CN105419572A - Protective layer composition and preparation method and application thereof - Google Patents
Protective layer composition and preparation method and application thereof Download PDFInfo
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- CN105419572A CN105419572A CN201510763269.XA CN201510763269A CN105419572A CN 105419572 A CN105419572 A CN 105419572A CN 201510763269 A CN201510763269 A CN 201510763269A CN 105419572 A CN105419572 A CN 105419572A
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to the field of film protection layers and discloses a protective layer composition. The protective layer composition contains matrix resin, a diluent and an initiator. The matrix resin is a mixture of epoxy acrylate resin, urethane acrylate resin, acrylic resin and optional epoxy resin containing no carbon-carbon double bond. The diluent comprises an acrylate monomer. The invention further discloses a preparation method of the protective layer composition and application of the protective layer composition for preparing a protective layer. According to the technical scheme, the specific components are used cooperatively, the components can achieve the cooperative effect of supplementing each other, and therefore the formed protective layer can have the good chemical corrosion resistance, physical loss resistance, shock resistance and tenacity and has the better protective performance.
Description
Technical field
The present invention relates to protective layer field, particularly, relate to a kind of protecting layer compositions, the preparation method of this protecting layer compositions, and this protecting layer compositions is preparing the application in protective layer.
Background technology
Along with the development of science and technology, numerous novel product is constantly developed and is put goods on the market, and brings great convenience to the material life of people.But, when people are while enjoying life, also puzzle by a large amount of counterfeit and shoddy goods.How to have protected this problem of the rights and interests of consumers in general also to amplify out various false proof mode and product.
In current product, usually by containing matcoveredn, anti-counterfeiting mark or false proof wide bar that the anti-counterfeiting mark that has optical anti-counterfeit element utilizes heat-sensitive glue or pressure-sensitive adhesive to be connected to plastics or paper to be formed thermoprint transfer.As a rule, protective layer also should have defencive function.
But; current holographic false proof target protective layer is just conceived to the physicalies such as Marresistance energy; and its chemical resistant properties and shock resistance poor; cause that the overall material of anti-counterfeiting mark is hard and crisp, toughness is poor; under HI high impact condition, be easy to broken; fragile in commodity circulation, do not have anti-fake effect well.
Summary of the invention
The object of the invention is the defect that shock resistance and toughness in order to overcome existing protective layer is lower; and provide a kind of have good chemical resistance, resistance to physical deterioration, shock resistance and toughness, and there is protecting layer compositions of better protecting performance and its preparation method and application.
To achieve these goals, the invention provides a kind of protecting layer compositions, this protecting layer compositions contains matrix resin, thinner and initiator, wherein,
Described matrix resin is the mixture of Epocryl, polyurethane acrylate resin and acrylic resin and the optional not epoxy resin of carbon-carbon double bonds; Described thinner comprises acrylate monomer.
Preferably, in described matrix resin, the weight ratio of the total amount of the epoxy resin of Epocryl and non-carbon-carbon double bonds, polyurethane acrylate resin and acrylic resin is 0.1-6:1-8:1.
Preferably, described acrylic resin is solid acrylic resin; Preferably, the number-average molecular weight of described solid-state acrylic resin is 20000-60000 gram/mol, second-order transition temperature is 30-60 DEG C, acid number is not more than 9mgKOH/g.
Preferably, the number-average molecular weight of described Epocryl is 500-1400, elongation at break is 110-200%, tensile strength is 1-20Mpa, acid number is not more than 5mgKOH/g;
Preferably, the epoxy equivalent (weight) of the epoxy resin of described not carbon-carbon double bonds is 130-210 gram/equivalent;
Preferably, the number-average molecular weight of described polyurethane acrylate resin is 1000-4000, elongation at break is 79-250%, tensile strength is 20-40Mpa, second-order transition temperature is 5-60 DEG C;
Preferably, in described thinner, the acrylate monomer of described acrylate monomer to be functionality be 1-6; Preferred, the acrylate monomer of described acrylate monomer to be functionality be 1-2 and functionality are the mixture of the acrylate monomer of 3-6.
Preferably, described thinner also comprises 4-acryloyl morpholine.
Second aspect, present invention also offers the preparation method of protecting layer compositions as above, and wherein, the method comprises: matrix resin, thinner and initiator are mixed.
Preferably, the step that matrix resin, thinner and initiator mix is comprised: by matrix resin and mixing diluents, obtain the slurries containing matrix resin; Described initiator is mixed with the described slurries containing matrix resin.
Preferably, be 30-60 DEG C by the temperature of matrix resin and mixing diluents, be more preferably 45-60 DEG C.
The third aspect, present invention also offers protecting layer compositions as above and is preparing the application in film protective layer.
Pass through technique scheme; will above specific component with the use of; complementary collaborative effect can be played between each component; thus make the protective layer formed can have good chemical resistance, resistance to physical deterioration, shock resistance and toughness, and there is better protecting performance.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of protecting layer compositions, this protecting layer compositions contains matrix resin, thinner and initiator, wherein, described matrix resin is the mixture of Epocryl, the epoxy resin of optional not carbon-carbon double bonds, polyurethane acrylate resin and acrylic resin; Described thinner comprises acrylate monomer.
The present inventor finds in the process of research, and Epocryl has excellent water tolerance, drug resistance corrodibility, cohesiveness and toughness; Containing acrylic-functional and amino-formate bond in the molecule of described polyurethane acrylate resin, not only there is the high-wearing feature of urethane, adhesive power, snappiness, high protection intensity and excellent resistance to low temperature, also having optical property and the weathering resistance of polyacrylate resin, is a kind of radiation curing material of excellent combination property; Acrylic resin is less due to the shrinking percentage of self, can improve coating at attachment fastness.By using them specifically with the use of the matrix resin as protecting layer compositions; and be dissolved in the thinners such as acrylate monomer; on the one hand; matrix resin with the use of playing complementary synergy; and the toughness of protecting layer compositions chemical resistance, resistance to physical deterioration, shock resistance and excellence can be given; on the other hand; described thinner can dissolve described matrix resin well and regulate solidification rate; make the curing performance of the protecting layer compositions obtained more excellent, thus complete the present invention.
The present inventor finds further, the cohesive strength of the epoxy resin of carbon-carbon double bonds, dielectric properties, hardness and toughness are all not fine, and there is good acid-alkali-corrosive-resisting, when it can be used as the raw material of matrix resin for the moment, the synergy between each component can be promoted further.
In described composition of the present invention, although as long as protecting layer compositions is containing above-mentioned each component, the protective layer of formation just has good chemical resistance, resistance to physical deterioration, shock resistance and toughness, and has better protecting performance.But in order to enable above-mentioned performance mate better, with the gross weight of described composition for benchmark, the content of described matrix resin is 20-55 % by weight, preferred 30-55 % by weight, more preferably 35-55 % by weight; The content of described thinner is 30-75 % by weight, preferred 35-60 % by weight, more preferably 40-60 % by weight; The content of described initiator is 1-15 % by weight, preferred 2-10 % by weight, more preferably 5-8 % by weight.
According to one of the present invention preferred embodiment, the weight ratio of the total amount of the epoxy resin of described Epocryl and non-carbon-carbon double bonds, polyurethane acrylate resin and solid-state acrylic resin is (0.1-6): (1-8): 1, is preferably (1-4): (1.5-6): 1.
It should be noted that herein, term " total amount of the epoxy resin of Epocryl and non-carbon-carbon double bonds " refers to, when epoxy resin simultaneously containing Epocryl and non-carbon-carbon double bonds in described matrix resin, the gross weight of what it referred to is these two kinds of resins; When epoxy resin not containing not carbon-carbon double bonds in described matrix resin, the weight of what it referred to is Epocryl.
The advantage of radical UV curing is that the fast and performance of speed of response is easy to regulate, and shortcoming is that after solidification, volumetric shrinkage is large and oxygen inhibition is serious; Compared with radical UV curing, cation photocuring has and the advantages such as the strong adhesion of the polymkeric substance that formed little without oxygen inhibition (can be cured in atmosphere), volumetric shrinkage.Polyurethane acrylate resin and Epocryl are free yl polymerizating monomers, and the epoxy resin of carbon-carbon double bonds is not cationic polymerization monomer.Therefore, according to one of the present invention preferred embodiment, described matrix resin is the mixture of Epocryl, the epoxy resin of non-carbon-carbon double bonds, polyurethane acrylate resin and acrylic resin.In this preferred situation, described protecting layer compositions not only has better chemical resistance, resistance to physical deterioration, shock resistance and toughness, also has more excellent resistance to the oxygen inhibiting polymerization performance.
When epoxy resin simultaneously containing Epocryl, non-carbon-carbon double bonds of as above preferred protecting layer compositions of the present invention; more preferred, the weight ratio of the epoxy resin of described Epocryl and non-carbon-carbon double bonds is (0.8-7): 1.
According to the present invention, described Epocryl is preferably epoxy acrylate oligomer resin.The number-average molecular weight of described epoxy acrylate oligomer resin is preferably 500-1400, is more preferably 850-1300, elongation at break is preferably 110-200%, tensile strength is preferably 1-20Mpa, acid number is preferably not more than 5mgKOH/g.
According to the present invention, the epoxy equivalent (weight) of the epoxy resin of described not carbon-carbon double bonds is preferably 130-210 gram/equivalent.
According to the present invention, described polyurethane acrylate resin is preferably urethane acrylate oligomer resin, the number-average molecular weight of described urethane acrylate oligomer resin is preferably 1000-4000, is more preferably 2000-3500, elongation at break is preferably 79-250%, tensile strength is preferably 20-40Mpa, second-order transition temperature is preferably 5-60 DEG C.
According to the present invention, described acrylic resin is preferably solid acrylic resin, and the number-average molecular weight of described solid acrylic resin is preferably 20000-60000 gram/mol (being more preferably 30000-50000 gram/mol), second-order transition temperature is preferably 30-60 DEG C, acid number is preferably not more than 9mgKOH/g.
Wherein, term " epoxy equivalent (weight) " refers to the amount of resin (gram/equivalent) containing an epoxy group(ing), and namely the molecular-weight average of epoxy resin is divided by the value of epoxy group(ing) quantity contained by each molecule.The required milligram number consuming potassium hydroxide of free acid during term " acid number " refers to and in 1g epoxy acrylate oligomer resin.
The present inventor finds in the process of research; when described thinner is the mixed diluent of acrylate monomer and 4-acryloyl morpholine; it more effectively can dissolve described matrix resin, regulate solidification rate, makes the curing performance of the protecting layer compositions obtained more excellent.Therefore, preferably, thinner of the present invention also comprises 4-acryloyl morpholine.Preferred further, the weight ratio of described acrylate monomer and 4-acryloyl morpholine is 1-6:1, is more preferably 1.5-4:1.
The present inventor finds in the process of research; when described acrylate monomer be functionality is the acrylate monomer of 1-6; it can dissolve described matrix resin better, regulate solidification rate, makes the curing performance of the protecting layer compositions obtained more excellent.
The present inventor finds further, when the acrylate monomer of described acrylate monomer to be functionality be 1-2 and functionality are the mixture of the acrylate monomer of 3-6, dilution effect, activity, the wear resistance of final formed paint film, hardness and erosion resistance effectively can must be taken into account.Preferred, the weight ratio of functionality to be the acrylate monomer of 1-2 and functionality the be acrylate monomer of 3-6 is 0.2-20:1, is preferably 1.5-5:1.
Wherein, term " functionality " refers to that monomer molecule is when condensation reaction occurs, and the functional group's number participating in reaction is called functionality, the namely actual monomer number reacted in reaction system.
The acrylate monomer of each functionality can be the selection of this area routine above.Such as, single functionality acrylate monomer can be selected from one or more in Hydroxyethyl acrylate (HEA), isobornyl acrylate, isobornyl methacrylate, Isooctyl acrylate monomer, propyl methacrylate, tetrahydrofuran (THF) acrylate, tetrahydrofuran methyl acrylate, glycidyl methacrylate, vinylformic acid caprolactone and ethoxyquin hydroxyethyl meth acrylate.Difunctionality acrylate monomer can be selected from tri (propylene glycol) diacrylate (TPGDA), 1, one or more in 6 hexanediyl esters (HDDA), 1,6 hexylene glycol dimethyl diacrylates (HDDMA), propylene glycol diacrylate, ethoxylated bisphenol A dimethacrylate and polyethyleneglycol diacrylate.The rare acid ester monomer of three-functionality-degree can be selected from Viscoat 295 (TMPTA), Viscoat 295, trimethylol propane trimethyl triacrylate, ethoxyquin Viscoat 295, pentaerythritol triacrylate and high reactivity glycerol propoxylate triacrylate one or more.Four functionality acrylate monomers can be selected from two-trimethylolpropane tetra-acrylate, tetramethylol methane tetraacrylate and (4) ethoxyquin tetramethylol methane tetraacrylate one or more.The rare acid ester monomer of five functionality can be selected from five acrylate and/or tetramethylolmethane five acrylate.The rare acid ester monomer of six functionality can be dipentaerythritol acrylate.
According to the present invention; described polyurethane acrylate resin in described protecting layer compositions, Epocryl, solid acrylic resin, acrylate monomer and 4-acryloyl morpholine are free yl polymerizating monomer, and the epoxy resin of described not carbon-carbon double bonds is then cationic polymerization monomer.Therefore, correspondingly, when containing the epoxy resin of not carbon-carbon double bonds in described protecting layer compositions, described initiator should be the mixed light initiator of free radical photo-initiation and cation light initiator; When not containing the epoxy resin of not carbon-carbon double bonds in described protecting layer compositions, described light trigger can be only free radical photo-initiation.
According to the present invention, the kind of described initiator and consumption are conventionally known to one of skill in the art, all can be commercially available.Such as, described free radical photo-initiation can be selected from one or more in alpha-alcohol ketone, thioxanthone and benzophenone.Wherein, alpha-alcohol ketone is cracking type free radical photo-initiation, usually can be selected from one or more in IHT-PI184, Irgacure184 and darocur1173; Described thioxanthone and benzophenone are hydrogen-abstraction free radical photo-initiation, the aided initiating that matches with it need be added to improve its initiating activity, usually N can be selected from, one or more in N-mesitylenic acid ethyl ester, N, N-mesitylenic acid-2-ethylhexyl, phenylformic acid dimethylaminoethyl.Wherein, described aided initiating can be response type amine.Described cation light initiator can be selected from triaryl phosphofluoric acid sulfosalt, aryl diazonium salts, dimethyl salt compounded of iodine and the luxuriant molysite of fragrance one or more.
According to the present invention, in described protecting layer compositions, auxiliary agent can also be contained.The kind of described auxiliary agent and consumption can add according to actual needs, and the present invention does not limit especially to this.Such as, described auxiliary agent specifically can be selected from flow agent, anti-wear agent and defoamer one or more, and with the gross weight of described composition for benchmark, the content of described auxiliary agent can be 0.1-10 % by weight, is preferably 0.1-5 % by weight.
The kind of described flow agent and consumption are conventionally known to one of skill in the art, and such as described flow agent can be selected from EFKA3883, EFKA3886, EFKA3600, BYK366, BYK333, BYK307 and DEGO410 one or more; Wherein EFKA series is Dutch Ai Fuka Products, and BYK series is BYK Products, and DEGO series is German enlightening height Products, and its trade mark above is conventionally known to one of skill in the art; With the gross weight of described protecting layer compositions for benchmark, the content of described flow agent can be 0-1.5 % by weight, is preferably 0.1-1 % by weight.
As a rule, the physical and mechanical properties after the solidification of described composition can be improved the adding of described anti-wear agent to a certain extent, strengthen the surface hardness of paint film.The add-on of anti-wear agent can not be too large, otherwise can affect the sticking power of paint film to ground, and its content can be the content of this area routine; in general; with the gross weight of described protecting layer compositions for benchmark, the content of described anti-wear agent can be 0-5 % by weight, is preferably 0.1-2 % by weight.The kind of described anti-wear agent is conventionally known to one of skill in the art, and it can be polymer or the inorganic material powders with certain physical strength, as one or more in nylon powder, talcum powder, polyethylene wax, limestone powder and titanium dioxide.
The kind of described defoamer and consumption are conventionally known to one of skill in the art, and such as, described defoamer can be selected from EFKA2022, EFKA2527, EFKA2040, BYK352, BYK354 and BYK357 one or more; With the gross weight of described protecting layer compositions for benchmark, the content of described defoamer can be 0-2 % by weight, is preferably 0.1-1.5 % by weight.
Second aspect, present invention also offers the preparation method of sheath composition described above, wherein, the method comprises: matrix resin, thinner and initiator are mixed.
According to the preparation method of protecting layer compositions provided by the invention, the mixing of described matrix resin, thinner and light trigger can be carried out simultaneously also can proceed step by step.Under preferable case, the step of described matrix resin, thinner and light trigger mixing comprises: by matrix resin and mixing diluents evenly, obtain the slurries containing matrix resin; And then described light trigger is mixed with the slurries containing matrix resin.
According to the present invention, under preferable case, during by matrix resin and mixing diluents, can improve the temperature of mixing, the temperature of described mixing can be 30-60 DEG C usually, is more preferably 45-60 DEG C.
The selection of described matrix resin, thinner, initiator and consumption can be selected with reference to description as above, and at this, it is no longer repeated in the present invention.
The third aspect, present invention also offers protecting layer compositions as above and is preparing the application in protective layer.
Preferably, protecting layer compositions provided by the invention is applicable to the protective layer preparing holographic anti-counterfeiting label, and the coating thickness of described protective layer is generally 0.8-5 micron, is preferably 1-3 micron, and after ultraviolet radiation-curable, obtains protective layer.The mode of described film can be selected from the coating of end charging trans anilox roll, the coating of top material inlet trans anilox roll, the coating of comma direct anilox roll, the trans anilox roll coating of comma and one or more directly in the mode such as anilox roll coating, and the present invention is to this not special restriction.
Below will be described the present invention by embodiment.Unless stated otherwise, in the following Examples and Comparative Examples,
Epoxy acrylate oligomer resin, purchased from Sartomer, CN131;
The not epoxy resin of carbon-carbon double bonds, purchased from DOW Chemical, UVR6105;
Urethane acrylate oligomer resin, purchased from ALLNEX, EBECRYL8411;
Solid acrylic resin, purchased from Degussa, LP65/11;
Single functionality acrylate monomer, purchased from Sartomer, SR256;
Two functionality acrylate monomers, purchased from Sartomer, SR238;
Three-functionality-degree and above acrylate monomer, purchased from Sartomer, SR444;
4-acryloyl morpholine, purchased from the emerging people of Japan;
Alpha-alcohol ketone, purchased from vapour bar-BASF AG, Darocur1173;
Thioxanthone, purchased from vapour bar-BASF AG, DarocurITX;
Triaryl phosphofluoric acid sulfosalt, purchased from Beijing Ying Li company, IHT432
Response type amine aided initiating, purchased from Changxing, 6420;
Flow agent is EFKA3883, purchased from Dutch Ai Fuka company.
Table 1
Embodiment 1-11
For illustration of protecting layer compositions provided by the invention and preparation method thereof
According to each component in table 1 and consumption; at 45 DEG C, matrix resin and mixing diluents is even, obtain the slurries containing matrix resin; again light trigger is mixed with the described slurries containing matrix resin, obtain protecting layer compositions X1-X11 of the present invention.
Embodiment 12
The present embodiment is for illustration of protecting layer compositions provided by the invention and preparation method thereof
Carry out the preparation of protecting layer compositions X12 according to the method for embodiment 1, difference is, the acrylic resin used is propylene liquid acid resin.
Embodiment 13
The present embodiment is for illustration of protecting layer compositions provided by the invention and preparation method thereof
Carry out the preparation of protecting layer compositions X13 according to the method for embodiment 1, difference is, directly all components is mixed.
Embodiment 14
The present embodiment is for illustration of protecting layer compositions provided by the invention and preparation method thereof
Carry out the preparation of protecting layer compositions X14 according to the method for embodiment 1, difference is, the preparation temperature of described protecting layer compositions is 20 DEG C.
Comparative example 1
This comparative example is for illustration of the protecting layer compositions and preparation method thereof of reference
Carry out the preparation of protecting layer compositions D1 according to the method for embodiment 1, difference is, not containing Epocryl in described matrix resin.The amount polishing of Epocryl is in the epoxy resin of not carbon-carbon double bonds.
Comparative example 2
This comparative example is for illustration of the protecting layer compositions and preparation method thereof of reference
Carry out the preparation of protecting layer compositions D2 according to the method for embodiment 1, difference is, not containing polyurethane acrylate resin in described matrix resin.The amount equivalent polishing of polyurethane acrylate resin is in epoxy acrylate oligomer resin and solid acrylic resin.
Comparative example 3
This comparative example is for illustration of the protecting layer compositions and preparation method thereof of reference
Carry out the preparation of protecting layer compositions D3 according to the method for embodiment 1, difference is, not containing solid acrylic resin in described matrix resin.The amount equivalent polishing of solid acrylic resin is in epoxy acrylate oligomer resin and urethane acrylate oligomer resin.
Comparative example 4
This comparative example is for illustration of the protecting layer compositions and preparation method thereof of reference
Carry out the preparation of protecting layer compositions D4 according to the method for embodiment 1, difference is, not containing acrylate monomer in described thinner.The amount polishing of acrylate monomer is in 4-acryloyl morpholine.
Test case 1
For illustration of the test of the surface free energy of protecting layer compositions, protective value, snappiness and film forming properties.
(1) preparation of test specimens:
Under the irradiation of ultraviolet lamp (model is LightHammer6, purchased from Fusion company), (light intensity is 30mW/cm
2), utilize charging trans anilox roll coating method in the end to be coated on PET transparent plastic film by the protecting layer compositions in embodiment 1-14 and comparative example 1-4, coating thickness is 1.5 microns, obtains test specimens.
(2) attachment fastness test:
According to Japanese Industrial Standards (JIS) classification, according to " scratch experiment of GBT9286-1998 paint and varnish, paint film " standard, 10 × 10 1mm × 1mm small grid are drawn with the test specimens surface that cross-cut tester obtains in step (1), each line should deeply and the bottom of coating, with the fragment wash clean of hairbrush by test zone.Firmly cling tested small grid with 3M600 adhesive tape, with eraser wiping adhesive tape, strengthen contact area and the dynamics in adhesive tape and tested region, shut down adhesive tape in the vertical direction, same position carries out 2 identical experiment.If protective layer and base material are (namely; PET transparent plastic film) be separated completely, be cited as " good "; if protective layer and base material have major part to be separated, be cited as " good "; if protective layer and base material have major part to be separated, be cited as " in ", if protective layer is not separated with base material, be cited as " poor ".Acquired results is as shown in table 2.
(3) snappiness test:
According to GB/T1731-1993 standard, the test specimens that step (1) obtains is cut into the sample of 10cm × 10cm size, rub instrument with resistance to (model is NBS, purchased from IGTTESTINGSYSTEM company) snappiness test is carried out to sample, if there is no obvious folding line, be cited as " good ", if there is obvious folding line maybe can not carry out doubling, be cited as " poor ".Acquired results is as shown in table 2.
(4) film forming flow leveling test:
According to JB3998-85, the film forming flow leveling of protecting layer compositions X1-X14 and D1-D4 is tested.Acquired results is as shown in table 2.
Table 2
| Numbering | Attachment fastness is tested | Resistance toly rub test | Film forming levelling property |
| Embodiment 1 | Good | Good | Good |
| Embodiment 2 | Good | Good | Good |
| Embodiment 3 | Good | Good | Good |
| Embodiment 4 | Good | Good | Good |
| Embodiment 5 | Good | Good | Good |
| Embodiment 6 | Good | Good | Good |
| Embodiment 7 | Good | Good | Good |
| Embodiment 8 | Good | Good | Good |
| Embodiment 9 | Good | Good | Good |
| Embodiment 10 | Good | Good | Good |
| Embodiment 11 | Good | Good | Good |
| Embodiment 12 | Good | In | Good |
| Embodiment 13 | Good | Good | Good |
| Embodiment 14 | Good | Good | Good |
| Comparative example 1 | Difference | Difference | Difference |
| Comparative example 2 | Difference | In | In |
| Comparative example 3 | Difference | In | Difference |
| Comparative example 4 | In | In | In |
Test case 2
For the protection of the resistance to chemical corrosion of anti-counterfeiting mark and the test of resistance to physical deterioration performance of the protective layer of layer composition formation.
(1) preparation of test specimens:
Under the irradiation of ultraviolet lamp (model is LightHammer6, purchased from Fusion company), (light intensity is 30mW/cm
2), utilize charging trans anilox roll coating method in the end to be coated on PET transparent plastic film by the protecting layer compositions in embodiment 1-15 and comparative example 1-4, coating thickness is 1.5 microns; Recycling end charging trans anilox roll coating holographic imaging layer, coating thickness is 1 micron; Carry out vacuum plating again; optical density value controls at 2.4-3.3; be coated with adhesion enhancement layer and thermoprint adhesive linkage successively again, coating thickness is 1.4 microns, thermal transfer film that obtain comprising the protective layer formed by protecting layer compositions of the present invention, that have multilayered structure.Utilize heat-sensitive glue or pressure sensitive adhesive to be bonded on plastics by above-mentioned thermal transfer film and form anti-counterfeiting mark.
(2) test of resistance to chemical corrosion:
According to GB/T1763-1979 standard, the test specimens that step (1) obtains is placed in respectively ketones solvent (acetone), esters solvent (ethyl acetate), benzene kind solvent (toluene), halogenated alkanes solvents (1,2-ethylene dichloride) and sodium hydroxide solution (concentration is 2 % by weight) in, each immersion is after 30 minutes, dry with deionized water rinsing and contrast with former state, being chosen as without during considerable change " good " when test specimens compares with former state; When test specimens compares with former state, if test specimens color has considerable change with gloss compared with former state, but be chosen as " good " without during obvious corrosion phenomenon; When test specimens compares with former state, if in test specimens corroded area lower than 20% time be chosen as " in "; When test specimens compares with former state, if be chosen as " poor " when in test specimens, corroded area is greater than 20%.Acquired results is as shown in table 3.
Table 3
| Numbering | Ketones solvent | Esters solvent | Benzene kind solvent | Halogenated alkanes solvents | Sodium hydroxide |
| Embodiment 1 | Good | Good | Good | Good | Good |
| Embodiment 2 | Good | Good | Good | Good | Good |
| Embodiment 3 | Good | Good | Good | Good | Good |
| Embodiment 4 | Good | Good | Good | Good | Good |
| Embodiment 5 | Good | Good | Good | Good | Good |
| Embodiment 6 | Good | Good | Good | Good | Good |
| Embodiment 7 | Good | Good | Good | In | Good |
| Embodiment 8 | Good | Good | Good | Good | Good |
| Embodiment 9 | In | Good | Good | Good | Good |
| Embodiment 10 | Good | Good | Good | Good | Good |
| Embodiment 11 | Good | Good | Good | Good | Good |
| Embodiment 12 | Good | Good | Good | Good | Good |
| Embodiment 13 | Good | In | Good | Good | Good |
| Embodiment 14 | Good | Good | Good | Good | Good |
| Comparative example 1 | Difference | Difference | In | Difference | Difference |
| Comparative example 2 | In | In | In | In | In |
| Comparative example 3 | Difference | Difference | In | In | Difference |
| Comparative example 4 | In | Difference | In | Difference | Difference |
(3) test of resistance to physical deterioration performance:
Temperature be 35 DEG C, under humidity is the condition of 50%, respectively according to GB/T1735-1979, GB/T1768-1979 and GB/T1732-1993 standard, the test specimens obtained step (1) carries out the test of heat resistance, Marresistance energy and impact resistance.Acquired results is as shown in table 4.
Table 4
| Numbering | Heat resistance | Marresistance energy | Impact resistance |
| Embodiment 1 | Good | Good | Good |
| Embodiment 2 | Good | Good | Good |
| Embodiment 3 | Good | Good | Good |
| Embodiment 4 | Good | Good | Good |
| Embodiment 5 | Good | Good | Good |
| Embodiment 6 | Good | Good | Good |
| Embodiment 7 | Good | Good | Good |
| Embodiment 8 | Good | Good | Good |
| Embodiment 9 | Good | Good | In |
| Embodiment 10 | Good | Good | Good |
| Embodiment 11 | Good | Good | Good |
| Embodiment 12 | Good | Good | Good |
| Embodiment 13 | Good | Good | Good |
| Embodiment 14 | Good | Good | Good |
| Comparative example 1 | Difference | Difference | Difference |
| Comparative example 2 | Difference | In | Difference |
| Comparative example 3 | In | In | Difference |
| Comparative example 4 | In | Difference | Difference |
Test result shows, protecting layer compositions of the present invention has good protective value, shock resistance and toughness, and has good chemical resistance and resistance to physical deterioration, can meet the demand of use.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. a protecting layer compositions, is characterized in that, this protecting layer compositions contains matrix resin, thinner and initiator, wherein,
Described matrix resin is the mixture of Epocryl, polyurethane acrylate resin and acrylic resin and the optional not epoxy resin of carbon-carbon double bonds;
Described thinner comprises acrylate monomer.
2. protecting layer compositions according to claim 1, wherein, with the gross weight of described composition for benchmark, the content of described matrix resin is 20-55 % by weight, and the content of described thinner is 30-75 % by weight, and the content of described initiator is 1-15 % by weight.
3. protecting layer compositions according to claim 1 and 2; wherein; described matrix resin is the mixture of Epocryl, the epoxy resin of non-carbon-carbon double bonds, polyurethane acrylate resin and acrylic resin; wherein, the weight ratio of the total amount of the epoxy resin of Epocryl and non-carbon-carbon double bonds, polyurethane acrylate resin and acrylic resin is 0.1-6:1-8:1.
4. according to the protecting layer compositions in claim 1-3 described in any one, wherein, described acrylic resin is solid acrylic resin.
5. protecting layer compositions according to claim 4, wherein,
The number-average molecular weight of described Epocryl is 500-1400, elongation at break is 110-200%, tensile strength is 1-20Mpa, acid number is not more than 5mgKOH/g;
Preferably, the epoxy equivalent (weight) of the epoxy resin of described not carbon-carbon double bonds is 130-210 gram/equivalent;
Preferably, the number-average molecular weight of described polyurethane acrylate resin is 1000-4000, elongation at break is 79-250%, tensile strength is 20-40Mpa, second-order transition temperature is 5-60 DEG C;
Preferably, the number-average molecular weight of described solid-state acrylic resin is 20000-60000 gram/mol, second-order transition temperature is 30-60 DEG C, acid number is not more than 9mgKOH/g.
6. protecting layer compositions according to claim 1, wherein, described thinner also comprises 4-acryloyl morpholine; Preferably, the weight ratio of described acrylate monomer and 4-acryloyl morpholine is 1-6:1, is preferably 1.5-4:1.
7. the protecting layer compositions according to claim 1,2 or 6, wherein, in described thinner, the acrylate monomer of described acrylate monomer to be functionality be 1-6;
Preferably, the acrylate monomer of described acrylate monomer to be functionality be 1-2 and functionality are the mixture of the acrylate monomer of 3-6; Preferred, the weight ratio of functionality to be the acrylate monomer of 1-2 and functionality the be acrylate monomer of 3-6 is 0.2-20:1, is preferably 1.5-5:1.
8. the protecting layer compositions according to claim 1 or 7, wherein, described acrylate monomer is selected from Hydroxyethyl acrylate, isobornyl acrylate, isobornyl methacrylate, Isooctyl acrylate monomer, propyl methacrylate, tetrahydrofuran (THF) acrylate, tetrahydrofuran methyl acrylate, glycidyl methacrylate, vinylformic acid caprolactone, ethoxyquin hydroxyethyl meth acrylate, tri (propylene glycol) diacrylate, 1,6 hexanediyl esters, 1,6 hexylene glycol dimethyl diacrylates, propylene glycol diacrylate, ethoxylated bisphenol A dimethacrylate, polyethyleneglycol diacrylate, Viscoat 295, Viscoat 295, trimethylol propane trimethyl triacrylate, ethoxyquin Viscoat 295, pentaerythritol triacrylate, high reactivity glycerol propoxylate triacrylate, two-trimethylolpropane tetra-acrylate, tetramethylol methane tetraacrylate and (4) ethoxyquin tetramethylol methane tetraacrylate, five acrylate, tetramethylolmethane five acrylate.With one or more in dipentaerythritol acrylate.
9. protecting layer compositions according to claim 1, wherein, also containing auxiliary agent in described composition, described auxiliary agent be selected from advection agent, anti-wear agent and defoamer one or more.
10. the preparation method of the protecting layer compositions in claim 1-9 described in any one, is characterized in that, the method comprises: matrix resin, thinner and initiator are mixed.
11. methods according to claim 10, wherein, comprise the step that matrix resin, thinner and initiator mix: by matrix resin and mixing diluents, obtain the slurries containing matrix resin; Described initiator is mixed with the described slurries containing matrix resin;
Preferably, be 30-60 DEG C by the temperature of matrix resin and mixing diluents, be more preferably 45-60 DEG C.
Protecting layer compositions in 12. claim 1-9 described in any one is preparing the application in protective layer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107512060A (en) * | 2017-09-08 | 2017-12-26 | 中国乐凯集团有限公司 | A kind of solar energy unmanned plane wing cover material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161862A (en) * | 2011-02-25 | 2011-08-24 | 上海长润发涂料有限公司 | Ultraviolet (UV) light-curable polyurethane acrylic resin composite |
| CN102504623A (en) * | 2011-09-28 | 2012-06-20 | 中钞特种防伪科技有限公司 | Peeling layer composition and its preparation method and application |
| CN102604510A (en) * | 2012-02-14 | 2012-07-25 | 山西省应用化学研究所 | UV (ultraviolet) coating applied on melamine veneer without applying ground coating |
| CN102796440A (en) * | 2011-09-15 | 2012-11-28 | 武汉虹之彩包装印刷有限公司 | Gildable gravure line UV (Ultraviolet) gloss oil and preparation method thereof |
| CN102925027A (en) * | 2012-11-15 | 2013-02-13 | 深圳市深赛尔股份有限公司 | UV (ultraviolet) duct gloss oil |
-
2015
- 2015-11-10 CN CN201510763269.XA patent/CN105419572B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161862A (en) * | 2011-02-25 | 2011-08-24 | 上海长润发涂料有限公司 | Ultraviolet (UV) light-curable polyurethane acrylic resin composite |
| CN102796440A (en) * | 2011-09-15 | 2012-11-28 | 武汉虹之彩包装印刷有限公司 | Gildable gravure line UV (Ultraviolet) gloss oil and preparation method thereof |
| CN102504623A (en) * | 2011-09-28 | 2012-06-20 | 中钞特种防伪科技有限公司 | Peeling layer composition and its preparation method and application |
| CN102604510A (en) * | 2012-02-14 | 2012-07-25 | 山西省应用化学研究所 | UV (ultraviolet) coating applied on melamine veneer without applying ground coating |
| CN102925027A (en) * | 2012-11-15 | 2013-02-13 | 深圳市深赛尔股份有限公司 | UV (ultraviolet) duct gloss oil |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107512060A (en) * | 2017-09-08 | 2017-12-26 | 中国乐凯集团有限公司 | A kind of solar energy unmanned plane wing cover material and preparation method thereof |
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