CN104017318B - Information Level resin for anodized aluminium and preparation method thereof and alumite thermoprinting foil - Google Patents
Information Level resin for anodized aluminium and preparation method thereof and alumite thermoprinting foil Download PDFInfo
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- CN104017318B CN104017318B CN201410201507.3A CN201410201507A CN104017318B CN 104017318 B CN104017318 B CN 104017318B CN 201410201507 A CN201410201507 A CN 201410201507A CN 104017318 B CN104017318 B CN 104017318B
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Abstract
The present invention discloses a kind of Information Level resin for anodized aluminium and preparation method thereof and alumite thermoprinting foil, the preparation method of the described Information Level resin for anodized aluminium, comprise the following steps: add acrylate monomer, Part I the first solvent and part initiator, it is heated to reacting temperature required, insulation reaction；Remaining initiator is dissolved in Part II the first solvent, adds at twice in reactor；After initiator is added, continue insulation reaction 6～8h；Stop heating, add remaining Part III the first solvent, cooling, obtain acrylic resin；Additive, the glue becoming solid content to be 15%～25% with the second solvent dilution is added in acrylic resin.Described Information Level resin is mainly used in the product that thermoprint base material is tobacco bale cork paper, and the advantage of described Information Level resin is mainly manifested in VOCS can reach tobacco bale requirement, and solvent resistance, and wearability is better than the product in existing market, and working life is long.
Description
Technical field
The present invention relates to functional film field, particularly relate to a kind of Information Level resin for anodized aluminium and preparation side thereof
Method and alumite thermoprinting foil.
Background technology
Alumite thermoprinting foil, is a kind of thermoprint material that is coated and vacuum aluminum-coated and that make in film substrate, is one
Plant common printing consumable material.Gold stamping picture and text have visual effect bright and glittering, magnificent, be widely used in clothing,
The various industries such as paper, plastic cement, glass, electronic apparatus, toy, gift and artware.Existing anodized aluminium is at mylar
On form the thermoprint material of 4 layers of coating through certain coating process, these coatings are respectively release layer, coloring from the bottom to top
Layer, aluminium coated, adhesive layer.Wherein dyed layer resin (i.e. Information Level resin) is prepared frequently with the isocyanates of double-component, and it is fitted
Short with the phase, often can cause raw-material waste, add production cost.Additionally, on market existing crylic acid resin
Chromatograph resin, its solvent resistance and wearing no resistance, and have and much can not meet VOCS examination criteria.
Therefore, existing technology need development.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of Information Level resin for anodized aluminium
And preparation method thereof and alumite thermoprinting foil, it is intended to solve to use the solvent resistance of Information Level resin of existing anodized aluminium and wear-resisting
Property difference etc. problem.
Technical scheme is as follows:
A kind of preparation method of the Information Level resin for anodized aluminium, wherein, the described Information Level resin for anodized aluminium
Preparation method, comprise the following steps:
Add acrylate monomer, Part I the first solvent and part initiator, be heated to reacting temperature required, insulation
Reaction；
Remaining initiator is dissolved in Part II the first solvent, adds at twice in reactor；Initiator is added
After, continue insulation reaction 6～8h；
Stop heating, add remaining Part III the first solvent, cooling, obtain acrylic resin；
Adding additive in acrylic resin, the resin becoming solid content to be 15%～25% with the second solvent dilution is molten
Liquid.
For the preparation method of the Information Level resin of anodized aluminium, wherein, described reaction is temperature required is 75～125 DEG C.
For the preparation method of the Information Level resin of anodized aluminium, wherein, the process adding initiator described in is often to react 2h
After add once, each additional time is 10～20min.
For the preparation method of the Information Level resin of anodized aluminium, wherein, described acrylate monomer comprise ethyl acrylate,
One or several in butyl acrylate, methyl methacrylate, acrylic acid, Hydroxypropyl methacrylate, styrene, acrylonitrile
Kind；
Described initiator is in benzoyl peroxide, t-butylperbenzoate, lauroyl peroxide, cumyl peroxide
One or more；
Described first solvent is one or more in ethyl acetate, butyl acetate, butanone；
Mass ratio 40:60:1.5～2.5 between acrylate monomer, the first solvent, initiator three.
For the preparation method of the Information Level resin of anodized aluminium, wherein, described novolac epoxy resin is o-cresol formaldehyde epoxy
Resin, epoxide equivalent is 95～210, and softening point is 65～75 DEG C, addition be the solids content of Information Level resin 1.5～
8wt%；
Described styrene-maleic anhydride copolymer weight average molecular weight 5500, glass transition temperature 155 DEG C, addition is
The 15～30wt% of the solids content of Information Level resin；
Described isocyanate curing agent is trimer, and solid content is 50%, and isocyanate group content is 8.5%, is using
Front need to add appropriate ethanol and block, addition is the 15～30wt% of the solids content of Information Level resin；
The number of seconds of described nitrocotton is 1/16, and addition is the 1.5～6wt% of the solids content of Information Level resin.
A kind of Information Level resin for anodized aluminium, wherein, the described Information Level resin for anodized aluminium uses as above institute
The preparation method for the Information Level resin of anodized aluminium stated prepares.
A kind of alumite thermoprinting foil, including aluminium coated and adhesive layer, including the adhesive layer from top to bottom set gradually, aluminizes
Layer, dyed layer, wherein, described dyed layer is to use the Information Level resin for anodized aluminium as above to make.
Described alumite thermoprinting foil, wherein, described alumite thermoprinting foil also includes base membrane layer and release layer；Described gluing
Layer, aluminium coated, dyed layer, release layer, base membrane layer are the most from top to bottom arranged.
Described alumite thermoprinting foil, wherein, described dyed layer and aluminium coated are attached to cork paper by described adhesive layer
On base material.
Beneficial effect: a kind of Information Level resin for anodized aluminium provided by the present invention, described Information Level resin mainly should
For the product that thermoprint base material is tobacco bale cork paper, the advantage of described Information Level resin is mainly manifested in VOCS can reach tobacco bale
Requirement, and solvent resistance, wearability is better than the product in existing market, and working life is long.
Detailed description of the invention
The present invention provides a kind of Information Level resin for anodized aluminium and preparation method thereof and alumite thermoprinting foil, for making this
Purpose, technical scheme and the effect of invention are clearer, clear and definite, and the present invention is described in more detail below.Should be appreciated that this
Specific embodiment described by place only in order to explain the present invention, is not intended to limit the present invention.
Specifically, the preparation method of the described Information Level resin for anodized aluminium (hereinafter referred to as Information Level resin) include with
Lower step:
One, the preparation of acrylic resin:
(1) first it is proportionally added into acrylate monomer, Part I the first solvent and part initiator in a kettle., adds
Heat to reacting temperature required, insulation reaction；
(2) remaining initiator is dissolved in Part II the first solvent, adds at twice in reactor；Initiator is mended
After adding, continue insulation reaction 6～8h；
(3) stop heating, add remaining Part III the first solvent, cooling, discharging, obtain acrylic resin.
Wherein, the mass ratio 40:60:1.5～2.5 between acrylate monomer, the first solvent, initiator three.
Described acrylate monomer comprises ethyl acrylate (EA), butyl acrylate (BA), methyl methacrylate
(MMA), the one or several in acrylic acid (AA), Hydroxypropyl methacrylate (β-HPMA), styrene (St), acrylonitrile (AN)
Kind.The consumption of each acrylate monomer in system, estimates according to FOX formula, the glass transition of design acrylic resin
Temperature is at 70 DEG C-95 DEG C.
Described FOX formula is shown below:
1/Tg=W1/Tg1+W2/Tg2+W3/Tg3.......Wn/Tgn；
Tg (unit is K) is monomer homopolymer vitrification point, and W is mass fraction.
Described initiator can be benzoyl peroxide (BPO), t-butylperbenzoate (TBPB), lauroyl peroxide
(LPO), one or more in cumyl peroxide (DCP).In the process, initiator is divided into two parts and adds, and first adds
The Part I initiator entering reactor is about the 40～60% of total initiator；The Part II initiator being subsequently used for adding is
The 40～60% of total initiator.Described add initiator process be often reaction 2h after add once, each additional time is 10
～20min.
Described first solvent is one or more in ethyl acetate, butyl acetate, butanone.Described first solvent is points three
Part joins in reactor, be initially charged Part I first solvent of reactor be about total first solvent load 40～
60%；It is about the 10～11% of total first solvent load for dissolving Part II first solvent of initiator；Remaining 3rd
Part the first solvent is about the 29～50% of total first solvent load.
Described reaction is temperature required is 75～125 DEG C.
In described acrylic resin systems, theoretical solid content is at 40wt%, needed for reach conversion ratio and should be more than 98%, body
Be viscosity be 100～200s.
Two, the preparation of Information Level resin
In acrylic resin, proportionally add certain additive, then become the solid content to be with the second solvent dilution
The resin solution of 15%～25%, after being completely dispersed, obtains described Information Level resin.
Wherein, described additive include novolac epoxy resin, styrene-maleic anhydride copolymer, isocyanate curing agent,
Nitrocotton etc..Described novolac epoxy resin is o-cresol formaldehyde epoxy resin, and epoxide equivalent is 95～210, and softening point is 65～75
DEG C, addition account for solid amount 1.5～8wt% (solids content of described solid amount the most described Information Level resin, for propylene
Solids content and additive solids content sum in acid resin).Described styrene-maleic anhydride copolymer weight average molecular weight
5500, glass transition temperature 155 DEG C, addition accounts for the 15～30wt% of solid amount.Described isocyanate curing agent is three
Aggressiveness, solid content is 50%, and isocyanate group content is 8.5%, and addition accounts for the 15～30wt% of solid amount；Described isocyanide
Acid esters firming agent needs add appropriate ethanol before use and carries out partially end-blocked (NCO:OH=1:1).The second of described nitrocotton
Number is 1/16, and addition accounts for the 1.5～6wt% of solid addition.
Described second solvent is one or more in butyl acetate, ethyl acetate and butanone.
Also providing for a kind of Information Level resin for anodized aluminium in the present invention, described Information Level resin is to use as mentioned above
The Information Level resin for anodized aluminium preparation method prepare.
The present invention also provides for a kind of alumite thermoprinting foil, including the adhesive layer from top to bottom set gradually, aluminium coated,
Chromatograph, wherein, described dyed layer is to use the Information Level resin for anodized aluminium provided by the present invention to make.
Before not carrying out thermoprint, described alumite thermoprinting foil also includes base membrane layer and release layer；Described adhesive layer, aluminize
Layer, dyed layer, release layer, base membrane layer are the most from top to bottom arranged.Described dyed layer is by being just coated with mode by institute with coating machine
State Information Level resin and be coated on release layer surface, after drying tunnel is dried, dyed layer can be formed on release layer surface.
Described alumite thermoprinting foil is mainly used in and carries out shifting thermoprint on cork paper base material, after thermoprint, described
Dyed layer and aluminium coated depart from described release layer, are attached on cork paper base material by described adhesive layer.Use described Information Level
The dyed layer that resin is made, its VOCS can reach tobacco bale requirement, and solvent resistance, and wearability is better than the product in existing market,
Working life is long.
The present invention will be further described by the following examples.
Embodiment 1
By 24kg Hydroxypropyl methacrylate, 5.2kg acrylic acid, 45kg styrene, 69.8g methyl methacrylate,
16kg acrylonitrile, 2kgBPO, 70kg butanone, 26kg ethyl acetate and 46g butyl acetate join in reactor, then heat to
90 DEG C, after insulation 2h, add BPO ethyl acetate solution and (BPO of 1kg is dissolved in the ethyl acetate of 13kg and prepares
), additional time 10～20min.After continuing insulation 2h, then add the BPO ethyl acetate solution of equivalent, then insulation reaction
6h.Finally add 72kg butanone, cooling down, discharging, obtain acrylic resin.
Taking 70kg trimer isocyanate curing agent, add 6kg ethanol and 24kg butanone, stirring reaction completely, obtains part
The isocyanate curing agent solution of end-blocking.
Take 15kg acrylic resin, add the partially end-blocked isocyanate curing agent solution of 5kg, 0.5kg o-cresol formaldehyde ring
Epoxy resins, 0.5kg nitrocotton and 3kg styrene-maleic anhydride copolymer, be subsequently adding 85kg butanone, after uniform stirring dispersion
Obtain Information Level resin.
Embodiment 2
By 20kg Hydroxypropyl methacrylate, 5.2kg acrylic acid, 50kg styrene, 64g methyl methacrylate, 16kg
Acrylonitrile, 2kgLPO, 70kg butanone, 26kg ethyl acetate and 46g butyl acetate join in reactor, then heat to 80
DEG C, after insulation 2h, add LPO ethyl acetate solution (be dissolved in by the LPO of 1kg and to prepare in the ethyl acetate of 13kg),
Additional time 10～20min.After continuing insulation 2h, then add the LPO ethyl acetate solution of equivalent, then insulation reaction 8h.?
After add 72kg butanone, cooling down, discharging, obtain acrylic resin.
Taking 70kg trimer isocyanate curing agent, add 6kg ethanol and 24kg butanone, stirring reaction completely, obtains part
The isocyanate curing agent solution of end-blocking.
Take 15kg acrylic resin, add the partially end-blocked isocyanate curing agent solution of 6kg, 1.0kg o-cresol formaldehyde ring
Epoxy resins, 0.5kg nitrocotton and 2kg styrene-maleic anhydride copolymer, be subsequently adding 85kg butanone, after uniform stirring dispersion
Obtain Information Level resin.
Embodiment 3
By 24kg Hydroxypropyl methacrylate, 5.2kg acrylic acid, 45kg styrene, 69.8g methyl methacrylate,
16kg acrylonitrile, 2kgBPO, 70kg butanone, 26kg ethyl acetate and 46g butyl acetate join in reactor, then heat to
90 DEG C, after insulation 2h, it is cooled to 80 DEG C, adds LPO ethyl acetate solution and (LPO of 1kg is dissolved in the ethyl acetate of 13kg
Prepare), additional time 10～20min.After continuing insulation 2h, then add the LPO ethyl acetate solution of equivalent, then protect
Temperature reaction 6h.Finally add 72kg butanone, cooling down, discharging, obtain acrylic resin.
Taking 70kg trimer isocyanate curing agent, add 6kg ethanol and 24kg butanone, stirring reaction completely, obtains part
The isocyanate curing agent solution of end-blocking.
Take 15kg acrylic resin, add the partially end-blocked isocyanate curing agent solution of 5kg, 0.5kg o-cresol formaldehyde ring
Epoxy resins, 0.5kg nitrocotton and 3kg styrene-maleic anhydride copolymer, be subsequently adding 85kg butanone, after uniform stirring dispersion
Obtain Information Level resin.
Embodiment 4
The mode of the right way is used to be coated on the release layer of alumite thermoprinting foil the Information Level resin of embodiment 1～3 gained
Surface, after drying, forms dyed layer on described release layer surface.Continue on described dyed layer successively coating formed aluminium coated and
Adhesive layer.Then, by the way of platen, carry out heat transfer thermoprint on the surface of cork paper.After thermoprint completes, described coloring
Layer, aluminium coated are attached to cork paper surface by described adhesive layer.The solvent resistance of dyed layer, wearability, VOCS content are entered
Row detection.
Method of testing and result are as follows:
1, solvent resistance test:
(1) ethanol-tolerant test: the dyed layer alcohol wipe that embodiment 1～3 is formed, the most colour-fast；Hot stamping pattern wine
Essence wiping 50 times, the most colour-fast.
(2) resistance to esters solvent: the dyed layer ethyl acetate wiping that embodiment 1～3 is formed 20 times, color is all almost without change
Change；Hot stamping pattern ethyl acetate wiping 10 times, color is all almost without change.
2, wearability test:
Using Gx-C1 scratch-resistant testing, the thing block friction hot stamping pattern of 200g 100 times, color is all almost without change.
3, VOCS detection:
According to YC/T207-2006 " tobacco shred and the mensuration head space-gas phase color of VOC in box packaging paper
Spectrometry ", carry out VOCS test at Agilent (GC) 7890A+ (HS) 7697, test result is as shown in table 1.
Table 1 anodized aluminium chromatograph resin VOCS testing result
In sum, compared with prior art, the information for electrochemical aluminium thermoprinting that the inventive method prepares is used
Layer resin has the advantage that (1) can reach the requirement of tobacco bale (thermoprint base material is cork paper) at VOCS；(2) have well
Solvent resistance, wearability, working life is long.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved according to the above description or to convert, all these modifications and variations all should belong to the guarantor of claims of the present invention
Protect scope.
Claims (10)
1. the preparation method for the Information Level resin of anodized aluminium, it is characterised in that the described Information Level for anodized aluminium
The preparation method of resin, comprises the following steps:
Add reaction monomers, Part I the first solvent and part initiator, be heated to reacting temperature required, insulation reaction；
Remaining initiator is dissolved in Part II the first solvent, adds at twice in reactor；Initiator is added complete
After, continue insulation reaction 6～8h；
Stop heating, add remaining Part III the first solvent, cooling, obtain acrylic resin；
Additive, the resin solution becoming solid content to be 15%～25% with the second solvent dilution is added in acrylic resin；
Described additive includes novolac epoxy resin, styrene-maleic anhydride copolymer, isocyanate curing agent and nitrocotton；
Described reaction monomers comprises ethyl acrylate, butyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl methacrylate
One or more in propyl ester, styrene, acrylonitrile.
The preparation method of the Information Level resin for anodized aluminium the most according to claim 1, it is characterised in that described reaction
Temperature required is 75～125 DEG C.
The preparation method of the Information Level resin for anodized aluminium the most according to claim 1, it is characterised in that described in add
The process of initiator be often reaction 2h after add once, each additional time is 10～20min.
The preparation method of the Information Level resin for anodized aluminium the most according to claim 1, it is characterised in that described initiation
Agent is one or more in benzoyl peroxide, t-butylperbenzoate, lauroyl peroxide, cumyl peroxide；
Described first solvent is one or more in ethyl acetate, butyl acetate, butanone；
Mass ratio 40:60:1.5～2.5 between reaction monomers, the first solvent, initiator three.
The preparation method of the Information Level resin for anodized aluminium the most according to claim 1, it is characterised in that described second
Solvent is one or more in butyl acetate, ethyl acetate and butanone.
The preparation method of the Information Level resin for anodized aluminium the most according to claim 5, it is characterised in that described phenolic aldehyde
Epoxy resin is o-cresol formaldehyde epoxy resin, and epoxide equivalent is 95～210, and softening point is 65～75 DEG C, and addition is Information Level
The 1.5～8wt% of the solids content of resin；
Described styrene-maleic anhydride copolymer weight average molecular weight 5500, glass transition temperature 155 DEG C, addition is information
The 15～30wt% of the solids content of layer resin；
Described isocyanate curing agent is trimer, and solid content is 50%, and isocyanate group content is 8.5%, needs before use
Adding appropriate ethanol to block, addition is the 15～30wt% of the solids content of Information Level resin；
The number of seconds of described nitrocotton is 1/16, and addition is the 1.5～6wt% of the solids content of Information Level resin.
7. the Information Level resin for anodized aluminium, it is characterised in that the described Information Level resin for anodized aluminium uses such as
The preparation method for the Information Level resin of anodized aluminium described in any one of claim 1～6 prepares.
8. an alumite thermoprinting foil, including aluminium coated and adhesive layer, including the adhesive layer from top to bottom set gradually, aluminizes
Layer, dyed layer, it is characterised in that described dyed layer is to use as claimed in claim 7 for the Information Level resin of anodized aluminium
Make.
Alumite thermoprinting foil the most according to claim 8, it is characterised in that described alumite thermoprinting foil also includes base membrane layer
And release layer；Described adhesive layer, aluminium coated, dyed layer, release layer, base membrane layer are the most from top to bottom arranged.
Alumite thermoprinting foil the most according to claim 8, it is characterised in that described dyed layer and aluminium coated are by described
Adhesive layer is attached on cork paper base material.
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| CN201410201507.3A CN104017318B (en) | 2014-05-13 | 2014-05-13 | Information Level resin for anodized aluminium and preparation method thereof and alumite thermoprinting foil |
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| CN201410201507.3A CN104017318B (en) | 2014-05-13 | 2014-05-13 | Information Level resin for anodized aluminium and preparation method thereof and alumite thermoprinting foil |
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| CN104531009B (en) * | 2014-12-31 | 2016-08-24 | 东莞光群雷射科技有限公司 | A kind of offset printing cold wave dual-purpose adhesive and preparation and application thereof |
| CN108102021A (en) * | 2017-12-30 | 2018-06-01 | 张义群 | Highlighted thermoprint packing box glazing transfer membrane and its manufacture craft |
| CN109651559B (en) * | 2018-12-11 | 2021-11-09 | 上海绘兰材料科技有限公司 | Acrylic resin for release-free ironing cloth electrochemical aluminum and preparation method and application thereof |
| CN109836754B (en) * | 2019-01-17 | 2021-08-10 | 广州致辉精化股份有限公司 | Solvent-resistant and boiling-resistant PC mirror resin and preparation method thereof |
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| CN103465668A (en) * | 2013-09-29 | 2013-12-25 | 云南玉溪东魅包装材料有限公司 | Hot stamping foil applied to overlapping hot stamping on gold stamping layer and preparation method of hot stamping foil |
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Denomination of invention: Information level resin for alumite and preparation method of alumite as well as alumite stamping foil Effective date of registration: 20190530 Granted publication date: 20170104 Pledgee: Guangdong Nanhai rural commercial bank Limited by Share Ltd Ping Chau Branch Pledgor: Foshan Nanhai Gotop Packaging Material Co., Ltd. Registration number: 2019990000489 |
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