明：本技术 一种抗低温led光固化喷墨打印光油及其制备和应用 (Low-temperature-resistant LED photocuring inkjet printing gloss oil and preparation and application thereof ) 是由 冉淑燕 宋雪霞 李文彬 于 2019-11-04 设计创作，主要内容包括：本发明涉及一种抗低温LED光固化喷墨打印光油及其制备和应用。该光油组分按照质量百分比包括：预聚体树脂10.0～30.0％,醛酮树脂2.0～8.0％,活性稀释剂30.0～60.0％,光引发剂5.0～10.0％,流平剂0.5～1.5％,阻聚剂0.3～1.5％,紫外吸收剂0.5～2.0％。该制备方法包括：将醛酮树脂和预聚体树脂加入到活性稀释剂中,搅拌,然后在避光的条件下加入光引发剂、流平剂、阻聚剂及紫外吸收剂,搅拌。该光油固化成膜后,抗低温性、柔韧性和抗弯折性好。(The invention relates to low-temperature-resistant LED photocuring inkjet printing gloss oil and preparation and application thereof. The gloss oil comprises the following components in percentage by mass: 10.0-30.0% of prepolymer resin, 2.0-8.0% of aldehyde ketone resin, 30.0-60.0% of reactive diluent, 5.0-10.0% of photoinitiator, 0.5-1.5% of flatting agent, 0.3-1.5% of polymerization inhibitor and 0.5-2.0% of ultraviolet absorbent. The preparation method comprises the following steps: adding aldehyde ketone resin and prepolymer resin into an active diluent, stirring, then adding a photoinitiator, a flatting agent, a polymerization inhibitor and an ultraviolet absorbent under the condition of keeping out of the sun, and stirring. After the gloss oil is solidified into a film, the low temperature resistance, the flexibility and the bending resistance are good.)

1. The LED photocuring inkjet printing gloss oil is characterized by comprising the following components in percentage by mass: 10.0-30.0% of prepolymer resin, 2.0-8.0% of aldehyde ketone resin, 30.0-60.0% of reactive diluent, 5.0-10.0% of photoinitiator, 0.5-1.5% of flatting agent, 0.3-1.5% of polymerization inhibitor and 0.5-2.0% of ultraviolet absorbent, wherein the aldehyde ketone resin has no reactive group.

2. The gloss oil according to claim 1, wherein the prepolymer resin is prepared by compounding polyurethane resin and polyether resin or polyester resin according to a mass ratio of 1: 1-1: 2.

3. The gloss oil of claim 1, wherein the aldehyde ketone resin is one of CT-1210, CT-120, a 81.

4. The gloss oil according to claim 1, wherein the reactive diluent is prepared by compounding a monofunctional monomer and a difunctional monomer in a mass ratio of 5: 2-5: 4, and the monofunctional monomer comprises one or more of tetrahydrofuran acrylate, tetrahydrofuran methacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, trimethylolpropane formal acrylate, dodecyl acrylate, monomethacrylate of methoxypolyethylene glycol, and monoacrylate of methoxypolyethylene glycol; the difunctional monomer comprises one or more of 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, tetraethylene glycol diacrylate, 1, 3-butanediol dimethacrylate, diethanol dimethacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated (2) dipropylene glycol acrylate and propoxylated (2) neopentyl glycol diacrylate.

5. The gloss oil according to claim 1, wherein the photoinitiator is prepared by compounding an acyl phosphorus oxide initiator and a thioxanthone initiator according to a mass ratio of 10: 1-5: 1; the leveling agent is an organic siloxane modified leveling agent containing reactive groups.

6. The gloss oil according to claim 1, wherein the polymerization inhibitor is at least one of a phenol polymerization inhibitor and an amine polymerization inhibitor; the ultraviolet absorbent is benzophenone ultraviolet absorbent.

7. A method of preparing the gloss oil of claim 1, comprising the steps of:

and adding the aldehyde ketone resin and the prepolymer resin into the reactive diluent, stirring, adding the photoinitiator, the flatting agent, the polymerization inhibitor and the ultraviolet absorbent under the condition of keeping out of the sun, continuously stirring, and filtering to obtain the LED photocuring inkjet printing gloss oil.

8. The method according to claim 7, wherein the stirring time is 30-60 min; and continuously stirring for 50-80 min.

9. Use of a gloss oil according to claim 1.

Technical Field

The invention belongs to the field of photocuring printing ink and preparation and application thereof, and particularly relates to low-temperature-resistant LED photocuring inkjet printing gloss oil and a preparation method and application thereof.

Background

The gloss oil is a transparent light-cured printing ink, and can be used for various printing base materials to improve the application properties of the base materials such as fading, wear resistance, gloss and the like, so that the light-cured gloss oil is rapidly developed. The photocuring of the gloss oil can be divided into LED light source curing and high-pressure mercury lamp curing according to different curing light sources, the LED light source curing has incomparable advantages compared with the high-pressure mercury lamp curing, the LED light source curing is energy-saving and environment-friendly, the service life is long, and the shrinkage deformation of a printing stock due to overheating can not be caused by heat, so that the LED photocuring technology is rapidly developed. Currently, studies on LED photocuring gloss oil are not many, and representative Chinese patent CN201510359136.6 discloses UV gloss oil for an LED curing light source, which is studied on scratch resistance and adhesion of the gloss oil, while Chinese patents CN201710515456.5 and CN201810122374.9 are studied on flame retardance, wear resistance and stain resistance of the gloss oil, but the low temperature resistance of the gloss oil is not studied, and the formula shows that the low temperature resistance of the gloss oil is obviously insufficient.

Due to the rapid development of the light-cured gloss oil, the application of the gloss oil is more and more extensive, and particularly, for products with special requirements, such as leather, touch products and the like, the flexibility and the bending resistance of the products are kept unchanged after the products are cured into a film in the extremely low temperature environment in the north, and the surface of the products does not crack.

Disclosure of Invention

The invention aims to solve the technical problem of providing low-temperature-resistant LED photocuring inkjet printing gloss oil, and a preparation method and application thereof, so as to overcome the defects of poor low-temperature resistance, poor flexibility and poor bending property, surface cracking and the like of the photocuring gloss oil at extreme cold low temperature such as-25 ℃ after the photocuring gloss oil is cured to form a film on the surface of a substrate in the prior art.

The invention provides LED photocuring inkjet printing gloss oil which comprises the following components in percentage by mass: 10.0-30.0% of prepolymer resin, 2.0-8.0% of aldehyde ketone resin, 30.0-60.0% of reactive diluent, 5.0-10.0% of photoinitiator, 0.5-1.5% of flatting agent, 0.3-1.5% of polymerization inhibitor and 0.5-2.0% of ultraviolet absorbent, wherein the aldehyde ketone resin has no reactive group.

The prepolymer resin is prepared by compounding polyurethane resin and polyether resin or polyester resin according to a mass ratio of 1: 1-1: 2.

The polyurethane resin is one of GU3010Z, GU3030Z, GU3100Z, GU4075B, GU3400Y and GU 4000N.

The polyether resin is one of GU8100W, GU8100Y and GU 8100Z.

The polyester resin is one of GU8400X, GU9600Y, GU9700Y, GU9900Y and GU 9600Z.

The aldehyde ketone has no reactive group, and is crosslinked with the prepolymer resin through self film forming, and the aldehyde ketone resin has good adhesiveness and yellowing resistance.

The aldehyde ketone resin is one of CT-1210, CT-120 and A81.

The reactive diluent is prepared by compounding a monofunctional monomer and a bifunctional monomer according to the mass ratio of 5: 2-5: 4.

The monofunctional monomer comprises one or more of tetrahydrofuran acrylate, tetrahydrofuran methacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, trimethylolpropane formal acrylate, dodecyl acrylate, monomethacrylate of methoxy polyethylene glycol and monoacrylate of methoxy polyethylene glycol.

The difunctional monomer comprises one or more of 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, tetraethylene glycol diacrylate, 1, 3-butanediol dimethacrylate, diethanol dimethacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated (2) dipropylene glycol acrylate and propoxylated (2) neopentyl glycol diacrylate.

The photoinitiator is prepared by compounding an acyl phosphorus oxide initiator and a thioxanthone initiator according to the mass ratio of 10: 1-5: 1; the leveling agent is an organic siloxane modified leveling agent containing reactive groups.

The acyl phosphorous oxide initiator includes one of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (photoinitiator 819).

The thioxanthone initiator comprises one of 2-isopropyl thioxanthone ITX and 2, 4-diethyl thioxanthone DETX.

The organic siloxane modified leveling agent containing the reactive group comprises one or more of UV special leveling agents Rad2100N, Rad2000N and Rad 2200N, Glide 432.

The polymerization inhibitor is at least one of a phenol polymerization inhibitor and an amine polymerization inhibitor; the ultraviolet absorbent is benzophenone ultraviolet absorbent.

The phenol polymerization inhibitor comprises one of 2, 6-di-tert-butylphenol and p-methylphenol.

The amine polymerization inhibitor comprises vulcanized diphenylamine.

The benzophenone ultraviolet absorbent comprises one of 2, 4-dihydroxy benzophenone, 2-hydroxy-4-n-octoxy benzophenone and 2-hydroxy-4-methoxy benzophenone.

The invention also provides a preparation method of the LED photocuring inkjet printing gloss oil, which comprises the following steps:

adding aldehyde ketone resin and prepolymer resin into an active diluent, stirring to completely dissolve the resin, then adding a photoinitiator, a leveling agent, a polymerization inhibitor and an ultraviolet absorbent under the condition of keeping out of the sun, continuously stirring to uniformly mix the components, and filtering to obtain the LED photocuring inkjet printing gloss oil.

The stirring time is 30-60 min, and the stirring speed is 3000-5000 rad/min.

The continuous stirring time is 50-80 min, and the continuous stirring speed is 2000-4000 rad/min.

The filtration is performed by a 0.5-1.0 μm filtration membrane.

The invention also provides application of the LED photocuring inkjet printing gloss oil.

The LED photocuring ink-jet printing gloss oil can be directly printed on various base materials needing polishing, and after the gloss oil is cured into a film, the flexibility and the bending resistance of the film are unchanged at the extreme low temperature of-25 ℃, the surface of the film is not cracked, and the film has excellent fluency and yellowing resistance.

The viscosity of the LED photocuring inkjet printing gloss oil is 9.0-11.0 cP at 40 ℃, the surface tension is 20-35 mN/m, and the LED photocuring inkjet printing gloss oil is suitable for industrial spray heads such as Ricoh (Ricoh), Konika (KONICA), Kyoco porcelain (KYOCERA), SeIKO (SEIKO) and the like.

Advantageous effects

(1) After the gloss oil is solidified into a film, the low-temperature resistance, the flexibility and the bending resistance are good. The addition of the aldehyde ketone resin reduces the film-forming cohesion of the photosensitive resin, greatly improves the low-temperature resistance, flexibility and bending resistance of the resin, and has great value for extreme cold weather.

(2) The invention adopts LED light to cure the film, thereby avoiding the situation that the printing stock shrinks and deforms due to overheating caused by heat generation.

(3) The method for printing the gloss oil on the printing substrate by the ink-jet printing has the advantages of simple process, uniform printing, less material consumption and the like.

(4) The invention carefully screens raw materials, and adds the ultraviolet absorbent in the formula, so that the yellowing resistance is good.

(5) The LED photocuring ink-jet printing gloss oil has good smoothness.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

The polyurethane resin in the invention is GU3010Z, GU3030Z, GU3100Z, GU4075B, GU3400Y and GU 4000N; the polyether resin is GU8100W, GU8100Y and GU 8100Z; polyester resins GU8400X, GU9600Y, GU9700Y, GU9900Y, GU 9600Z; the aldehyde ketone resin CT-1210 and CT-120 can be purchased from Jinan Changtai chemical Co., Ltd; the aldehyde ketone resin A81 is available from Pasteur (China) Inc.

The monofunctional monomer of the present invention includes tetrahydrofuran acrylate, tetrahydrofuran methacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, trimethylolpropane formal acrylate, dodecyl acrylate, monomethacrylate of methoxypolyethylene glycol, monoacrylate of methoxypolyethylene glycol, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, tetraethylene glycol diacrylate, 1, 3-butanediol dimethacrylate, diethanol dimethacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated (2) dipropylene glycol acrylate, propylene glycol diacrylate, Propoxylated (2) neopentyl glycol diacrylate is available from sandoman, guangzhou chemical co.

The acyl phosphorous oxide initiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819) and the thioxanthone initiator including 2-isopropyl thioxanthone ITX and 2, 4-diethyl thioxanthone DETX are commercially available from IGM of the Netherlands.

The UV specialized leveling agents of the present invention, Rad2100N, Rad2000N, Rad 2200N, Glide 432, are commercially available from German Digao (TEGO).

The polymerization inhibitor 2, 6-di-tert-butylphenol, diphenylamine sulfide, p-methylphenol and ultraviolet absorbent 2, 4-dihydroxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone and 2-hydroxy-4-methoxybenzophenone can be purchased from IGM company in the Netherlands.