CN104710890B - A kind of peelable protection ink and preparation method thereof - Google Patents
A kind of peelable protection ink and preparation method thereof Download PDFInfo
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- CN104710890B CN104710890B CN201510105534.5A CN201510105534A CN104710890B CN 104710890 B CN104710890 B CN 104710890B CN 201510105534 A CN201510105534 A CN 201510105534A CN 104710890 B CN104710890 B CN 104710890B
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/108—Hydrocarbon 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/14—Printing inks based on carbohydrates
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- 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
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
Abstract
The present invention relates to peelable protection ink of one kind and preparation method thereof.It takes into account the performances such as adhesive force, elasticity, peel strength, high temperature resistant simultaneously, its membrance casting condition is simple, film body has the performances such as good adhesive force, elasticity, peel strength, high temperature resistant, it can realize that quick monoblock is peeled off, without any residual after stripping, and resistance to elevated temperatures is significantly, and adhesion, do not haze, chemical-resistant reagent ability is strong.The maleic acid copolymerized resin of chloridized polyolefin, vinyl chloride-vinyl acetate, polystyrene polyurethane unsaturated polyester resin and the organosilicon-modified acrylate rubber for the modified by maleic acid anhydride graft that the peelable protection ink is used are used as main film forming matter；Using epoxy resin, the film forming subsidiary material of the peelable protection ink of acetylbutyrylcellulose, blocked polyurethane.
Description
Technical field
The present invention relates to peelable protection ink of one kind and preparation method thereof, belong to functional high polymer material field.
Background technology
Peelable protection materials are a kind of temporary protective materials, different from most of common adhesives, ink, coating,
Peelable protection materials play protection base material while, in addition it is also necessary to protection basal plane have suitable adhesive force with it is peelable
Property, while also requiring that film has certain elasticity, intensity and chemical proofing etc..
WO2005012434A1 discloses kind of a releasable composition, and it contains in specific film-forming material (2) can
Exfoliated particle (3), peelable type particle (3) has the 1st peelable type resin and the 2nd peelable type resin, wherein, the 1st can
Exfoliated resin formation core material (5), the 2nd peelable type resin formation lining material (4).And with the 2nd peelable type tree
Lipid phase ratio, the easily peelable degree of the 1st peelable type resin is of a relatively high.The surface tension of such as the 1st peelable type resin is
0.01N/m~0.025N/m, and the surface tension of the 2nd peelable type resin is 0.026N/m~0.05N/m.
CN103923414A discloses a kind of antistatic, fire-retardant and ambient stable peelable protective film and its preparation side
Method, by the bipolymer or vinyl chloride, the vinylacetate and Malaysia that include 60-80 weight % vinyl chloride and vinylacetate
The terpolymer of acid or vinyl alcohol, and the raw material of 10-30 weight % polyurethane resins are made.The specific insulation of dry film
Less than 108Ω m, just disclosure satisfy that in the case where that need not add conductive titanium dioxide or add seldom conductive titanium dioxide
General antistatic needs, fire resistance is up to V0 grades, the erosion of acidproof alkali salt, with good environmental stability.Diaphragm can
To carry out application on various surfaces by various modes, the cohesive force to substrate surface can be easily changed by raw material composition
Species and ratio regulated and controled, can be applied to decoration and the protection of distinct device and device.
CN103031053A discloses a kind of interim peelable protection ink of protection UV solidifications of touch-screen and its preparation side
Method, the peelable protection ink formulations of UV solidifications, which are constituted, is：50~70 parts of modified acrylic ester resin, acrylate monomer 20~30
Part, 1.0-5.0 parts of light curing agent, 0.1-1.0 parts of thixotropic agent, 0.1-5.0 parts of auxiliary agent, 0.1-1.0 parts of pigment；The preparation method
For：Various raw materials are accurately weighed by formula rate, first by modified acrylic ester resin, acrylate monomer, light curing agent, help
Agent, pigment are sequentially added in reactor and stirred, it is to be mixed it is uniform after, add thixotropic agent, discharged after being uniformly dispersed.The UV of the present invention
The peelable protection ink of solidification is non-solvent and is free of phthalate substance system, more safety and environmental protection.
CN102807785A discloses peelable protection ink of a kind of non-solvent high temperature resistant and preparation method thereof, and it includes
It is prepared from by the raw material of following weight proportion：55~65 parts of vinyl chloride-vinyl acetate resin, 35~45 parts of plasticizer, epoxy resin 0.2~0.5
Part, 0.5~1 part of heat stabilizer, 1~2 part of aerosil, 0.3~0.5 part of toner, 0.6~1 part of levelling agent, defoamer
0.6~1 part and 0.6~1 part of surfactant.The ink uses solventless formulation, printing and non-volatility thing in film forming procedure
Matter, is non-reactive ink, and membrance casting condition is simple, the function admirable of film body.
The film forming matter of peelable protection materials, determines the main performance of peelable protection materials.It is peelable in the prior art
The film forming matter the more commonly used from protection materials has polyurethane, polystyrene, polyvinyl alcohol, organosilicon, vinyl chloride-vinyl acetate resin, acrylic acid tree
Fat etc..In use, being generally blended to use using several film forming matters, however, different film forming matters is when playing the effect of oneself, but
Have impact on the effect of other film forming matters, as used polyurethane elastomer and unsaturated polyester (UP) by physical blending with reach it is modified
Purpose, but other machinery performance often is also reduced while its impact flexibility, reduction cure shrinkage is improved, so as to cause
The hydraulic performance decline of peelable protection materials.Peelable protection ink generally there are problems with the prior art：UV curing systems
Peelable protection ink due to crosslink density it is too high, paint film is really up to the mark, causes adhesive force to be deteriorated, and easily comes off；Non-solvent
Need largely to use plasticizer in peelable protection ink, in high temperature film forming, plasticizer is easily migrated to paint film both sides, is caused
Adhesive force, heat resistance etc. are deteriorated, and do not have the effect of protection, and plasticizer is unfriendly to human body.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of combination property is excellent for above-mentioned the problems of the prior art
Different peelable protection ink and preparation method thereof, it is not contained, and plasticizer, membrance casting condition are simple, and film body has well peelable
From performances such as property, moderate adhesive force, high temperature resistants.Peelable glue pliability and elasticity prepared by the present invention is good, and adhesive force is moderate, energy
Realize that quick monoblock is peeled off, without any residual after stripping, and resistance to elevated temperatures is notable, and adhesion, do not haze, chemical-resistant reagent
Ability is strong.
The technical solution adopted in the present invention is：
A kind of peelable protection ink, its main film forming substance：Polystyrene-poly urethane-unsaturated polyester resin 25-30
Part；20-40 parts of the chloridized polyolefin of modified by maleic acid anhydride graft；Vinyl chloride-vinyl acetate-maleic acid copolymerized resin 20-
30 parts；30-40 parts of organosilicon-modified acrylate rubber；
It is preferred that, described polystyrene-poly urethane-unsaturated polyester (UP) copolymer, it has the residue of acryloxy.
It is preferred that, described polystyrene-poly urethane-unsaturated polyester (UP) copolymer preparation method is：
Step (1)：The synthesis of unsaturated polyester (UP) containing terminal hydroxy group
In four mouthfuls of reaction vessels with stirring and condensation, 70-100 parts of monounsaturated dicarboxylic acids, 10-70 parts of insatiable hungers are put into successively
With binary acid and/or 10-40 parts of unsaturated dicarboxylic acid anhydrides, 80-160 parts of polyalcohols, 0.1-3 parts of catalyst, 100-200 parts it is molten
Agent, logical nitrogen is simultaneously stirred, and is to slowly warm up to 120-140 DEG C, is maintained gradually to heat up 150~190 DEG C again after 2-3h and is continued to react 1-
4h, until acid number close to or up 40mgKOH/g, continues to add polyalcohol, reacts 0.5-2h, stretched system acid number is less than
10mgKOH/g, and water yield it is unchanged when be reaction end.Vacuumize, wash, dry.Obtain the insatiable hunger containing terminal hydroxy group
And polyester；In this step, many 0.5-10.5mol% of the consumption of-OH consumption relative to-COOH (molar percentage)；
Step (2)：The synthesis of polyurethane unsaturated polyester (UP) copolymer
Take 60-160 parts of 50-120 parts of unsaturated polyester (UP), polyisocyanates containing terminal hydroxy group, the catalysis of first step synthesis
In 0.1-3 parts of agent, 100-300 parts of addition reaction vessels of solvent, temperature reaction 2-4h, when-NCO% is stable, obtain end group for-
NCO polyurethane unsaturated polyester (UP) copolymer；Wherein, many 1-5mol% (Mole percents of the consumption of-NCO consumption relative to-OH
Than)；
30-90 parts of (methyl) hydroxyalkyl acrylate is added, while 0.1-3 parts of catalyst, 0.1-3 parts of polymerization inhibitor are added, after
Continuous reaction, into system, NCO exhausts, and stops reaction.Vacuumize, wash, dry.Obtain the polyurethane that end group is acryloxy
Unsaturated polyester (UP) copolymer.In this step, the consumption of (methyl) hydroxyalkyl acrylate is controlled, so that it has just reacted system
In-NCO.
Step (3)：The synthesis of polystyrene-poly urethane-unsaturated polyester (UP) copolymer
The end group for taking second step to synthesize is 50-100 parts of the polyurethane unsaturated polyester (UP) copolymer of acryloxy, benzene second
Alkene, 0.5-2 parts of initiator, 50-300 parts of solvent, heating response 1-4h continue temperature reaction 0.5-2 hours, stop reaction, take out
Vacuum, is washed, and is dried.Obtain described polystyrene-poly urethane-unsaturated polyester resin；The end group is acryloyl-oxy
The polyurethane unsaturated polyester (UP) copolymer of base and the mol ratio of styrene are preferably 1: 1.5-3.
Described binary acid is monounsaturated dicarboxylic acid and unsaturated dibasic acid.Wherein, monounsaturated dicarboxylic acid selects monoethyl two
Formic acid, tetrabromophthalate, octadecane diacid.Contain tetrachlorophthalic acid, tetrabromophthalate in copolymer so that
There is good compatibility with vinyl chloride-vinyl acetate resin, and there is moderate adhesive force to base material；And select the octadecane diacid of long-chain, then
The compliance of copolymer molecule can be balanced.Unsaturated dibasic acid selects maleic acid；Unsaturated dicarboxylic acid anhydride is from rich horse
Acid anhydrides, chlordene endo-methylene group phthalic anhydride.Polyalcohol is from TMPD, 2- ethyl -2- butyl -1,3- the third two
Alcohol.Polyisocyanates selects 4,4 '-methyl diphenylene diisocyanate.(methyl) hydroxyalkyl acrylate selects (methyl) third
Olefin(e) acid hydroxy dodecyl acrylate, introduces (methyl) dihydroxypropyl dodecyl ester of hydroxyl in copolymer molecule structure,
So that strand is freely rotatable, there is resin excellent flexible while having preferable adhesive force.
It is preferred that described polystyrene-poly urethane-unsaturated polyester (UP) copolymer number-average molecular weight is 7000~170000；Point
Son amount is distributed in less than 3.
Polystyrene-poly urethane-the unsaturated polyester resin have concurrently the low-shrinkage of polystyrene, polyurethane it is flexible
The adhesive force of property and unsaturated polyester resin.It is poly- except playing in the composition by adding the copolymer containing the three block
Styrene, polyurethane, outside the characteristic of unsaturated polyester (UP), good synergy is also created, its using effect is much better than will be poly-
Styrene, polyurethane, unsaturated polyester (UP) are used for peelable material as independent component；By MOLECULE DESIGN, gathered from optimal
Monomer is closed to balance the combination property of peelable material, material structure, the controllable design of performance is realized.From monoethyl diformazan
Acid, tetrabromophthalate, chlordene endo-methylene group phthalic anhydride, add and often use film forming matter chlorine vinegar tree with peelable material
The compatibility of fat so that prepared polystyrene-poly urethane-unsaturated polyester resin has well compatible with vinyl chloride-vinyl acetate resin
Property；From TMPD, 2- ethyls -2- butyl -1,3-PD, octadecane diacid, (methyl) dihydroxypropyl 12
The long-chain molecules such as Arrcostab so that polymer molecular chain is freely rotatable, then take into account very well the adhesive force of peelable material with it is soft
It is soft；Polystyrene block then ensure that the excellent film forming of peelable material.
It is preferred that, 25-30 parts of the chloridized polyolefin of modified by maleic acid anhydride graft；Vinyl chloride-vinyl acetate-maleic acid copolymerized
25-30 parts of resin；35-40 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane-unsaturated polyester resin 25-
30 parts；
Wherein, the chloridized polyolefin of preferably described modified by maleic acid anhydride graft is the chlorination second of modified by maleic acid anhydride graft
Alkene/propene/but-1-ene random terpolymer；Wherein, ethylene contents are 3-5mol%；Butene content is 1-3mol%；Chlorinity
For 12-16 weight %；The content of maleic anhydride is 5~9 weight %, and its number-average molecular weight is 7000-400.000；It is further preferred that its
Middle ethylene contents are 4.0mol%；Butene content is 2.5mol%；Chlorinity is 15 weight %；The content of maleic anhydride is 7 weights
% is measured, number-average molecular weight is 10000-200.000.It has been found that in the system of the application, being less than 12wt% in chlorinity
Situation, paint film adhesion be deteriorated；Its chlorinity is higher than 16 weight %, and the strippable property of paint film declines.
It is preferred that, the equal number-average molecular weight of weight of vinyl chloride-vinyl acetate-maleic acid copolymerized resin is 40.000-
80.000；
It is preferred that, silicone content described in organosilicon-modified acrylate rubber is 5-10wt%；The equal number-average molecular weight of weight
For 50.000-600.000；The acrylate monomer can be the one or more of following material：(methyl) methyl acrylate,
(methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) i-butyl base ester, (first
Base) acrylic acid amyl group ester, (methyl) acrylic acid hexyl ester, (methyl) acrylic acid octyl group ester, (methyl) nonylphenol acrylate ester, (first
Base) lauryl acrylate, (methyl) trimethylcyclohexylacrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid uncle
Butylcyclohexyl acetate.Organic silicon monomer can be the one or more of following material：γ-acryloxypropyl trimethoxy silicon
Alkane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl three (2- methoxy ethoxies)
Silane, vinyltrimethoxy silane, VTES and vinyl three (2- methoxy ethoxies) silane, propylene
Acyloxy silane, methacryloxypropyl silane, vinyl alkoxysilicone, vinyl methyl diacetoxy silane, third
Olefin(e) acid root closes propyl group triacetoxysilane, and (methyl) propylene acid group closes propyl group triacetoxysilane.
Applicant has been surprisingly found that, not by theoretical restriction of the prior art, four kinds of polymer of above-mentioned consumption are in film forming mistake
Cheng Zhong, in addition to respective characteristic is played, cooperates between component, learns from other's strong points to offset one's weaknesses, can produce good synergy, its effect
It is much better than one or two kinds of resins therein are used alone；Film forming matter, paint film energy are used as using four kinds of polymer of above-mentioned consumption
Adhesive force and strippable property are balanced very well；Especially described polystyrene-poly urethane-unsaturated polyester resin, it is being assigned very well
While giving paint film good strippable property, the heat-resisting quantity of ink is significantly improved.
Applicant is more had been surprisingly found that, the subsidiary film forming matter of following consumption is added in above-mentioned formula, and decapacitation is further put down
Weigh outside adhesive force and strippable property, moreover it is possible to improve the heat-resisting quantity of paint film, and be produced from levelling effect, without adding other levellings
Agent.Described subsidiary film forming matter is constituted：Acetylbutyrylcellulose, 10-15 parts；Epoxy resin, 10-15 parts, enclosed type is gathered
Urethane, 10-15 parts；It is preferred that, subsidiary film forming matter also contains：Organic tin catalyst, 1-2 parts.
Because epoxy resin is material known in the art, it will not be repeated here.Preferred epoxy is that epoxide number is
0.8~1.2 epoxy resin；Suitable epoxy resin epoxy resin commonly used in the art, such as using polyethylene glycol, polypropylene glycol,
The glycidol ether such as hexylene glycol, trimethylolpropane, glycerine, pentaerythrite, D-sorbite compound, cycloaliphatic epoxy,
One or more in epoxy resin E-39, epoxy resin E-44, epoxy resin E-51, epoxy resin E-56D；
Based on reactivity, stability, color inhibition etc., preferably in blocked polyurethane-NCO content in 6-9wt%, it is minimum
Solidification temperature is more than 120 DEG C, such as B1370B.
It is any one in the preferred dibutyl tin dilaurate of organotin, Butyl Tin Trilaurate or sulfydryl oleic acid methyl tin
Kind；
It is preferred that, the peelable ink also contains pigment, thixotropic agent, defoamer, antioxidant, solvent etc.；
It is preferred that content be 1-3 parts of pigment；0.1-0.5 parts of thixotropic agent；Defoamer, 0.1-0.5 parts；Antioxidant, 0.1-0.5
Part；20-60 parts of solvent.
The pigment commonly uses pigment commonly used in the art, such as one or both of barba hispanica, ultramarine blue, cobalt blue or phthalocyanine blue with
On mixture；
The preferred fumed silica of thixotropic agent；
The defoamer be organic silicon defoamer, its act on be reduce manufacture and use during produced by bubble.
Described antioxidant is selected from alkylation of hindered phenol, diphenyl phosphite, triphenyl phosphite, thioester, alkyl
Change one or more of mixtures in hindered amine or hydroxybenzotriazole；It is preferred that (the β-(3,5- of alkylated hindered phenolic material four
Di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (Irganox1010) or phosphorous acid three (2,4- di-tert-butyl-phenyl)
Ester (Irganox168).
The solvent selects organic solvent commonly used in the art；Can enumerate ester system, ketone system, chlorine system, alcohol system, ether system, hydrocarbon system,
Ether-ether system etc..Ethylcarbitol acetate, butyl cellosolve acetic acid esters, propylene glycol alkyl ether acetic acid ester, N- can be for example enumerated as
Methyl pyrrolidone (NMP), methyl proxitol acetate, cyclohexanone, methyl ethyl ketone (MEK), methyl isopropyl Ketone, second two
Alcohol methyl ether, ethylene glycol ethyl ether, glycol propyl ether, butyl glycol ether, diethylene glycol diethyl ether ethyl acetate, MEK, methyl are different
Butyl ketone, monomethyl ether glycol ester, gamma-butyrolacton, propionic acid -3- ether ethyl ester, butyl carbitol, butyl carbitol acetic acid
Ester, methyl proxitol, propylene glycol methyl ether acetate, diethylene glycol ether acetate, ethoxyl ethyl propionate, hexamethylene, diformazan
One or more in benzene.
The peelable viscosity of the protection ink at 25 DEG C is preferably 2000~60,000cps, and preferably 20,000~30,
000cps。
The preparation method of the peelable protection ink, its preparation method uses method commonly used in the art, such as：Will be described
Raw material carries out the dispersed rear formation peelable protection ink.
It is preferred that preparation method comprises the following steps：
1) the various raw materials of precise；
2) main film forming matter and solvent are uniformly dispersed, obtain mixed solution 1；
3) and then pigment, defoamer, antioxidant (if desired, and add time film forming matter) are added, three-roll grinder is ground
Mill, obtains mixed solution 2；
4) then add thixotropic agent, be uniformly dispersed discharging.
It is described it is peelable protection ink application process, the ink by silk-screen printing technique be printed in ito glass or
On PET film base material, screen printing net plate mesh number is 250 mesh or 300 mesh, and it is in 45° angle to keep scraper, ink is evenly applied to base material
On.Through overbaking film forming after finishing printing, the film is fully peeled off from base material.
Relative to prior art, the advantage of the application：
1) peelable protection ink in the prior art, is used as using vinyl chloride-vinyl acetate resin, epoxy resin, acrylate more
Main film forming substance.However, vinyl chloride-vinyl acetate resin is as conventional film forming matter, its combination property is bad, and conventional acrylate tree
Fat (such as (methyl) methacrylate resin, PMMA) does not have good elasticity, and the adhesive force of epoxy resin is not good, causes such
Peelable protection ink generally can not take into account the adhesive force and strippable property of film simultaneously in use, and being unable to monoblock when peeling off peels off
Or adhesive force is too poor.It is found by the applicant that the chloridized polyolefin of the modified by maleic acid anhydride graft of above-mentioned consumption, vinyl chloride-vinyl acetate
Ester-maleic acid copolymerized resin, organosilicon-modified acrylate rubber, polystyrene-poly urethane-unsaturated polyester resin into
In membrane process, in addition to respective characteristic is played, cooperated between component, learn from other's strong points to offset one's weaknesses, good synergy, energy can be produced
The adhesive force and strippable property of balance paint film, and resistance to elevated temperatures is excellent very well.
2) a certain amount of addition acetylbutyrylcellulose, epoxy resin, closing are added simultaneously in above-mentioned main film-forming components
Type polyurethane is as the film forming subsidiary material of peelable protection ink, and its effect is more excellent.Acetylbutyrylcellulose is commonly used for ink
Auxiliary agent, applicant is had been surprisingly found that acetylbutyrylcellulose as film forming matter, with epoxy resin, blocked polyurethane compounding conduct
Film forming subsidiary material, by between epoxy resin, blocked polyurethane, acetylbutyrylcellulose (it contains hydroxyl, carboxyl etc.)
Chemical reaction, three forms micro- crosslinking in film forming procedure, forms microcosmic tridimensional network, is not weakening paint film other property
In the case of energy, further improve the performances such as strippable property, high temperature resistant, chemical-resistant resistance.And primary and secondary film forming described herein
Thing, generates good synergy in ink film forming procedure so that the performance of paint film is significantly lifted.
3) in herein described peelable ink, without adding levelling agent, it has Self-leveling effect；And increase without adding
Agent is moulded, it is more environmentally friendly.
4) using polystyrene-poly urethane-unsaturated polyester resin except performance polystyrene, polyurethane, unsaturated polyester (UP)
Characteristic outside, moreover it is possible to significantly improve the heat-resisting quantity of ink, and solve polystyrene, polyurethane, unsaturated polyester resin and exist
Consistency problem in composition, its effect is much better than to be separately added into polystyrene, polyurethane, unsaturated polyester (UP).Moreover, polyphenyl
Ethene-polyurethane-unsaturated polyester resin generates good synergy with remaining component, improves the combination property of material.
Test event
Film forming is tested
20 are toasted under the conditions of the ito glass substrate for printing the peelable protection ink of the present invention is placed in into 145-160 DEG C
Taken out after~30min, observe film forming situation, including whether edge contracting ink, shrinkage cavity, film cracking, the tactile film forming of finger are dry and comfortable.If film forming
There is no a kind of any of the above described situation, be designated as "○"；If film forming has a kind of any of the above described situation, "×" is designated as.
Adhere to strippable property test
By the peelable protection ink silk screen printing of the present invention in ito glass substrate 25mm*20cm, and under the conditions of 145-160 DEG C
Toast 20-30min film forming, then, stretch by peeling rate 300mm/min along 180 ° of directions (inverse approach), start stripping
Masterpiece is peeling force, unit " gf/inch ".When peeling force is in 10-30gf/inch, monoblock peels off noresidue and then adheres to strippable property
Preferably, it is designated as " 00 "；When peeling force is in 10-30gf/inch, monoblock is peeled off but has minimal residue (revolution mark is less than 5%)
Then adhesion strippable property is good, is designated as "○"；The peelable noresidue but adhesiveness is poor when peeling force is less than 10gf/inch, is designated as
“△”；When peeling force is more than 30gf/inch, then good difficult peel off of adhesiveness has residual, is designated as "×".
High temperature resistant is tested
By the peelable protection ink silk screen printing of the present invention in glass substrate, and toast under the conditions of 145-160 DEG C 20-30min
Film forming, is then placed on heat baking 250 DEG C × 2 hours, the phenomenon such as whether observation film shrinks, is cracked, yellowing；Such as either with or without upper
State phenomenon and show that heat resistance preferably, is designated as " 00 "；If a small amount of yellowing, cracking or micro contraction show heat-resist, note
For "○"；If above-mentioned three kinds of phenomenons, which exist, shows that heat resistance is poor simultaneously, "×" is designated as.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Preparation example 1
Prepare polystyrene-poly urethane-unsaturated polyester (UP) copolymer
Step (1)：The synthesis of unsaturated polyester (UP) containing terminal hydroxy group
In four mouthfuls of reaction vessels with stirring and condensation, 40 parts of tetrachlorophthalic acids, 20 parts of tetrabromo neighbours are put into successively
Phthalic acid, 35 parts of octadecane diacids, 45 parts of maleic acids, 15 parts of fumaric acid anhydrides, 15 parts of chlordene endo-methylene group O-phthalics
Acid anhydrides, 55 parts of TMPDs, 60 parts of 2- ethyls -2- butyl -1,3-PDs, 0.3 part of catalyst, 150 parts of hexamethylenes, lead to
Nitrogen is simultaneously stirred, and is to slowly warm up to gradually heat up 165 DEG C again after 125 DEG C, maintenance 2h and is continued to react 3h, until acid number is close or reaches
To 40mgKOH/g, continue to add 2- ethyls -2- butyl -1,3-PD, react 1h, stretched system acid number is less than 10mgKOH/g,
And water yield it is unchanged when be reaction end, obtain the unsaturated polyester (UP) containing terminal hydroxy group；In this step ,-OH consumption
The many 1.5mol% of consumption relative to-COOH；
Step (2)：The synthesis of polyurethane unsaturated polyester (UP) copolymer
Take 80 parts of the unsaturated polyester (UP) containing terminal hydroxy group, 4,4 '-methyl diphenylene diisocyanate 120 of first step synthesis
In part, 0.1 part of catalyst, 200 parts of addition reaction vessels of hexamethylene, temperature reaction 2h, when-NCO% is stable, obtains end group
For-NCO polyurethane unsaturated polyester (UP) copolymer；Wherein, many 1.5mol% of the consumption of-NCO consumption relative to-OH (mole
Percentage)；
The dihydroxypropyl dodecyl ester accurately measured is added, while 0.3 part of catalyst, 0.3 part of polymerization inhibitor are added, after
Continuous reaction, into system, NCO exhausts, and stops reaction；Vacuumize；Washing；Dry；Obtain the polyurethane that end group is acryloxy
Unsaturated polyester (UP) copolymer.In this step, the consumption of dihydroxypropyl dodecyl ester has just reacted the-NCO in system.
Step (3)：The synthesis of polystyrene-poly urethane-unsaturated polyester (UP) copolymer
The end group for taking second step to synthesize is 00 part of polyurethane unsaturated polyester (UP) copolymer 1, the styrene 150 of acryloxy
Part, 0.5 part of initiator, 300 parts of hexamethylene, heating response 4h continue temperature reaction 0.5 hour, stop reaction；Vacuumize；Wash
Wash；Dry；Obtain described polystyrene-poly urethane-unsaturated polyester resin；
Described polystyrene-poly urethane-unsaturated polyester (UP) copolymer number-average molecular weight is 9500, and molecular weight distribution is 2.
Embodiment 1
The peelable protection ink contains the following raw material：
The ethlyene dichloride of modified by maleic acid anhydride graft/28 parts of propene/but-1-ene random terpolymer；Vinyl chloride-acetic acid second
Alkene ester -25 parts of maleic acid copolymerized resin；37 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane-unsaturation is gathered
30 parts of ester resin；2 parts of pigment；0.2 part of thixotropic agent；Defoamer, 0.3 part；Antioxidant, 0.5 part；40 parts of solvent.
Its preparation method is：
1) the various raw materials of precise；
2) by main film forming matter and solvent (mass ratio, NMP: hexamethylene: MEK=50: 30: 20) be uniformly dispersed, mixed
Solution 1；
3) then add pigment, defoamer, antioxidant, three-roll grinder grinding, obtain mixed solution 2；
4) then add thixotropic agent, be uniformly dispersed discharging.
Embodiment 2
The peelable protection ink contains the following raw material：
The ethlyene dichloride of modified by maleic acid anhydride graft/30 parts of propene/but-1-ene random terpolymer；Vinyl chloride-acetic acid second
Alkene ester -30 parts of maleic acid copolymerized resin；35 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane-unsaturation is gathered
25 parts of ester resin；Acetylbutyrylcellulose, 10 parts；Epoxy resin, 10 parts, blocked polyurethane, 15 parts；Organotin, 1 part；Face
3 parts of material；0.4 part of thixotropic agent；Defoamer, 0.5 part；Antioxidant, 0.4 part；20 parts of solvent.
Its preparation method is：
1) the various raw materials of precise；
2) main film forming matter and solvent are uniformly dispersed, obtain mixed solution 1；
3) then add pigment, defoamer, antioxidant, secondary film forming matter, three-roll grinder grinding, obtain mixed solution 2；
4) then add thixotropic agent, be uniformly dispersed discharging.
Embodiment 3
The peelable protection ink contains the following raw material：
The ethlyene dichloride of modified by maleic acid anhydride graft/35 parts of propene/but-1-ene random terpolymer；Vinyl chloride-acetic acid second
Alkene ester -25 parts of maleic acid copolymerized resin；30 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane-unsaturation is gathered
30 parts of ester resin；Acetylbutyrylcellulose, 11 parts；Epoxy resin, 12 parts, blocked polyurethane, 10 parts；Organotin, 2 parts；Face
2 parts of material；0.3 part of thixotropic agent；Defoamer, 0.5 part；Antioxidant, 0.4 part；30 parts of solvent.
Its preparation method is：
1) the various raw materials of precise；
2) main film forming matter and solvent are uniformly dispersed, obtain mixed solution 1；
3) then add pigment, defoamer, antioxidant, secondary film forming matter, three-roll grinder grinding, obtain mixed solution 2；
4) then add thixotropic agent, be uniformly dispersed discharging.
Embodiment 4
The peelable protection ink contains the following raw material：
The ethlyene dichloride of modified by maleic acid anhydride graft/28 parts of propene/but-1-ene random terpolymer；Vinyl chloride-acetic acid second
Alkene ester -25 parts of maleic acid copolymerized resin；37 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane-unsaturation is gathered
30 parts of ester resin；Acetylbutyrylcellulose, 12 parts；Epoxy resin, 12 parts, blocked polyurethane, 15 parts；Organotin, 1.5 parts；
2 parts of pigment；0.3 part of thixotropic agent；Defoamer, 0.5 part；Antioxidant, 0.4 part；30 parts of solvent.
Its preparation method is：
1) the various raw materials of precise；
2) main film forming matter and solvent are uniformly dispersed, obtain mixed solution 1；
3) then add pigment, defoamer, antioxidant, secondary film forming matter, three-roll grinder grinding, obtain mixed solution 2；
4) then add thixotropic agent, be uniformly dispersed discharging.
Comparative example 1
The peelable protection ink contains the following raw material：
The ethlyene dichloride of modified by maleic acid anhydride graft/80 parts of propene/but-1-ene random terpolymer；Vinyl chloride-acetic acid second
Alkene ester -20 parts of maleic acid copolymerized resin；20 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane-unsaturation is gathered
5 parts of ester resin；2 parts of pigment；0.2 part of thixotropic agent；Defoamer, 0.3 part；Antioxidant, 0.5 part；40 parts of solvent.
Its preparation method be the same as Example 1.
Comparative example 2
The peelable protection ink contains the following raw material：
The ethlyene dichloride of modified by maleic acid anhydride graft/50 parts of propene/but-1-ene random terpolymer；Vinyl chloride-acetic acid second
Alkene ester -40 parts of maleic acid copolymerized resin；30 parts of organosilicon-modified acrylate rubber；2 parts of pigment；0.2 part of thixotropic agent；Froth breaking
Agent, 0.3 part；Antioxidant, 0.5 part；40 parts of solvent.
Its preparation method be the same as Example 1.
Comparative example 3
The peelable protection ink contains the following raw material：
The ethlyene dichloride of modified by maleic acid anhydride graft/28 parts of propene/but-1-ene random terpolymer；Vinyl chloride-acetic acid second
Alkene ester -25 parts of maleic acid copolymerized resin；37 parts of organosilicon-modified acrylate rubber；Polystyrene, 10 parts；Polyurethane, 10
Part；Unsaturated polyester resin, 10 parts；Acetylbutyrylcellulose, 12 parts；Epoxy resin, 12 parts, blocked polyurethane, 15 parts；Have
Machine tin, 1.5 parts；2 parts of pigment；0.3 part of thixotropic agent；Defoamer, 0.5 part；Antioxidant, 0.4 part；30 parts of solvent.
Its preparation method be the same as Example 1.
Comparative example 4
The peelable protection ink of prior art, contains following components：Vinyl chloride-vinyl acetate resin, 40 parts；MMA resins, 15 parts；Epoxy
Resin, 10 parts；Dioctyl adipate, 23 parts；Epoxidized soybean oil, 10 parts
Using identical technique, the peelable protection ink of embodiment, comparative example is uniformly applied by silk-screen printing technique
Cover on glass baseplate, tested.
Test result is as described in Table 1
Table 1
| Numbering | Film forming | Adhere to strippable property | High temperature resistant | Comprehensive Assessment |
| Embodiment 1 | ○ | ○ | ○ | It is good |
| Embodiment 2 | ○○ | ○○ | ○○ | It is excellent |
| Embodiment 3 | ○○ | ○○ | ○○ | It is excellent |
| Embodiment 4 | ○○ | ○○ | ○○ | It is excellent |
| Comparative example 1 | ○ | × | ○ | Difference |
| Comparative example 2 | × | △ | × | Difference |
| Comparative example 3 | × | △ | × | Difference |
| Comparative example 4 | × | × | × | Difference |
From the test result of table 1, simultaneously containing the main film forming matter (maleic acid in herein described specific amount ranges
Chloridized polyolefin, vinyl chloride-vinyl acetate-maleic acid copolymerized resin, the organosilicon-modified acrylate of acid anhydride graft modification
Rubber, polystyrene-poly urethane-unsaturated polyester resin) peelable protection ink simultaneously take into account adhesive force, peel strength,
The performances such as elasticity, high temperature resistant, with unexpected technique effect, its performance is much better than to use vinyl chloride-vinyl acetate resin, (methyl) propylene
Sour late resin, epoxy resin as film forming matter peelable protection ink.And by experimental data it can clearly be seen that adopt simultaneously
With the chloridized polyolefin of modified by maleic acid anhydride graft, vinyl chloride-vinyl acetate-maleic acid copolymerized resin, organic-silicon-modified
The peelable protection ink of ACM, polystyrene-poly urethane-unsaturated polyester resin, its effect is much better than individually
Using one or more peelable protection ink therein, there is good synergy between these three polymer；Using
Epoxy resin, acetylbutyrylcellulose, blocked polyurethane are as film forming subsidiary material, and it adheres to strippable property, heat-resisting quantity and obtained
Greatly improve；Relative to individually epoxy resin is used, it does not reach epoxy resin and acetylbutyrylcellulose, blocked polyurethane
Between synergy；The high temperature resistant of peelable protection ink can be improved by adding polystyrene-poly urethane-unsaturated polyester resin
Property.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than to present invention guarantor
The limitation of scope is protected, although being explained with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Work as understanding, technical scheme can be modified or equivalent substitution, without departing from the reality of technical solution of the present invention
Matter and scope.
Claims (10)
1. a kind of peelable protection ink, it is characterised in that the component and consumption of its film forming matter be：Polystyrene-poly urethane-
25-30 parts of unsaturated polyester resin；20-40 parts of the chloridized polyolefin of modified by maleic acid anhydride graft；Vinyl chloride-vinyl acetate-
Maleic acid copolymerized resin 20-30 parts；30-40 parts of organosilicon-modified acrylate rubber；
Wherein, the polystyrene-poly urethane-unsaturated polyester resin contains the residue of (methyl) acryloxy；It is synthesized
Raw material includes：Tetrachlorophthalic acid, tetrabromophthalate, octadecane diacid, maleic acid, fumaric acid anhydride, chlordene bridge
Methylene phthalic anhydride, TMPD, 2- ethyls -2- butyl -1,3-PD, 4,4 '-diphenyl methane two is different
Cyanate；
Wherein, the chloridized polyolefin of the modified by maleic acid anhydride graft is ethlyene dichloride/propylene/fourth of modified by maleic acid anhydride graft
Alkene random terpolymer；Wherein, ethylene contents are 3-5mol%；Butene content is 1-3mol%；Chlorinity is 12-16 weights
Measure %；The content of maleic anhydride is 5~9 weight %；Its number-average molecular weight is 7,000-400,000.
2. peelable protection ink as claimed in claim 1, it is characterised in that described except film forming beyond the region of objective existence described in claim 1
Secondary film forming matter of the film forming matter also containing following component and content：10-15 parts of acetylbutyrylcellulose；Epoxy resin 10-15
Part；10-15 parts of blocked polyurethane.
3. peelable protection ink as claimed in claim 1 or 2, it is characterised in that preferably：The chlorine of modified by maleic acid anhydride graft
Change 25-30 parts of polyolefin；Vinyl chloride-vinyl acetate -25-30 parts of maleic acid copolymerized resin；Organosilicon-modified acrylate
35-40 parts of rubber；Polystyrene-poly urethane -25-30 parts of unsaturated polyester resin.
4. peelable protection ink as claimed in claim 2, it is characterised in that secondary film forming matter, which is constituted, is：Acetate butyrate fiber
Element, 10-15 parts；10-15 parts of epoxy resin；10-15 parts of blocked polyurethane；1-2 parts of organic tin catalyst.
5. the peelable protection ink as described in claim any one of 1-2, it is characterised in that
Ethylene contents are 4.0mol% in the chloridized polyolefin of the modified by maleic acid anhydride graft；Butene content is 2.5mol%；
Chlorinity is 15 weight %；The content of maleic anhydride is 5~9 weight %；Vinyl chloride-vinyl acetate-maleic acid tree
Fat content of vinylchloride is 61.0 ± 1.0wt%；39.0 ± 1.0wt% of vinyl acetate content.
6. the peelable protection ink as described in claim any one of 1-2, it is characterised in that the polystyrene-poly urethane-
The polymerization of unsaturated polyester resin is：
Step (1)：The synthesis of unsaturated polyester (UP) containing terminal hydroxy group
In four mouthfuls of reaction vessels with stirring and condensation, 70-100 parts of monounsaturated dicarboxylic acids, 10-70 parts of unsaturations two are put into successively
First acid and/or 10-40 parts of unsaturated dicarboxylic acid anhydrides, 80-160 parts of polyalcohols, 0.1-3 parts of catalyst, 100-200 parts of solvents, lead to
Nitrogen is simultaneously stirred, and is to slowly warm up to 120-140 DEG C, is maintained gradually to heat up 150~190 DEG C again after 2-3h and is continued to react 1-4h, directly
To acid number close to or up 40mgKOH/g, continue to add polyalcohol, react 0.5-2h, until system acid number is less than 10mgKOH/
G, and water yield it is unchanged when be reaction end, obtain the unsaturated polyester (UP) containing terminal hydroxy group；In this step ,-OH use
Measure many 0.5-10.5mol% of consumption (molar percentage) relative to-COOH；
Step (2)：The synthesis of polyurethane unsaturated polyester (UP) copolymer
60-160 parts of 50-120 parts of unsaturated polyester (UP), polyisocyanates, the catalyst containing terminal hydroxy group for taking the first step to synthesize
0.1-3 parts, in 100-300 parts of addition reaction vessels of solvent, temperature reaction 2-4h, when-NCO% is stable, obtain end group for-
NCO polyurethane unsaturated polyester (UP) copolymer；Wherein, many 1-5mol% (Mole percents of the consumption of-NCO consumption relative to-OH
Than)；
30-90 parts of (methyl) dihydroxypropyl dodecyl ester is added, while adding 0.1-3 parts of catalyst, polymerization inhibitor 0.1-3
Part, continue to react, NCO exhausts into system, stop reaction；Vacuumize；Washing；Dry；It is acryloxy to obtain end group
Polyurethane unsaturated polyester (UP) copolymer；
Step (3)：The synthesis of polystyrene-poly urethane-unsaturated polyester (UP) copolymer
Take the end group that second step is synthesized for 50-100 parts of the polyurethane unsaturated polyester (UP) copolymer of acryloxy, styrene, draw
0.5-2 parts of agent, 50-300 parts of solvent are sent out, heating response 1-4h continues temperature reaction 0.5-2 hours, stops reaction；Vacuumize；
Washing；Dry；Obtain described polystyrene-poly urethane-unsaturated polyester resin.
7. the peelable protection ink as described in claim any one of 1-2, it is characterised in that it also contains：1-3 parts of pigment；
0.1-0.5 parts of thixotropic agent；0.1-0.5 parts of defoamer；0.1-0.5 parts of antioxidant；20-60 parts of solvent.
8. a kind of preparation side of polystyrene-poly urethane-unsaturated polyester resin as any one of claim 1-7
Method, it is characterised in that it comprises the following steps：
Step (1)：The synthesis of unsaturated polyester (UP) containing terminal hydroxy group
In four mouthfuls of reaction vessels with stirring and condensation, 70-100 parts of monounsaturated dicarboxylic acids, 10-70 parts of unsaturations two are put into successively
First acid and/or 10-40 parts of unsaturated dicarboxylic acid anhydrides, 80-160 parts of polyalcohols, 0.1-3 parts of catalyst, 100-200 parts of solvents, lead to
Nitrogen is simultaneously stirred, and is to slowly warm up to 120-140 DEG C, is maintained gradually to heat up 150~190 DEG C again after 2-3h and is continued to react 1-4h, directly
To acid number close to or up 40mgKOH/g, continue to add polyalcohol, react 0.5-2h, stretched system acid number is less than 10mgKOH/g,
And water yield it is unchanged when be reaction end, obtain the unsaturated polyester (UP) containing terminal hydroxy group；In this step ,-OH consumption
The many 0.5-10.5mol% of consumption (molar percentage) relative to-COOH；
Step (2)：The synthesis of polyurethane unsaturated polyester (UP) copolymer
60-160 parts of 50-120 parts of unsaturated polyester (UP), polyisocyanates, the catalyst containing terminal hydroxy group for taking the first step to synthesize
0.1-3 parts, in 100-300 parts of addition reaction vessels of solvent, temperature reaction 2-4h, when-NCO% is stable, obtain end group for-
NCO polyurethane unsaturated polyester (UP) copolymer；Wherein, many 1-5mol% (Mole percents of the consumption of-NCO consumption relative to-OH
Than)；
30-90 parts of (methyl) dihydroxypropyl dodecyl ester is added, while adding 0.1-3 parts of catalyst, polymerization inhibitor 0.1-3
Part, continue to react, NCO exhausts into system, stop reaction；Vacuumize；Washing；Dry；It is acryloxy to obtain end group
Polyurethane unsaturated polyester (UP) copolymer；
Step (3)：The synthesis of polystyrene-poly urethane-unsaturated polyester (UP) copolymer
Take the end group that second step is synthesized for 50-100 parts of the polyurethane unsaturated polyester (UP) copolymer of acryloxy, styrene, draw
0.5-2 parts of agent, 50-300 parts of solvent are sent out, heating response 1-4h continues temperature reaction 0.5-2 hours, stops reaction；Vacuumize；
Washing；Dry；Obtain described polystyrene-poly urethane-unsaturated polyester resin；
Described polystyrene-poly urethane-unsaturated polyester (UP) copolymer number-average molecular weight is 7,000~170,000；Molecular weight point
Cloth is below 3.
9. a kind of peelable protection ink of Self-leveling, it is characterised in that it is made up of following component and content：
Main film forming matter：25-30 parts of the chloridized polyolefin of modified by maleic acid anhydride graft；Vinyl chloride-vinyl acetate-maleic acid copolymerized
25-30 parts of resin；35-40 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane-unsaturated polyester resin 25-
30 parts；
Subsidiary film forming matter is constituted：10-15 parts of acetylbutyrylcellulose；10-15 parts of epoxy resin；Blocked polyurethane 10-
15 parts；1-2 parts of organic tin catalyst；
1-3 parts of pigment；0.1-0.5 parts of thixotropic agent；0.1-0.5 parts of defoamer；0.1-0.5 parts of antioxidant；20-60 parts of solvent；
Polystyrene-poly urethane-unsaturated polyester (UP) the copolymer is prepared using following methods：
Step (1)：The synthesis of unsaturated polyester (UP) containing terminal hydroxy group
In four mouthfuls of reaction vessels with stirring and condensation, 40 parts of tetrachlorophthalic acids, 20 parts of tetrabromo-phthalics two are put into successively
Formic acid, 35 parts of octadecane diacids, 45 parts of maleic acids, 15 parts of fumaric acid anhydrides, 15 parts of chlordene endo-methylene group phthalic anhydrides,
55 parts of TMPDs, 60 parts of 2- ethyls -2- butyl -1,3-PDs, 0.3 part of catalyst, 150 parts of solvents, logical nitrogen is simultaneously
Stirring, is to slowly warm up to 125 DEG C, maintains gradually to heat up 165 DEG C again after 2h and continues to react 3h, until acid number close to or up
40mgKOH/g, continues to add 2- ethyls -2- butyl -1,3-PD, reacts 1h, and stretched system acid number is less than 10mgKOH/g, and
It is reaction end when water yield is unchanged；Vacuumize；Washing；Dry；Obtain the unsaturated polyester (UP) containing terminal hydroxy group；Walk herein
In rapid ,-OH many 1.5mol% of consumption of the consumption relative to-COOH；
Step (2)：The synthesis of polyurethane unsaturated polyester (UP) copolymer
Take the first step synthesize 80 parts of the unsaturated polyester (UP) containing terminal hydroxy group, 4,120 parts of 4 '-methyl diphenylene diisocyanate,
In 0.1 part of catalyst, 200 parts of addition reaction vessels of solvent, temperature reaction 2h, when-NCO% is stable, obtains end group for-NCO
Polyurethane unsaturated polyester (UP) copolymer；Wherein, many 1.5mol% (Mole percents of the consumption of-NCO consumption relative to-OH
Than)；
The dihydroxypropyl dodecyl ester accurately measured is added, while adding 0.3 part of catalyst, 0.3 part of polymerization inhibitor, continues anti-
Should, into system, NCO exhausts, and stops reaction；Vacuumize；Washing；Dry；Obtain the polyurethane insatiable hunger that end group is acryloxy
And polyester copolymer；In this step, the consumption of dihydroxypropyl dodecyl ester has just reacted the-NCO in system；
Step (3)：The synthesis of polystyrene-poly urethane-unsaturated polyester (UP) copolymer
Take second step synthesize end group for acryloxy 150 parts of 00 part of polyurethane unsaturated polyester (UP) copolymer 1, styrene,
0.5 part of initiator, 300 parts of solvent, heating response 4h continue temperature reaction 0.5 hour, stop reaction；Vacuumize；Washing；It is dry
It is dry；Obtain described polystyrene-poly urethane-unsaturated polyester resin.
10. one kind peelable protection ink or Self-leveling as claimed in claim 9 as described in claim any one of 1-7 is peelable
Protect the application of ink.
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| CN109467981A (en) * | 2018-10-31 | 2019-03-15 | 深圳市金达盛化工有限公司 | A kind of ink for screen printing and preparation method thereof |
| CN109664573B (en) * | 2018-12-25 | 2020-07-17 | 常州市华健药用包装材料股份有限公司 | Printable high-strength solid medicinal cold stamping forming composite hard sheet |
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| JPS60206881A (en) * | 1984-03-30 | 1985-10-18 | Pentel Kk | Ink for writing utensil |
| JP4138598B2 (en) * | 2003-07-30 | 2008-08-27 | ソニーケミカル＆インフォメーションデバイス株式会社 | Peelable composition, thermal transfer recording medium, and transferable protective film |
| CN102807785B (en) * | 2012-08-06 | 2014-04-09 | 武汉理工大学 | Non-solvent type high-temperature resistant strippable protection ink, and preparation method thereof |
| CN103031053B (en) * | 2013-01-06 | 2015-07-29 | 北京海斯迪克新材料有限公司 | Touch-screen temporary protection UV solidifies peelable blue gel and preparation method thereof |
| CN103923414B (en) * | 2014-04-16 | 2016-01-20 | 潍坊胜达科技股份有限公司 | Peelable protective film and its production and use |
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