CN100535064C - Thermoforming plastic printing ink adopting ultraviolet-infra red drying technology - Google Patents
Thermoforming plastic printing ink adopting ultraviolet-infra red drying technology Download PDFInfo
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- CN100535064C CN100535064C CN 200610114766 CN200610114766A CN100535064C CN 100535064 C CN100535064 C CN 100535064C CN 200610114766 CN200610114766 CN 200610114766 CN 200610114766 A CN200610114766 A CN 200610114766A CN 100535064 C CN100535064 C CN 100535064C
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Abstract
The invention discloses a heat moulding plastic printing ink based on ultraviolet-infrared drying technique, which comprises the following parts: 100-300g prepolymer-ultraviolet solidified resin, 50-200g activated monomer, 20-200g optical initiator, 10-150g infrared solidified resin, 79-150g dye, 10-30% titanic acid ester coupling agent 401, defoamer, levelling agent and inhibitor.
Description
Technical field
The invention belongs to the printing-ink field, relate to a kind of employing ultraviolet ray---the thermoforming plastic printing ink of infra red drying technology.
Background technology
In the prior art, plastic printing ink is divided into two classes substantially, one class is a solvent-based ink, its advantage is in " vacuum thermoforming " technology, there is good temperature and pressure to fit property, can stand the temperature in the commercial run, pressure change, weak point is, have a large amount of inflammable in such printing ink, explosive, volatile, and the organic solvent that is detrimental to health, as dimethylbenzene, acetone, vinyl acetic monomer etc., therefore give not only that the workman is healthy to cause very big harm, also bring great pollution to environment, therefore listed national hazardous substance control catalogue in, western countries have adopted legal means that this class printing ink is limited; Another kind of is the UV curing curing inks, mainly by prepolymer, reactive monomer, light trigger, pigment and corresponding adjuvants are formed, this printing ink is when accepting the UV-irradiation of certain wavelength and intensity, just can solidify by complete drying, its advantage is to have overcome the deficiency that solvent-based ink exists, the harm and the environmental pollution that do not have organic solvent that HUMAN HEALTH is brought, its weak point is: accept can make in the UV-light dry solidification process the inner stress that produces at it, thereby influence the snappiness of ink film, and excessive stress and tangible slight crack can appear in ink film really up to the mark under the temperature and pressure of " vacuum thermoforming " technology, curve transition place when especially occurring in the plastics distortion, because transition position is an area of stress concentration, thereby it is discontinuous very easily to appear at the transition position colour, imperfect, produce defect ware.
Summary of the invention
The technical problem that solves:
A kind of employing ultraviolet ray---the thermoforming plastic printing ink of infra red drying technology is provided, can overcome the deficiencies in the prior art, both solve harm and environmental pollution that solvent-based ink brings HUMAN HEALTH, overcome the product quality problem that the UV curing curing inks brings again; Especially can satisfy the printability of the plastics of employing " vacuum thermoforming " technology; Easily manufacture, be convenient to use, safety non-pollution in the use, and can improve the quality of products.
The technical scheme that adopts:
Adopt ultraviolet ray---the thermoforming plastic printing ink of infra red drying technology, contain prepolymer---ultraviolet curable resin, reactive monomer, light trigger, pigment, it is characterized in that: also contain infrared ray cured resin, each components contents portion rate is as follows: prepolymer is 100～300 parts; Reactive monomer is 50～200 parts; Light trigger is 10～150 parts; Infrared ray cured resin is 20～200 parts; Pigment is 70～150 parts; Infrared ray cured resin is formed Resins, epoxy (C by a kind of in the following material or two kinds
15H
16O
2C
2H
7ONC
3H
5OCl) n CAS:38891-59-7; Unsaturated polyester resin (C
8H
4O
3C
4H
10O
3C
4H
2O
3) n CAS:26123-45-5,189,191 or 192 types; Urethane (C
10H
8N
2O
2C
6H
14O
3) n CAS:51852-81-4, heat curing-type; Aminoresin (C
3H
6N
6CH
2O) n CAS:9003-08-1; Resol (C
12H
10OC
10H
14OCH
2O) n CAS:52469-00-8,7529 types; Silicone resin CAS:67763-03-5; Synolac CAS:63148-69-6,300 types; Xylene formaldehyde resin (C
8H
10CH
20) nCAS:26139-75-3; Furane resin (C
5H
6O
2) nCAS:25212-86-6.
Beneficial effect:
Owing in the ultraviolet curing plastic printing ink, added infrared ray cured resin, therefore can be to the plastics printing of having printed, through the ultraviolet curing mode ink film being reached just earlier does, and then printing product carries out " vacuum thermoforming " under the ultrared effect of certain wavelength, in the thermoforming process, ink film reaches completely solidified by ultra red ray drying simultaneously, can satisfy the printability that especially adopts the plastics of " vacuum thermoforming " technology, can avoid ink film especially to produce excessive stress in its curve transition place at plastics, and the ink film snappiness is good, therefore slight crack or colored discontinuous can not appear in curve transition place ink film, incomplete phenomenon, thereby can improve the quality of products the final product rate; Safe, pollution-free in using simultaneously, be convenient to manufacture and use.
Embodiment
One, about the raw material of component and select for use
1, described prepolymer, claim oligopolymer again, i.e. ultraviolet curable resin is hereinafter to be referred as A, it is the low-molecular(weight)polymer that contains unsaturated functional group, be most important component in the ultraviolet curing ink, its performance plays a decisive role to the character of solidification process and cured film, and the light trigger under the uviolizing can make prepolymer and reactive monomer become excited state, continuous crosslinking polymerization, the fast setting film forming can be made up of a kind of, two kinds or three kinds of materials, selects for use material as follows:
Epoxy acrylic resin, as: HL-103 series bisphenol A epoxy acrylate [2], modified epoxy acrylate resin HL-140[1]; Ethoxylation dihydroxyphenyl propane diacrylate resin [1];
Polyurethane acrylic resin, as: aliphatic polyurethane acrylic resin HL-203Z[2]; Polyethers aromatic urethane acrylic resin HL-205F[1]; Aromatic urethane CALCIUM ACRYLATE HL-204F[2];
The acrylated polyacrylic resin, as: vinylformic acid-2-hydroxy propyl ester (HPA) [2]; 2-Hydroxy ethyl acrylate (HEA) [2].
2, described reactive monomer, claiming cross-linking monomer again, hereinafter to be referred as B, is a kind of micromolecular compound that has unsaturated group because of (as two keys), under illumination can with the prepolymer crosslinking polymerization, its molecular weight is the viscosity of regulating the UV curing curing inks, and controls its curing cross-linked density between hundreds of is to several thousand, improve the physical and mechanical properties of cured film, as flexible and hardness etc., can form by a kind of or two kinds of materials, select for use material as follows:
Methacrylic acid-beta-hydroxy ethyl ester (HEMA) CH
2=C (CH
2) COOCH
2CH
2OH; Iso-bornyl acrylate (IBOA) C
13H
20O
2CAS:5888-33-5[2]; 2-phenoxyethyl acrylate (PHEA) C
15H
20O
3CAS:65983-31-5; Hexanediyl ester (HDDA) C
12H
18O
4CAS:13048-33-4; Neopentylglycol diacrylate (NPGDA) C
11H
16O
4[1], [2]; Tri (propylene glycol) diacrylate (TPGDA) C
15H
24O
6Viscoat 295 (TMPTA) C
15H
20O
6[2]; Vinylbenzene (ST) C
8H
8CAS:100-42-5; Vinyl pyrrolidone (NVP) C
6H
9NO CAS:9003-39-8; Vinyl-acetic ester (VA) C
4H
6O
2CAS:108-05-4; Tetramethylol methane tetraacrylate (PETTA) C
17H
20O
8CAS:4986-89-4[1]; Pentaerythritol triacrylate [2]; Two trimethylolpropane tetra-acrylate (DTEMPTTA) that contract; Double pentaerythritol C5 methacrylate (DPEPA) C
22H
24O
8, double pentaerythritol methacrylate (DPHA) and ethoxyquin product thereof.
3, described light trigger hereinafter to be referred as C, is the main component that any ultraviolet curing system all needs, generally be to be under 200～400nm UV-irradiation at wavelength, can resolve into free radical, the material of initiated polymerization crosslinked action selects for use material as follows: benzophenone C
13H
10O CAS:119-61-9; Benzoin methyl ether C
15H
14O
2CAS:3524-62-7[1]; Alpha-hydroxy isopropyl benzene ketone C
10H
10O
2Alpha-hydroxy phenylcyclohexane ketone C
13H
16O
2CAS:947-19-3, IHT-PI type [1]; 2-isopropyl thioxanthone C
8H
14Cl
2N
2O
2CAS:66522-95-5, IHT-PTITX type [1]; 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (TPO) CAS:75980-60-8, structural formula:
IHT-PI TPO type [1].
4, described infrared ray cured resin, hereinafter to be referred as D, this kind resin is under the ultrared effect of certain wavelength (being generally the 2.5-6 micron), energy is crosslinking curing fast, simultaneously good with the ultraviolet curable resin intermiscibility, and can satisfy the printability of various printing process, especially adopt the printability of the plastics of " vacuum thermoforming " technology, select for use material as follows:
Resins, epoxy (EP) (C
15H
16O
2C
2H
7ONC
3H
5OC1) nCAS:38891-59-7; Unsaturated polyester resin (UP) (C
8H
4O
3C
4H
10O
3C
4H
2O
3) n CAS:26123-45-5,189,191 or 192 types [3]; Urethane (PUR) (C
10H
8N
2O
2C
6H
14O
3) n CAS:51852-81-4, heat curing-type; Aminoresin (C
3H
6N
6CH
2O) n CAS:9003-08-1; Resol (PF) (C
12H
10OC
10H
14OCH
2O) n CAS:52469-00-8,7529 types [4]; Silicone resin CAS:67763-03-5; Synolac CAS:63148-69-6,300 types [5]; Xylene formaldehyde resin (C
8H
10CH
20) n CAS:26139-75-3; Furane resin (C
5H
6O
2) nCAS:25212-86-6.
5, described pigment hereinafter to be referred as E, is the painted colorant of printing ink, selects for use as required:
3144 Lithol Reds; Bronze red C [6]; Carbon black C; Fast Yellow G [7]; Phthalocyanine blue b-G[8]; Phthalocyanine Green G; Titanium dioxide [9].
6, about auxiliary agent
Defoamer: methyl-silicone oil 201, dimethyl silicone oil [10];
Flow agent: HX-2010 type [11], T-3 type [12];
Stopper: the nitroxyl free radical piperazine pure stopper 701[13 that forms sediment], p-ten.-butylcatechol stopper TBC[14];
Coupling agent, its effect are to improve ink adhesion and infrared ray cured performance, select for use: titanate coupling agent NDZ-101,102 or 401 types [15], chlorinatedpolyethylene of chlorinatedpolyolefins class [16] or Chlorinated Polypropylene III [17] etc.
Two, about component and content portion rate (ratio is portion rate in each table)
1, printing ink of the present invention contains A, B, C, D and five kinds of components of E, portion rate as shown in Table 1:
Table one,
Attached: when component A was two kinds of materials compositions, wherein a kind of material accounted for 1/3～1/2 of its total umber, and all the other are the umber of another kind of material; When B component was two kinds of materials compositions, wherein a kind of material accounted for 1/3～1/2 of its total umber, and all the other are the umber of another kind of material; When component D was two kinds of materials compositions, wherein a kind of material accounted for 1/3～1/2 of its total umber, and all the other are the umber of another kind of material.
Respective embodiments is as shown in table two, three, four, five.
In the table two feed composition select for use for: A is a modified epoxy acrylate resin, and B is an iso-bornyl acrylate, and C is benzoin methyl ether or 2-isopropyl thioxanthone IHT-PI ITX type, and D is unsaturated polyester resin 189 types or Synolac 300 types, and E is a bronze red.
Table two
In the table three feed composition select for use for: A is vinylformic acid-2-hydroxy propyl ester, and B is a neopentylglycol diacrylate, and C is benzoin methyl ether or Alpha-hydroxy phenylcyclohexane ketone IHT-PI type, and D is Synolac 300 types or resol 7529 types, and E is an organic yellow.
Table three
In the table four feed composition select for use into, A is by A
1, A
2Two kinds of materials are formed, and are respectively aliphatic urethane acrylate HL-203Z type and HL-103 series bisphenol A epoxy acrylate; B is by B
1, B
2Two kinds of materials are formed, and are respectively pentaerythritol triacrylate and neopentylglycol diacrylate, and selecting for use of all the other C, D, E is same as table two respectively.
Table four
In the table five feed composition select for use into, D is by D
1, D
2Two kinds of materials are formed D
1Be unsaturated polyester resin 189 or 191, D
2Be resol 7529 types or Synolac 300 types, selecting for use of all the other A, B, C, E is same as table two respectively.
Table five
2, printing ink of the present invention also contains coupling agent, and portion rate as shown in Table 6
Table six
Respective embodiments is as shown in table seven
In the table seven feed composition select for use for: A is aliphatic polyurethane acrylic resin HL-203Z type or modified epoxy acrylate resin, B is iso-bornyl acrylate or tetramethylol methane tetraacrylate, C is a benzoin methyl ether, D is unsaturated polyester resin 189 types or resol 7529 types, and E is phthalocyanine blue b-G; Coupling agent is titanate coupling agent NDZ-101,401 types, and chlorinatedpolyethylene or Chlorinated Polypropylene III, coupling agent also can be made up of two kinds of materials, and wherein a kind of material accounts for 1/5～1/3 of its total umber, and all the other are the umber of another kind of material.
Table seven
3, printing ink of the present invention also contains defoamer, flow agent, stopper, and portion rate as shown in Table 8
Table eight
Respective embodiments is as shown in table nine
In the table nine feed composition select for use for: defoamer is selected methyl-silicone oil 201 types for use, or the dimethyl silicone oil flow agent selects HX-2010 or T-3 type for use, and stopper is selected p-ten.-butylcatechol TBC type for use, and all the other A, B, C, D, selecting for use of E are same as table two respectively.
Table nine
4, printing ink of the present invention contains coupling agent, defoamer, flow agent and stopper simultaneously, and portion rate as shown in Table 10
Table ten
Respective embodiments is as shown in table ten one
In the table ten one feed composition select for use for: A is aliphatic polyurethane acrylic resin HL-203Z type or modified epoxy acrylate resin, B is iso-bornyl acrylate or tetramethylol methane tetraacrylate, C is a benzoin methyl ether, D is unsaturated polyester resin 189 types or resol 7529 types, and E is phthalocyanine blue b-G; Coupling agent is titanate coupling agent NDZ-101,401 types, or chlorinatedpolyethylene, or Chlorinated Polypropylene III, and defoamer is selected methyl-silicone oil 201 types or dimethyl silicone oil for use, and flow agent is selected HX-2010 or T-3 type for use, and stopper is selected p-ten.-butylcatechol TBC type for use.
Table ten one
Three, about the preparation method of printing ink of the present invention:
1, when only containing five kinds of component A, B, C, D, E
At first with prepolymer A, reactive monomer B and the full and uniform mixing of infrared ray cured resin D of proportional, the pigment E of additional proportion amount then, full and uniform once more mixing, then grind, be generally and grind 3～4 roads, require mesh-of-grind, the light trigger C of last additional proportion amount less than 15 μ m, full and uniform once more mixing gets final product behind the homodisperse.
2, when containing component A, B, C, D, E and coupling agent, then the coupling agent of proportional will be in the end with light trigger C common add and homodisperse after get final product.
3, when containing component A, B, C, D, E and defoamer, flow agent, stopper, wherein about 1/5 of defoamer ratio total amount add jointly with pigment E earlier, and the flow agent of remaining defoamer and proportional, stopper will be in the end with light trigger C common add and homodisperse after get final product.
4, when containing component A, B, C, D, E and defoamer, flow agent, stopper and coupling agent simultaneously, wherein about 1/5 of defoamer ratio total amount add jointly with pigment E earlier, and the flow agent of remaining defoamer and proportional, stopper and coupling agent all need in the end to add jointly with light trigger C, and get final product behind the homodisperse.
Four, about the application of printing ink of the present invention
Adopt silk screen print method to be printed onto surface of plastic products, elder generation is according to the drying means of UV curing curing inks, through action of ultraviolet radiation, ink film is reached just to be done, be to carry out vacuum thermoforming processing under the infrared rays effect of 2.5-6 micron at wavelength to plastics then, make ink film in plastics thermoforming process, drying arrives completely solidified by the infrared rays effect simultaneously, satisfies the printability of thermoforming plastic goods.Wavelength is 2.5～6 microns a infrared rays, can make temperature rise reach 150～170 ℃, can satisfy the processing requirement of plastics vacuum thermoforming.
Attached: at " raw material of component and select for use " content part, all Arabic numerals group codes of closelying follow after " CAS: " are shown the code of this material in the U.S. chemical abstract.
Annotate: [1] Jiangmen city sky constant force UV-light Materials Co., Ltd
[2] Beijing Dongfang Yakeli Chemical Science Co., Ltd
[3] the good and unsaturated polyester factory in Dacheng County, Hebei province
[4] Suzhou letter Dehua worker company limited
[5] Xinhua Resin Factory, Shanghai
[6] the Anping County hat reaches pigment industry company limited
[7] the Gangu Xiang reaches chemical industry company limited
[8] the blue pigment chemical industry of Yancheng City section company limited
[9] the luxuriant Xinghua of Yixing City worker company limited
[10] Guangzhou became organosilicon raw material company limited in poly-million months
[11] Fanyu, Guangzhou China auxiliary agent company limited
[12] Changfeng Chemical Plant, Shanghai
[13] magnificent chemical industry limited liability company is contained in the Nangong City
[14] the prosperous chemical industry of Liaoyang ancient cooking vessel company limited
[15] NanJing Shuguang Chemical Group Co., Ltd.
[16] north, Henan plastics chemical industry company limited
[17] Guangzhou three inscription trade Co., Ltds
Claims (4)
1, adopts ultraviolet ray---the thermoforming plastic printing ink of infra red drying technology, contain prepolymer---ultraviolet curable resin, reactive monomer, light trigger, pigment, it is characterized in that: also contain infrared ray cured resin, each components contents portion rate is as follows: prepolymer is 100～300 parts; Reactive monomer is 50～200 parts; Light trigger is 10～150 parts; Infrared ray cured resin is 20～200 parts; Pigment is 70～150 parts; Infrared ray cured resin is formed Resins, epoxy (C by a kind of in the following material or two kinds
15H
16O
2C
2H
7ONC
3H
5OC1) nCAS:38891-59-7; Unsaturated polyester resin (C
8H
4O
3C
4H
10O
3C
4H
2O
3) nCAS:26123-45-5,189,191 or 192 types; Urethane (C
10H
8N
2O
2C
6H
14O
3) nCAS:51852-81-4, heat curing-type; Aminoresin (C
3H
6N
6CH
2O) nCAS:9003-08-1; Resol (C
12H
10OC
10H
14OCH
2O) nCAS:52469-00-8,7529 types; Silicone resin CAS:67763-03-5; Synolac CAS:63148-69-6,300 types; Xylene formaldehyde resin (C
8H
10CH
20) nCAS:26139-75-3; Furane resin (C
5H
6O
2) nCAS:25212-86-6.
2, employing ultraviolet ray according to claim 1---the thermoforming plastic printing ink of infra red drying technology, it is characterized in that: also contain coupling agent, form by a kind of in the following material or two kinds, titanate coupling agent NDZ-101,102 or 401 types, or chlorinatedpolyethylene, or Chlorinated Polypropylene III; Each components contents portion rate is as follows, 100～300 parts of prepolymers; 50～200 parts of reactive monomers; 10～150 parts of light triggers; 20～200 parts of infrared curing resins; 70～150 parts of pigment; 10～30 parts of coupling agents.
3, employing ultraviolet ray according to claim 1---the thermoforming plastic printing ink of infra red drying technology, it is characterized in that: also contain defoamer methyl-silicone oil 201 types or dimethyl silicone oil, flow agent HX-2010 type or T-3 type, stopper p-ten.-butylcatechol TBC type; Each components contents portion rate is as follows, 100～300 parts of prepolymers; 50～200 parts of reactive monomers; 10～150 parts of light triggers; 20～200 parts of infrared ray cured resins; 70～150 parts of pigment; 5～100 parts of defoamers; 10～100 parts of flow agents; 1～8 part of stopper.
4, employing ultraviolet ray according to claim 2---the thermoforming plastic printing ink of infra red drying technology, it is characterized in that: also contain defoamer methyl-silicone oil 201 types or dimethyl silicone oil, flow agent HX-2010 type or T-3 type, stopper p-ten.-butylcatechol TBC type; Each components contents portion rate is as follows, 100～300 parts of prepolymers; 50～200 parts of reactive monomers; 10～150 parts of light triggers; 20～200 parts of infrared ray cured resins; 70～150 parts of pigment; 5～100 parts of defoamers; 10～100 parts of flow agents; 1～8 part of stopper; 10～30 parts of coupling agents.
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| CN 200610114766 CN100535064C (en) | 2006-11-23 | 2006-11-23 | Thermoforming plastic printing ink adopting ultraviolet-infra red drying technology |
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|---|---|---|---|
| CN 200610114766 CN100535064C (en) | 2006-11-23 | 2006-11-23 | Thermoforming plastic printing ink adopting ultraviolet-infra red drying technology |
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| CN100535064C true CN100535064C (en) | 2009-09-02 |
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| EP1212195A1 (en) * | 1999-09-03 | 2002-06-12 | L & P Property Management Company | Method and apparatus for uv ink jet printing on fabric and combination printing and quilting thereby |
| US6737122B2 (en) * | 2000-07-24 | 2004-05-18 | Basf Aktiengesellschaft | Method for coating substrates |
| CN1529718A (en) * | 2001-02-09 | 2004-09-15 | �Ϻ���ͨ��ѧ | Non-chlorinated adhension assistant capable of solidifying by ultraviolet ray |
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