CN104559827A - Compressible micron-sized polymer particle, application of compressible micron-sized polymer particle, solidifiable composition, preparation method of solidifiable composition, pressure-sensitive adhesive and adhesive tape - Google Patents

Abstract

The invention provides a compressible micron-sized polymer particle, an application of the compressible micron-sized polymer particle, solidifiable composition, a preparation method of the solidifiable composition, a pressure-sensitive adhesive and an adhesive tape. The compressible micron-sized polymer particle comprises a polymer microparticle and a metal layer, wherein the polymer microparticle comprises a casing made of a polymer material and a cavity defined by the casing, and the casing is covered with the metal layer. The compressible micron-sized polymer particle is used in the polyacrylate pressure-sensitive adhesive, and the pressure-sensitive adhesive is enabled to be black enough under the condition that the strength of the pressure-sensitive adhesive is not reduced.

Description

Compressible micrograde polymer particle and uses thereof, curable compositions and preparation method thereof, pressure sensitive adhesive, adhesive tape

Technical field

The invention belongs to pressure sensitive adhesive technical field, be specifically related to a kind of compressible micrograde polymer particle and uses thereof, curable compositions and preparation method thereof, pressure sensitive adhesive, adhesive tape.

Background technology

Acrylate adhesive tape is the one of Pressuresensitive Tape, and it has the character such as the compressibility of similar foam tape (as polyurethane foam tape) and attaching property, therefore is also referred to as " foam shape adhesive tape ".But it is different from foam tape, acrylate adhesive tape is not made up of the binder layer of foam core and core surfaces, and completely form (i.e. polyacrylate(s) pressure sensitive adhesive play core and binder layer effect) by polyacrylate(s) pressure sensitive adhesive simultaneously, the stress of bonding like this head dissipates by the mechanical relaxation of adhesive tape entirety, thus the bonding head of available protecting; Meanwhile, polyacrylate(s) pressure sensitive adhesive has very strong resistance to heat, ultraviolet, chemical reagent, therefore acrylate adhesive is with good weathering resistance, weather resistance etc.

Acrylate adhesive tape can for realizing bonding and sealing in the fields such as consumer electronics, building, automobile, household electrical appliance, concrete, as mobile phone display panel being bonded in shell, or first-class for automobile Logo is bonded in car body.In actual applications, in a lot of situation, wish that acrylate adhesive tape is black, exist to conceal it from background.Because polyacrylate(s) pressure sensitive adhesive itself is colourless, therefore need to add black pigment wherein or black dyes is black to make it.But mostly acrylate adhesive tape is by ultraviolet light polymerization, and black pigment or black dyes can absorb UV-light in a large number, cause the solidification of acrylate adhesive tape influenced, the reduction such as cohesive strength and cohesive strength; Or, for reduce to acrylate adhesive tape solidification influenced, will reduce the add-on of black pigment or black dyes, cause adhesive tape lighter (as being only grey etc.), outward appearance does not reach requirement.

Summary of the invention

An object of the present invention is to provide a kind of compressible micrograde polymer particle, it can be used in pressure sensitive adhesive, thus when not reducing the intensity of pressure sensitive adhesive, makes pressure sensitive adhesive present enough black.

Compressible micrograde polymer particle of the present invention comprises:

Polymer particles, this polymer particles has the shell be made up of polymer materials and the cavity surrounded by described shell;

Cover the metal level on described shell outside surface.

Wherein, the shape of described polymer particles is preferably spherical substantially.

Wherein, described metal layer thickness preferably between 5 nanometer to 80 nanometers, most preferably between 20 nanometer to 60 nanometers.

Another object of the present invention is to provide a kind of curable compositions containing above-mentioned compressible micrograde polymer particle, can form pressure sensitive adhesive after its solidification.

Curable compositions of the present invention comprises:

Slurry polymerization thing, it comprises the mixture by the copolymerization of at least two kinds of polymerisable monomer parts, and described mixture comprises the described polymerisable monomer that polymerization does not occur and the multipolymer formed by described polymerisable monomer copolymerization;

Light trigger;

Above-mentioned compressible micrograde polymer particle.

Wherein, polymerisable monomer preferably includes: as the acrylic ester monomer of the first monomer, and as the non-ester unsaturated monomer with at least one ethylene linkage of second comonomer; This first monomer is more preferably (methyl) acrylate monomer of non-tertiary alcohol, and second comonomer is more preferably the non-ester unsaturated monomer with at least one ethylene linkage of sour official energy.

Another object of the present invention is to provide a kind of preparation method of foregoing curable composition, and it comprises:

Make the copolymerization of above-mentioned polymerisable monomer generating portion, obtain above-mentioned slurry polymerization thing;

Light trigger and above-mentioned compressible micrograde polymer particle are mixed with described slurry polymerization thing.

Another object of the present invention is to provide a kind of pressure sensitive adhesive, and it can be used in adhesive tape, and can present enough black not falling in low intensive situation.

Pressure sensitive adhesive of the present invention is formed by the solidification of above-mentioned curable compositions.

Another object of the present invention is to provide a kind of adhesive tape, and it can present enough black when intensity does not reduce.

Adhesive tape of the present invention comprises above-mentioned pressure sensitive adhesive.

Another object of the present invention is to provide the purposes of a kind of above-mentioned compressible micrograde polymer particle for polyacrylate(s) pressure sensitive adhesive.

Accompanying drawing explanation

Fig. 1 is the structural representation of the vacuum sputtering equipment for forming metal level at expanded polymeric microspheres outside surface;

In the present invention, Reference numeral is:

10, vacuum sputtering equipment; 12, outer cover; 14, vacuum cavity; 16, particulate matter stirs Fluidizer; 18, bottom surface; 20, interface; 28, end face; 34, opening; 40, axle; 42, stirring piece; 44, hole.

Embodiment

For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.

term is explained

In the present invention, the meaning of following term or describing mode is as follows:

The situation while that the description of " A and/or B " representing wherein any one or two kinds all may occur, and namely comprises " A and B ", " A ", " B " three kinds of situations.

The description of " A to B " comprises the value of A, the value of B, and any A of being greater than be less than the value of B; Such as, 1 to 10 comprises 1,10, and any be greater than 1 and be less than 10 value, such as 2,3,4,5,6,7,8,9,2.3,3.5,5.26,7.18,9.999 etc.

The description of " A is B substantially " refer to when with the yardstick of A self for reference, it meets feature B on the whole, but can there is small differences with B in part details.Such as, " A is spherical substantially " represents when being of a size of standard sight with A, it is spherical on the whole, but this spherical shape can not be strict, as coarse surface can be had, tiny depression or projection can be had on the surface, or tiny distortion (as being elliposoidal, pyriform) etc. can occur on the whole.

The description " being about A " represents that target value is A, but can have between actual value and A value under prior art conditions inevitably, can tolerance.

" viscosity ", if no special instructions, then alleged in the present invention viscosity all obtains with Ubbelohde viscometer measurement.

" molecular weight ", if no special instructions, then alleged in the present invention molecular weight is weight-average molecular weight, and is all obtained by gel gas chromatography (GPC).The concrete testing method of weight-average molecular weight comprises: take the sample bottle that 0.1 gram of sample is placed in 5 milliliters, adds 3 milliliters of tetrahydrofuran (THF)s (TEDIA company limited, Ohio, the U.S.) and dissolves; Add in sample bottle after solution is filtered with the filtering membrane of 0.45 micron pore size; Test with chromatographic instrument (Waters company, the Maryland State, the U.S.), gained chromatographic column uses standard known molecular amount polystyrene carry out demarcating and set up calibration curve by linear least square analysis, thus finally obtains molecular weight.

" material consumption ", if no special instructions, then in the present invention, the consumption of material or amount ratio all refer to weight or weight ratio.

The description of " (methyl) vinylformic acid " represents vinylformic acid and methacrylic acid two kinds of situations.

" tertiary alcohol " refers to that other three groups that the carbon atom at hydroxyl place connects are the substituent alcohol of non-hydrogen atom; " non-tertiary alcohol " then refers to the alcohol not belonging to the tertiary alcohol.

" micrograde polymer particle " refers to that the particle diameter of polymer beads is in micron dimension, and namely particle diameter is more than or equal to 1 micron and is less than 1000 microns.

" compressible polymer beads " refers to when being subject to ambient pressure, and polymer beads in not impaired situation, compression set can occur, when pressure is removed, polymer beads can recover before shape and size.

" polymer materials form shell " refers to housing that is that be made up of polymkeric substance, complete, that close, this housing by its internal space and space outerpace separated; Space in housing is " cavity surrounded by shell ".

" part copolymerization " refers to that in polymerisable monomer, some polymerization has occurred and has defined multipolymer; Meanwhile, some polymerisable monomer is polymerized not yet, keeps the form of monomer.

" multipolymer " refers to the material obtained by least two kinds of different monomer copolymerizations, and it comprises random copolymers, segmented copolymer, graft copolymer, alternating copolymer or their mixing.

" pressure sensitive adhesive " refers to can by two bond matrix material together, and it at least meets under envrionment temperature (5 DEG C to 40 DEG C): (1) has lasting viscosity; (2) under the pressure pressed with finger, just bonding can be realized; (3) shape can be changed to be attached on matrix; (4) cohesive strength is enough to make its substantially clean removing from adherend.

" solidification " refers to that liquid material is by the polymerization of wherein component and crosslinked and by liquid state be the process of solid-state (be all pressure sensitive adhesive because of what solidify gained in the present invention) with viscous-elastic behaviour.

" adhesive tape " refers to that can be bonded on matrix can be maybe banded product substantially by two bond matrix shape together.

compressible micrograde polymer particle

Embodiments of the invention provide a kind of compressible micrograde polymer particle, and it comprises:

Polymer particles, this polymer particles has the shell be made up of polymer materials and the cavity surrounded by described shell;

Cover the metal level on described shell outside surface.

Described compressible micrograde polymer particle can be used in pressure sensitive adhesive, in particular in polyacrylate(s) pressure sensitive adhesive, thus when not reducing the performances such as pressure sensitive adhesive intensity, makes pressure sensitive adhesive present enough black.

Compressible micrograde polymer particle of the present invention makes pressure sensitive adhesive present the reason possibility following (but following description does not form the restriction to its action principle) of black: the surface of compressible micrograde polymer particle is metal level, metal level has good reflective function, thus wide part reflection (scattering) be mapped on it can be gone out, and due to the compressible micrograde polymer amounts of particles in pressure sensitive adhesive numerous, therefore the light injecting pressure sensitive adhesive can reflection (scattering) repeatedly between each particle, and absorbed by pressure sensitive adhesive gradually during this period, thus can not penetrate from pressure sensitive adhesive, pressure sensitive adhesive is made to present black.Compressible micrograde polymer particle surface of the present invention has metal level, therefore it does not absorb light substantially, therefore both can not affect the solidification of pressure sensitive adhesive because absorbing UV-light, but pressure sensitive adhesive can be made again to present enough black simultaneously.

Meanwhile, the shell of the polymer particles of compressible micrograde polymer particle of the present invention is made up of the polymer materials that quality is softer, but not is made up of mechanically resistant material, therefore itself is compressible.Therefore, compressible micrograde polymer particle can not cause detrimentally affect to the compressibility of pressure sensitive adhesive, sticking nature, die-cutting performance (representing the performance whether sticky cutter easily occurs when whether being easily cut and cutting) etc., also can improve above performance on the contrary.

Wherein, polymer particles is preferably essentially spherical.Like this, compressible micrograde polymer particle can evenly, stable being distributed in pressure sensitive adhesive, and can uniformly to all directions reflection (scattering) light.

Wherein, the polymkeric substance forming the shell of polymer particles is preferably thermoplastic polymer, and is filled with gas in its cavity.That is, polymer particles can be the form of " expanded polymeric microspheres ".Expanded polymeric microspheres is a kind of commercially available filler, and it is normally used for adding in composition to reduce composition density; Expanded polymeric microspheres is obtained through adding thermal expansion by " expended microsphere "; Expended microsphere then comprises the ball wall of thermoplastic polymer and is positioned at the gas of ball wall, and when heating, its internal gas expands, thus makes ball wall be expanded to different size, forms expanded polymeric microspheres.Wherein, the concrete size of expanded polymeric microspheres by the decision such as Heating temperature, heat-up time.

Preferred, the thermoplastic polymer forming the shell of polymer particles is thermoplastic polypropylene acid resin, and the gas in its cavity is alkane (as methane, ethane etc.).On the one hand, above material is the most frequently used material of commercially available expanded polymeric microspheres; On the other hand, because compressible micrograde polymer particle of the present invention is preferred in polyacrylate(s) pressure sensitive adhesive, if therefore the shell of polymer particles is made up of esters of acrylic acid material, then when the metal level on it covers not full-time, the material of this shell can have good consistency with pressure sensitive adhesive.

For ensureing reflecting properties, compressible performance, dispersibility etc., the particle diameter (i.e. the external diameter of shell) of above-mentioned polymer particles is preferably between 10 microns to 100 microns, and the thickness of its shell (i.e. wall thickness) is preferably between 2 microns to 15 microns.

The outside surface of the shell of polymer particles is also provided with metal level, and namely above expanded polymeric microspheres is " metallization ".

Wherein, the material of metal level is preferably selected from any one metal in tungsten, titanium, aluminium, chromium, niobium, zirconium or its alloy.Above metal cost is lower, and pressure sensitive adhesive can be made to have enough erosion resistances and required black.

Wherein, the thickness of metal level can produce significantly impact to the reflective function, compressible performance etc. of compressible micrograde polymer particle; Find after deliberation, when with polymer particles as matrix, metal layer thickness is preferably between 5 nanometer to 80 nanometers, more preferably between 6 nanometer to 70 nanometers, preferred between 12 nanometer to 60 nanometers further; Most preferably between 20 nanometer to 60 nanometers; Because the metal level in above thickness range had both had enough reflecting properties, detrimentally affect can not be produced to compressibility again.

Wherein, metal level is formed in polymer particles outside surface preferably by vacuum sputtering.

Typically, form the method for metal level and comprise vacuum sputtering, chemical vapour deposition, plating, electroless plating etc., and due to the material of the substrate that will form metal level in the present invention be polymkeric substance, and form is microgranular, therefore Part Methods inapplicable, and preferably vacuum sputtering can be adopted.

Wherein, concrete vacuum sputtering methods can with reference to following US Patent No. 8664148, US8518854, US7989384, US7727931, US7458693, US7156528, the US6767745 etc. licensing to 3M company.Vacuum sputtering can carry out in vacuum sputtering equipment 10 as shown in Figure 1, and this vacuum sputtering equipment 10 comprises outer cover 12, is vacuum cavity 14 in outer cover 12.The particulate matter be provided with in vacuum cavity 14 for splendid attire granule materials stirs Fluidizer 16, and particulate matter stirs in Fluidizer 16 stirring piece 42 having with holes 44, and stirring piece 42 is connected on rotating axle 40.Particulate matter stirs Fluidizer 16 upper end opening 34, and the end face 28 of the outer cover 12 corresponding with opening 34 is provided with round mouth, and this round mouth place is used for arranging magnetically controlled DC sputtering negative electrode and metal sputtering target (not shown).The bottom surface 18 of outer cover 12 establishes the interface 20 for connecting vacuum pump in addition.When sputtering, granular material (as expanded polymeric microspheres) is placed in particulate matter and stirs in Fluidizer 16, sputtering particle deposits to material surface from opening 34, due to the rotation of stirring piece 42, therefore the material that particulate matter stirs in Fluidizer 16 constantly overturns, thus the particle accepting sputtering particle constantly changes, the surface of final each particle is all deposited uniformly metal level.

curable compositions

Embodiments of the invention also provide a kind of curable compositions, and said composition can form pressure sensitive adhesive or adhesive tape after carrying out ultraviolet light polymerization.

1, the composition of curable compositions

Curable compositions of the present invention comprises:

Slurry polymerization thing;

Above-mentioned compressible micrograde polymer particle;

Light trigger.

Preferably, also can comprise in curable compositions of the present invention in following component any one or multiple:

Linking agent;

Hydrophobicity aerosil;

Expanded polymeric microspheres (not being with metal level);

Tackifying resin;

Glass microballon;

Chain-transfer agent;

Other additive (softening agent, dyestuff, antioxidant, dispersion agent, anti-sedimentation agent, UV stabilizer etc.) and functional component.

Below the effect of each component, concrete optional substance, content etc. are introduced one by one.

1) slurry polymerization thing

Slurry polymerization thing comprises the mixture by the copolymerization of at least two kinds of polymerisable monomer parts, and this mixture comprises the polymerisable monomer that polymerization does not occur and the multipolymer formed by polymerisable monomer copolymerization.That is, have at least two kinds of polymerisable monomers in slurry polymerization thing, and the part in these polymerisable monomers there occurs polymerization, defined multipolymer, and all the other polymerisable monomers still keep the form of monomer.

Because the polymerisable monomer in slurry polymerization thing is partially polymerized, therefore wherein do not occur crosslinked or only have the crosslinked of few part, the multipolymer generated still may be dissolved in unpolymerized polymerisable monomer; So slurry polymerization thing is still liquid homogeneous system on the whole, has mobility, can be carried out the operations such as coating.Meanwhile, slurry polymerization thing is partially polymerized again, therefore has higher viscosity, thus is convenient to be formed the product (as adhesive tape) with certain thickness and shape.

Wherein, the viscosity of slurry polymerization thing 22 DEG C time preferably between 500cPs (centipoise) to 10000cPs, more preferably between 2000cPs to 6000cPs.In above range of viscosities, compressible micrograde polymer particle ratio is easier to be mixed into wherein, is also convenient to carry out the operations such as coating, can form again the adhesive tape meeting thickness requirement (as thickness 5 millimeters) simultaneously.

The weight-average molecular weight of the multipolymer in slurry polymerization thing is preferably between 500000 dalton (Daltons, gram/mol) to 10000000 dalton.That is, in slurry polymerization thing, there is material (the i.e. multipolymer be polymerized, not very also do not occur be polymerized monomer) weight-average molecular weight between 500000 dalton to 10000000 dalton, more preferably between 750000 dalton to 6000000 dalton, more preferably between 1000000 dalton to 5000000 dalton.

Meanwhile, in slurry polymerization thing, relative to the polymerisable monomer occurring to be polymerized and the gross weight that the polymerisable monomer be polymerized does not occur, there is the ratio of the weight of the polymerisable monomer be polymerized between 1% to 30%.That is, if whole polymerisable monomers of slurry polymerization thing (be polymerized with unpolymerized) are 100 weight parts, then wherein occurred to be polymerized and become the polymerisable monomer of multipolymer amount just at 1 weight part to 30 weight part, the transformation efficiency of polymerisable monomer is 1% to 30% in other words.Preferred, the transformation efficiency of polymerisable monomer is 2% to 20%, preferred 5% to 15% further, most preferably 7% to 12%.

Under above molecular weight and transformation efficiency, the Nature comparison such as viscosity, intensity of slurry polymerization thing entirety is suitable, is easy to mix with compressible micrograde polymer particle.

Wherein, polymerisable monomer comprises: as the acrylic ester monomer of the first monomer, as the non-ester unsaturated monomer with at least one ethylene linkage of second comonomer; Further, polymerisable monomer also optionally comprises: the ethylenic unsaturated polar monomer of non-acid official energy and/or vinyl monomer.Below, each polymerisable monomer is further introduced.

(1) acrylic ester monomer

This acrylic ester monomer is more preferably (methyl) acrylate monomer of non-tertiary alcohol, namely the ester that formed of (methyl) vinylformic acid and non-tertiary alcohol.

Wherein, the non-tertiary alcohol forming (methyl) acrylate monomer of above non-tertiary alcohol, preferably containing 1 to 20 carbon atom, more preferably containing 2 to 18 carbon atoms, preferably has 4 to 12 carbon atoms further; The segment of this non-tertiary alcohol can be straight chain, also can with side chain or both combinations.Concrete, above non-tertiary alcohol includes but not limited to: methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl-1-butanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 2-ethyl-n-butyl alcohol, 3, in 5,5-trimethylammonium-1-hexanol, 3-enanthol, 1-octanol, sec-n-octyl alcohol, isooctyl alcohol, 2-ethyl-1-hexanol, 1-decanol, 2-propyl enanthol, DODECANOL, 1-, 1-tridecyl alcohol, 1-tetradecanol any one or multiple.

Although above non-tertiary alcohol is all applicable, but some preferred embodiment in, non-tertiary alcohol is preferably any one or multiple (corresponding ester is Isooctyl acrylate monomer, ethyl acrylate, butyl acrylate) in butanols, isooctyl alcohol, 2-Ethylhexyl Alcohol; And other preferred embodiment in, non-tertiary alcohol is the alcohol derived from renewable source, as any one in sec-n-octyl alcohol, geraniol, dihydro-citronellol or multiple.

At whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized) in, (methyl) acrylate monomer of non-tertiary alcohol preferably accounts for 80 weight part to 99.5 weight parts, more preferably account for 85 weight part to 99.5 weight parts, preferably account for 87 weight part to 98 weight parts further.

In (methyl) acrylate monomer of non-tertiary alcohol, but some has higher Tg (second-order transition temperature), and namely the Tg of its homopolymer is at least 25 DEG C, and is preferably at least 50 DEG C.This (methyl) acrylate monomer with the non-tertiary alcohol of higher Tg includes but not limited to: methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the secondary butyl ester of methacrylic acid, methacrylic acid octadecane alcohol ester, phenyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl methacrylate, vinylformic acid 3, 3, 5-3-methyl cyclohexanol ester, cyclohexyl acrylate, in N-octyl acrylamide and propyl methacrylate any one or multiple.

At whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized) in, this (methyl) acrylate monomer with the non-tertiary alcohol of higher Tg preferably accounts for 0 weight part to 40 weight part (0 expression can be free of), more preferably account for 1 weight part to 35 weight part, preferably account for 5 weight part to 35 weight parts further.Wherein, this content with (methyl) acrylate monomer of the non-tertiary alcohol of higher Tg is included in the content of (methyl) acrylate monomer of above non-tertiary alcohol; Such as, if not the amount of (methyl) acrylate monomer of the tertiary alcohol is 85 weight parts, and the amount with (methyl) acrylate monomer of the non-tertiary alcohol of higher Tg is 35 weight parts, then represent in (methyl) acrylate monomer of the non-tertiary alcohol of 85 weight parts altogether, have 35 weight parts to have higher Tg, all the other 50 weight parts are then (methyl) acrylate monomers of other the non-tertiary alcohol with lower Tg.

(2) there is the non-ester unsaturated monomer of at least one ethylene linkage

This non-ester unsaturated monomer with at least one ethylene linkage is more preferably the non-ester unsaturated monomer with at least one ethylene linkage of sour official energy, namely wherein comprise ethylene linkage and acid functional group simultaneously, this acid functional group can be acid, as carboxylic acid, may also be the salt of acid, as an alkali metal salt of carboxylic acid, but it can not be ester.The non-ester unsaturated monomer with at least one ethylene linkage of this sour official's energy can be ethylenic unsaturated carboxylic acid, ethylenic unsaturated sulfonic acid, the unsaturated phosphonic acids of ethylenic etc.; Concrete, it includes but not limited to: in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, β-crotonic acid, citraconic acid, toxilic acid, oleic acid, styrene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic, vinyl phosphonate any one or multiple.Consider exploitativeness, the non-ester unsaturated monomer with at least one ethylene linkage of this sour official's energy is more preferably ethylenic unsaturated carboxylic acid, as acrylic or methacrylic acid.

Wherein, at whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized) in, the non-ester unsaturated monomer with at least one ethylene linkage of acid official energy preferably accounts for 0.5 weight part to 20 weight part, more preferably account for 0.5 weight part to 15 weight part, preferably account for 2 weight part to 12.5 weight parts further.

(3) the ethylenic unsaturated polar monomer of non-acid official energy

Preferably, the ethylenic unsaturated polar monomer (ester can be comprised) of non-acid official energy can also be comprised in slurry polymerization thing.Wherein, available non-acid official can ethylenic unsaturated polar monomer include but not limited to: (methyl) vinylformic acid 2-hydroxyl ethyl ester, NVP, N-caprolactam, acrylamide, list-N-AAM, two-N-AAM, N-tert-butyl acrylamide, dimethylaminoethylacrylamide, N-octyl acrylamide, gather in (alkoxyalkyl) (methyl) acrylate any one or multiple; Wherein, poly-(alkoxyalkyl) (methyl) acrylate comprise in (methyl) vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-methoxyethoxyethyl acrylate, methacrylic acid 2-methoxy acrylate, polyethyleneglycol (methyl) acrylate any one or multiple.Most preferred, the ethylenic unsaturated polar monomer of non-acid official energy is (methyl) vinylformic acid 2-hydroxyl ethyl ester and/or NVP.

Wherein, at whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized) in, the polar monomer of non-acid official energy preferably accounts for 0 weight part to 10 weight part (0 expression can be free of), more preferably account for 0.5 weight part to 8 weight part, preferably account for 1 weight part to 6 weight part further.

(4) vinyl monomer

Preferably, also vinyl monomer can be comprised in slurry polymerization thing, this vinyl monomer refers to vinyl group to be the monomer of integral part, and it can include but not limited to: in the vinylbenzene (as alpha-methyl styrene) of vinyl ester (as vinyl-acetic ester, propionate), vinylbenzene, replacement, vinyl halide any one or multiple.Obviously, vinyl monomer described herein does not comprise other monomer foregoing.

Wherein, at whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized) in, this vinyl monomer preferably accounts for 0 weight part to 5 weight part (0 expression can be free of), more preferably account for 0.5 weight part to 5 weight part, preferably account for 1 weight part to 4 weight part further.

2) above-mentioned compressible micrograde polymer particle

Above-mentioned compressible micrograde polymer particle joins in curable compositions, can, when performances such as the intensity not reducing the pressure sensitive adhesive generated by this curable compositions, make pressure sensitive adhesive present enough black.

Wherein, relative to the polymerisable monomer occurring to be polymerized and the gross weight that the polymerisable monomer be polymerized does not occur, the ratio of the weight of compressible micrograde polymer particle is between 0.1% to 7%.That is, in curable compositions, for whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized), the add-on of compressible micrograde polymer particle is preferably 0.1 weight part to 7 weight part, be more preferably 1 weight part to 7 weight part, more preferably 1 weight part to 6 weight part.Obviously, here and component described below be not the part of slurry polymerization thing, therefore their add-on is all the outer dosage relative to slurry polymerization thing.

Obviously, the add-on of compressible micrograde polymer particle is very few can not play a role; But, find after deliberation, if its add-on is too much, then can have an impact to the solidification of curable compositions, therefore its add-on is preferably in above scope meanwhile.

3) light trigger

Light trigger is used for producing free radical under UV-irradiation, thus makes curable compositions solidify to form pressure sensitive adhesive.Wherein, available light trigger includes but not limited to: benzoin ether, as benzoin methylether, benzoin iso-propylether; The methyl phenyl ketone replaced, as 2,2-dimethoxy-acetophenone; Dimethoxy hydroxy acetophenone; The α-one alcohol replaced, as 2-methyl-2-hydroxypropiophenonepreparation; Aromatics SULPHURYL CHLORIDE, as 2-naphthalene-SULPHURYL CHLORIDE; Photosensitive oxime, as 1-phenyl-1,2-propanedione-2-(O-ethoxy-carbonyl) oxime; 1-hydroxycyclohexylphenylketone; 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-third-1-ketone; (4-methylthio phenyl formyl radical)-1-methyl isophthalic acid-morpholinyl ethane; (4-morpholinyl benzoyl)-1-benzyl-1-dimethylaminopropanecompounds; (4-morpholinyl benzoyl)-1-(4-methyl-benzyl)-1-dimethylaminopropanecompounds; Two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide; In 1-hydroxy cyclohexyl phenylketone any one or multiple.Wherein, particularly preferred light trigger is the methyl phenyl ketone replaced.

Wherein, in curable compositions, for whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized), the add-on of light trigger is 0.001 weight part to 3 weight part, be preferably 0.005 weight part to 1 weight part, be more preferably 0.01 weight part to 0.5 weight part.

It should be noted that, the consumption of light trigger mentioned here, it is the total amount in curable compositions, but this light trigger may not be disposable adding, it first can add a part to make the copolymerization of polymerisable monomer part obtain slurry polymerization thing in polymerisable monomer, and remaining light trigger can join in slurry polymerization thing to form pressure sensitive adhesive with it again.Typically, the light trigger joined in advance in polymerisable monomer accounts for 1/10 to 1/5 of total amount.

4) linking agent

Preferably, in curable compositions, also can contain linking agent, linking agent add the cohesive strength that can improve prepared pressure sensitive adhesive.The present invention can linking agent be Photosensitive linking agent, it activates by UV-irradiation, and common Photosensitive linking agent includes but not limited to: benzophenone; Can the aromatic ketone of copolymerization; Triazines material (Triazine), as two (trichloromethyl)-6-(4-the anisole)-triazines of 2,4-etc.The present invention can another kind of linking agent be multifunctional (methyl) acrylate, as two (methyl) acrylate, three (methyl) acrylate, four (methyl) acrylate etc., its object lesson includes but not limited to: 1, 6-hexylene glycol two (methyl) acrylate, PEG two (methyl) acrylate, polyhutadiene two (methyl) acrylate, urethane two (methyl) acrylate, propenoxylated glycerine three (methyl) acrylate, in tetramethylolmethane three (methyl) acrylate any one or multiple.The present invention can another kind of linking agent be thermal activation type linking agent, as polyfunctional aziridine, isocyanic ester, epoxy resin etc., specifically can be 1,1'-(1,3-phenyl-diformyl)-bis--(2-methylaziridine).The present invention can linking agent also comprise aziridines linking agent etc.

Wherein, in the present invention, most preferred linking agent is multifunctional (methyl) acrylate and/or triazines material.

Wherein, in curable compositions, for whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized), the add-on of linking agent is preferably less than or equal to 5 weight parts, more preferably at 0.01 weight part to 2 weight part, preferred at 0.03 weight part to 1 weight part further.

5) hydrophobicity aerosil

Preferably, for improving poly-strong (as shear at high temperature performance) and viscosity in prepared pressure sensitive adhesive, also hydrophobicity aerosil can be added in curable compositions.Wherein, aerosil refers to the silicon-dioxide formed by gas phase process, and it is porous material, is also referred to as gas phase White Carbon black.

Wherein, in curable compositions, for whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized), the add-on of hydrophobicity aerosil is preferably 0.1 weight part to 15 weight part, be more preferably 0.5 weight part to 15 weight part, more preferably 1.5 weight part to 10 weight parts.

6) expanded polymeric microspheres (not being with metal level)

Preferably, in curable compositions, also can add the expanded polymeric microspheres not having splash-proofing sputtering metal layer, this expanded polymeric microspheres can improve the compressibility of product adhesive tape.

Wherein, in curable compositions, for whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized), the add-on of expanded polymeric microspheres is preferably less than or equal to 10 weight parts, be more preferably less than or equal to 8 weight parts, be preferably less than or equal to 6 weight parts further.

7) tackifying resin

Preferably, in curable compositions, also tackifying resin can be contained, to improve the cohesive strength of pressure sensitive adhesive.Common tackifying resin comprises Gum Rosin, terpene phenolic resin, petroleum resin, anine etc.Obviously, the prerequisite that tackifying resin uses does not affect the solidification of curable compositions and the performance of final adhesive tape product; But in ultraviolet light polymerization process, most tackifying resin seriously can hinder the carrying out of curing reaction, as caused occurring phase-splitting between pressure sensitive adhesive and tackifying resin, or reduce polymericular weight and make tackiness agent force of cohesion cross difference etc., or causing solidifying completely.Tackifying resin used in the present invention comprises hydrogenated rosin resin Foral 85 (Pinova company, the Georgia State, the U.S.), hydriding terpene resol UH115 (Yasuhara chemical company, Hiroshima city, Japan) etc. in the market.

Wherein, in curable compositions, for whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized), the add-on of tackifying resin is preferably less than or equal to 40 weight parts, be more preferably less than or equal to 30 weight parts, be preferably less than or equal to 25 weight parts further.

8) glass microballon

Preferably, the glass microballon adding appropriate particle size in curable compositions can strengthen the foam shape characteristic of product adhesive tape, and the preferable particle size of glass microballon is generally at 5 microns to 200 microns.

Wherein, in curable compositions, for whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized), the add-on of glass microballon is preferably less than or equal to 10 weight parts, be more preferably less than or equal to 9 weight parts, be preferably less than or equal to 8 weight parts further.

9) chain-transfer agent

Preferably, in curable compositions, the molecular weight that chain-transfer agent can control the multipolymer in prepared pressure sensitive adhesive is added.The chain-transfer agent that the present invention is suitable for includes but not limited to: in carbon tetrabromide, alcohol, mercaptan any one or multiple.Wherein, most preferred chain-transfer agent is iso-octyl sulfo-glycolate and/or carbon tetrabromide.

Wherein, in curable compositions, for whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized), the add-on of chain-transfer agent preferably at 0.01 weight part to 0.5 weight part, more preferably at 0.05 weight part to 0.2 weight part.

10) other additive (as softening agent, dyestuff, antioxidant, dispersion agent, anti-sedimentation agent, UV stabilizer etc.) and functional component

Preferably, for improving the different performance of product adhesive tape, also can add other additives known various in curable compositions, optional additive includes but not limited to: in softening agent, dyestuff, antioxidant, dispersion agent, anti-sedimentation agent, UV stabilizer any one or multiple.

In addition, preferably, in order to make product adhesive tape have required specific function, also functional component can be added, as having the particle, staple fibre, thin slice etc. of particular conductivity, magnetic conduction, heat conductivility to curable composition species; Such as, mention in Chinese patent CN103320037A and can add conductive particle with the foam shape conductive tape obtained.

Of course it is to be understood that adding of above each selectable components all should be as the criterion with the performance not affecting product adhesive tape itself.Meanwhile, if needed, those skilled in the art also can add other known component to curable compositions.

2, the preparation method of curable compositions

The preparation method of foregoing curable composition comprises:

Make the copolymerization of at least two kinds of above-mentioned polymerisable monomer generating portions, obtain slurry polymerization thing;

Above-mentioned light trigger and compressible micrograde polymer particle are mixed with described slurry polymerization thing.

That is, curable compositions is conventionally mixed to get by slurry polymerization thing and other component (compressible micrograde polymer particle, light trigger etc.).Therefore to curable compositions be prepared, just need first to prepare above-mentioned slurry polymerization thing.Above-mentioned slurry polymerization thing is obtained by the copolymerization of polymerisable monomer part, and its concrete preparation method has two kinds, a kind of mass polymerization being UV-light and causing, be called for short UV-light and cause method, another kind is the solution polymerization process of thermal initiation, is called for short solution method, is introduced one by one below to it.

1) UV-light causes method

Plus solvent is not used in UV-light initiation method preparation process, but directly each polymerisable monomer mixed and carry out being polymerized (mass polymerization), using the multipolymer that the polymerisable monomer wherein not occurring to be polymerized generates as dissolution with solvents polymerization, thus obtain slurry polymerization thing.

The process that UV-light causes method specifically comprises:

(1) above-mentioned each polymerisable monomer is mixed with light trigger

Wherein, if there is (methyl) acrylate monomer with the non-tertiary alcohol of higher Tg, then it can all add in this step, or also only can add a part, or can not add and wait for that other polymerisable monomer adds after completing part copolymerization again.This is because the copolymerization with (methyl) acrylate monomer of the non-tertiary alcohol of higher Tg is often comparatively slow, adds in this step and also generally can not be polymerized in a large number.

Wherein, the light trigger added in this step is only a part for light trigger in final curable compositions, usually only accounts for 1/10 to 1/5 of total amount.

(2) the above polymerizable monomer mixture of UV-irradiation, makes the copolymerization of polymerisable monomer part and obtains slurry polymerization thing

Wherein, available ultraviolet source is divided into two kinds: one to be low strength light source usually, and as black light, its wavelength is in 280 nanometer to 400 nanometers, and intensity is generally 10mw/cm ²below; Two is high-intensity light sources, and as medium pressure mercury lamp, its intensity is greater than 10mw/cm usually ², more preferably at 15mw/cm ²to 450mw/cm ²between; Wherein, above intensity is with UVIMAPTM UM 365 L-S radiometer (universal electric technical device company limited, Virginia, the U.S.) according to the specifying measurement of American National Standard and technological associations (NIST, United States National Institute of Standards and Technology).In this step, the ultraviolet ray intensity preferably used is at 0.1mw/cm ²to 150mw/cm ², more preferably at 0.5mw/cm ²to 100mw/cm ², preferred at 0.5mw/cm further ²to 50mw/cm ².And the time of UV-irradiation can adjust according to the situation of the intensity of light and polymerization, usually about several minutes.

In the course of the polymerization process, available Ubbelohde viscometer constantly measures the viscosity of slurry polymerization thing, and the specific refractory power of continuous measurement slurry polymerization thing is to judge monomer conversion (polymerisable monomer namely having occurred to be polymerized accounts for the ratio of whole polymerisable monomer) wherein, reach after preassigned can remove UV-light until them, and air or oxygen is passed in slurry polymerization thing, make free radical cancellation, polymerization stops.

UV-light causes method in preparation process, does not use extra organic solvent (solvent namely except polymerisable monomer), thus makes essentially no waste water, exhaust emission in whole production process, and more environmental protection, efficiency are high.Meanwhile, in UV-light initiation method, use uv-light polymerization, therefore it does not heat on the one hand, simple and easy to do, energy consumption is low, efficiency is high; On the other hand, when turning off ultraviolet source and pass into air, can termination reaction immediately, therefore the viscosity of its product, monomer conversion, weight-average molecular weight etc. can accurately control.

Therefore, UV-light causes the method that method is preferred prepared slarry polymkeric substance in the present invention, and in various embodiments of the present invention, slurry polymerization thing is all prepared by present method.

2) solution method

Slurry polymerization thing also can use solution method to prepare, and namely polymerisable monomer can be dissolved in other organic solvent and be polymerized, remove additional organic solvent again after being polymerized, the surplus materials obtained is slurry polymerization thing.

The concrete steps of solution method can comprise:

(1) above-mentioned polymerisable monomer, thermal initiator are dissolved in a solvent and lead to nitrogen and fully purify

Wherein, available solvent includes but not limited to: in methyl alcohol, tetrahydrofuran (THF), ethanol, Virahol, acetone, methylethylketone, methyl acetate, ethyl acetate, toluene, dimethylbenzene, ethylene glycol alkyl oxide any one or multiple.

In solution method, need to use thermal initiator, thermal initiator is the organo-peroxide, organic hydroperoxide, azo compound etc. that can produce free radical.Available organo-peroxide includes but not limited to: benzoyl peroxide, lauroyl peroxide, two t-amyl peroxy compounds, peroxidized t-butyl perbenzoate, 2,5-dimethyl-2,5-bis--(t-butylperoxy) hexane, 2, in 5-dimethyl-2,5-bis--(t-butylperoxy) hexin-3, dicumyl peroxide any one or multiple.Available organic hydroperoxide includes but not limited to: tertiary cyclopentadienyl hydrogen peroxide and/or tertbutyl peroxide.Available azo compound includes but not limited to: in 2,2'-azo two (isopropyl cyanide), 2,2'-azos two (2-methylbutyronitrile), 2,2'-azos two (2,4-methyl pentane nitrile) any one or multiple.

Wherein, for whole polymerisable monomer of every 100 weight parts (namely all for the formation of the monomer of slurry polymerization thing, comprise be polymerized with unpolymerized), the add-on of thermal initiator is preferably 0.001 weight part to 3 weight part, be more preferably 0.05 weight part to 1 weight part, more preferably 0.1 weight part to 0.5 weight part.

(2) heated solution, makes polymerisable monomer generating portion polymerization wherein

Wherein, Heating temperature is usually in the scope of 40 DEG C to 100 DEG C, and heat-up time is usually little in 20 hours 1; Total material consumption, required monomer conversion etc. are depended in their concrete selection.

(3) remove additional solvent by vacuum distilling, obtain slurry polymerization thing

Although it should be noted that by solution method prepared slarry polymkeric substance be also feasible, it is not best practice, because wherein need to use additional solvent and the step that will increase except desolventizing, therefore the high and complex process of its cost; It needs heating simultaneously, and energy consumption is high; In addition, monomer polymerization is in the solution often slower, therefore time longer (usually needing a few hours, as long as and UV-light causes method several minutes usually) needed for it, efficiency are low.

After obtaining above-mentioned slurry polymerization thing, namely obtaining curable compositions product as long as it mixed with other component in curable compositions by conventional mode (as stirred), being not described in detail at this.

pressure sensitive adhesive and adhesive tape

Embodiments of the invention also provide a kind of pressure sensitive adhesive, and it is solidified by foregoing curable composition and obtains.

Wherein, it can be made to solidify completely by carrying out UV-irradiation to foregoing curable composition.Solidification preferably adopts above-mentioned low intensity ultraviolet light source, and the time of UV-irradiation is as the criterion to make the complete curing molding of curable compositions, usually about several minutes.

Embodiments of the invention also provide a kind of adhesive tape, and it comprises above-mentioned pressure sensitive adhesive.

As a kind of mode of the present invention, adhesive tape can be made up of above-mentioned pressure sensitive adhesive completely, that is, pressure sensitive adhesive both as the core of adhesive tape, simultaneously also as binder layer.

Or as a kind of mode of the present invention, adhesive tape can be also core with above-mentioned pressure sensitive adhesive, and is also formed with the binder layer of other type in the one or both sides of core, thus give adhesive tape more various performance.

Wherein, the material of available binder layer comprises conventional acrylic binder, rubber adhesive, silicone adhesive etc., and its thickness can between 0.001 millimeter to 0.5 millimeter.The composition, thickness etc. of the binder layer in the both sides of pressure sensitive adhesive core can identical also can be different.

Meanwhile, for improving the bonding force of core and binder layer, before applying binder layer, also can carry out conventional pre-treatment, as corona, plasma, brushing silane coupling agent etc. to core and/or binder layer.

Wherein, as adhesive tape product, its one or both sides also can be pasted with release film or separate-type paper, so that its actual use.Available release film or separate-type paper include but not limited to: silicone coated kraft paper, Ge Laxin paper, pouring mould kraft paper, poly-(ethylene glycol terephthalate) etc.

Wherein, when preparing above-mentioned adhesive tape, curable compositions can be coated in release film or separate-type paper, and form specific shape and thickness, making curable compositions solidify to form pressure sensitive adhesive afterwards again.

Wherein, the mode of available coating curable compositions includes but not limited to roller coat, flow coat, dip-coating, spin coating, spraying, blade coating, mould painting etc., and it can be selected according to required coating thickness.Typically, in adhesive tape, the thickness of pressure sensitive adhesive (dry glue) is preferably at 0.05 millimeter to 5 millimeters, more preferably at 0.1 millimeter to 2.5 millimeters, preferred at 0.1 millimeter to 2 millimeters further.Wherein, owing to the addition of above-mentioned compressible micrograde polymer particle, thus adhesive tape of the present invention be easy to preparation shaping, and thickness thicker or thinner time, its performance such as intensity, compressibility also meets the requirements; Therefore, the thickness range that adhesive tape of the present invention (say accurately be pressure sensitive adhesive) wherein allows is larger, minimumly reaches 0.05 millimeter, and reach as high as 5 millimeters, this is all beyond the thickness range that existing adhesive tape can reach.

Containing above-mentioned compressible micrograde polymer particle in adhesive tape of the present invention, therefore enough black can be presented when not affecting the performances such as intensity.Thus, in the colour system represented according to L value a value b value (i.e. L*a*b*), the colored L value of this glue is preferably between 0 to 30, more preferably between 0 to 25, preferred between 0 to 20 further.Wherein, the colour system that L value a value b value represents is also referred to as Lab color space, and it is formulated in 1976 by International Commission on Illumination (CIE), and its L value, a value, b value are three mutually perpendicular coordinate axis, is used for expression color space; L value represents lightness, and 0 is the most black, and 100 represent the whitest; Positive a value represents magenta, and negative a value represents green; Positive b value represents yellow, and negative b values represents blue.A value, the b value of usual adhesive tape of the present invention all between-5 to 5, therefore generally need not be considered, as long as and consider that its L value can determine that whether its black is up to standard.

embodiment

Below according to above description, select different formulas and parameter, prepare different adhesive tapes as embodiment and comparative example, with exemplary explanation the present invention.

1, material table

The material used in each embodiment is as shown in the table:

The material information slip used in table 1, each embodiment

2, testing method

To adhesive tape prepared by each comparative example and embodiment, carry out some performance tests, its concrete testing method is as follows:

1) 90 ° of release adhesive Force meansurement

Adhesive tape is carefully cut the batten of about 25.4 mm wides, 115 millimeters long along glue application direction cutting knife, remove the release film of one side, batten is adhered between two parties stainless steel plate (Chemsultants international corporation, Ohio, the U.S.) on, adhesive tape upper end is concordant with steel plate edge, and before adhering to, stainless steel plate first uses Virahol (Chemical Reagent Co., Ltd., Sinopharm Group, Shanghai) wiping three times, and guarantee that Virahol volatilizees completely.

Pull the release film of another side, then stick the anodic oxidation aluminium foil (Lawerence and Fredrick company, Illinois, the U.S.) of 0.13 mm thick, the oxide side of anodic oxidation aluminium foil and glue surface plaster are closed.

Roll stone roller one back and forth by the rubber rollers of 6.8 kilograms with the speed of 305 mm/min, then place specified time; This adhesive tape is peeled off power needed for (namely edge is peeled off perpendicular to the direction of adhesive tape adhesive face) from stainless steel plate by the angle measured along 90 ° with the peeling rate of 305 mm/min again, the equipment that test uses is Instron 3343 type test machine (Chemsultants international corporation, Ohio, the U.S.), the mean value of the measuring result of three samples got by often kind of adhesive tape.

Wherein, placement condition be:

First condition: the temperature of 23 ± 2 DEG C and 50 ± 5% relative humidity under place 20 minutes;

Second condition: the temperature of 23 ± 2 DEG C and 50 ± 5% relative humidity under place 3 days;

Article 3 part: to the adhesive tape (adhesive tape namely do not adhered to) with release film, place under temperature prior to 65 DEG C and the relative humidity of 95% 7 days with test its hot and humid under ageing resistance, again in 23 ± 2 DEG C temperature and 50 ± 5% relative humidity under place 1 day, carry out the operations such as above shearing, adhesion more afterwards, the adhesive tape after adhesion 23 ± 2 DEG C temperature and 50 ± 5% relative humidity under place 20 minutes.

2) T-shaped peel test force

Adhesive tape is carefully cut the batten of about 25.4 mm wides, 127 millimeters long along glue application direction cutting knife, remove the release film of one side, be attached on the oxide side of above-mentioned anodic oxidation aluminium foil.

Pull the release film of another side, be attached to equally (namely adhesive tape is two-layer is pasted with anodic oxidation aluminium foil respectively) on the oxide side of another anodic oxidation aluminium foil, ensure that tape edge does not exceed aluminium foil edge extent.

Roll stone roller one back and forth by the rubber rollers of 6.8 kilograms with the speed of 305 mm/min, then place specified time; The elongation end by the anodic oxidation aluminium foil on two sides gently (namely not with the end of tape adhesion) curves with adhesive tape is again 90 °, thus test block is "T"-shaped (the both sides transverse part of this T-shaped is respectively two sections of anodic oxidation aluminium foils, and vertical part is the adhesive tapes of both sides with anodic oxidation aluminium foil).

"T"-shaped test block is contained in the test cartridge of Instron 3343 type test machine, ensure adhesive tape position (namely the anodic oxidation aluminium foil of both sides is equally long) placed in the middle and there is no torsional deformation, test cartridge is moved with the speed of 305 mm/min, measures and aluminium foil is peeled off required pulling force from adhesive tape.

Wherein, condition of placing is identical with the placement condition in above 90 ° of release adhesive Force meansurement.

3) the colored measurement of glue

The color of adhesive tape is measured with HunterLab color difference meter (HunterLab company, Virginia, the U.S.).

Use the reflection angle of 10 ° during measurement, and only record L value; Wherein, the thickness of measured adhesive tape should be at least 0.8 millimeter, and as the thickness low LCL of individual layer adhesive tape, then stacked multiple adhesive tape is until its thickness is up to standard.

The color (i.e. black, grey etc.) of adhesive tape by visual inspection, as a reference.

4) measurement of tape thickness

Tape thickness measurement uses digital display thickness tester (Mitutoyo company, Tokyo, Japan).

Before test, the release film on adhesive tape is all removed, two measuring heads being placed on digital display thickness tester between, ensure the smooth and tensionless winkler foundation of adhesive tape, fall the presser feet (not collision) of digital display thickness tester gently, reading after 2 seconds, every bar adhesive tape is got three, left, center, right point in the direction of the width and is tested respectively, with its mean value for measuring result.

3, the preparation of compressible micrograde polymer particle

With above-mentioned vacuum sputtering, according to material and the parameter of table 2, at the forming metal layer on surface of expanded polymeric microspheres, obtain compressible micrograde polymer particle MA to ML.

Wherein, the outer cover of vacuum sputtering equipment is erect cylindrical, high 45 centimetres, diameter 50 centimetres; It is horizontal cylindrical that particulate matter stirs Fluidizer, long 12 centimetres, diameter 9.5 centimetres; Particulate matter stirs Fluidizer split shed and is of a size of 6.5 cm x 7.5 centimetres, and and distance between metal sputtering target be 7 centimetres; Being located in thing stirs on the central axis of Fluidizer, it is provided with 4 pieces of orthogonal stirring pieces, stirring piece is of a size of 11 cm x 4 centimetres, each stirring piece has the hole of two diameters 2 centimetres, and stirring piece end and the particulate matter distance stirred between Fluidizer inwall is 2 millimeters to 3 millimeters; Magnetic control sputtering cathode diameter 3 inches, metal sputtering target diameter 7.6 centimetres, thick 0.48 centimetre; Magnetron sputtering power supply selects U.S. MDX-10 type power supply (Advanced Energy Industries company, the state of Colorado, the U.S.), and mate Sparc-le 20 type aura stabilizer (Advanced Energy Industries company, the state of Colorado, the U.S.).

In table 2, metal layer thickness is calculated by the weight metal of sputtering and the total surface area of polymer particles.Obviously, when ignoring the surface-area change that the thickness of metal level own brings (because metal layer thickness is much smaller than polymer particles particle diameter), metal layer thickness can be obtained with the volume of the metal of sputtering divided by the total surface area of polymer particles.Wherein, the metal volume of sputtering can be obtained divided by density metal by the weight metal sputtered, and the weight metal of sputtering namely sputter before and after the weight difference of expanded polymeric microspheres.And the total surface area of polymer particles calculates in such a way:

Object due to sputtering is expanded polymeric microspheres, therefore can think that it is spherical, according to spheroid theory of close packing (Principles of closing packing of spheres), be 74.05% etc. most space-efficient during large spheroid packing space, therefore, the number of the spheroid can filled at most in the space of unit volume is 0.7405/ (4 π R ³, and the surface-area of each spheroid is 4 π R/3) ², therefore in the space of unit volume, the theoretical total surface area of spheroid is:

$\frac{0.7405}{4{\mathrm{\πR}}^3/3}\×\left({4\mathrm{\πR}}^2\right)=2.2215/R,$ Wherein R is the radius of spheroid.

Because expanded polymeric microspheres can be compressed, is not that perfectly spherical, particle diameter has the factors such as certain distribution range, therefore also need to revise above area.We are respectively difference splash-proofing sputtering metal layer on the expanded polymeric microspheres of 20 microns, 40 microns, 75 microns in median size, and with Quanta 600 type scanning electron microscope (FEI Co., Oregon, the U.S.) observe the actual metal layer thickness formed, again by the anti-total surface area pushing away expanded polymeric microspheres of this metal layer thickness, found that, the total surface area of the expanded polymeric microspheres of trying to achieve according to actual metal layer thickness is about 3 times of above theoretical value.Therefore can think, the estimation total surface area of the expanded polymeric microspheres in the space of unit volume is: 3 × 2.2215/R.

In an experiment, contain with the container that can weigh volume and get expanded polymeric microspheres weigh its weight; Afterwards the vacuum sputtering of different time is carried out to expanded polymeric microspheres, obtain compressible micrograde polymer particle (namely with the expanded polymeric microspheres of metal level), and again take its weight, obtain the weight of the metal sputtered; Metal layer thickness is calculated according to above mode with the weight of metal sputtered, the particle diameter of the volume of density metal, expanded polymeric microspheres, expanded polymeric microspheres.

The parameter of table 2, compressible micrograde polymer particle

4, the preparation of slurry polymerization thing

In 1 quart of wide mouth glass bottle, each polymerisable monomer (wherein the total amount of the polymerisable monomer of each example is 100 weight parts) is added in the ratio of table 3, and add the light trigger Irgacure 651 of 0.04 weight part, use nitrogen purge under magnetic stirring 15 minutes, be then exposed to wavelength 365nm, intensity 1.5mw/cm ²low intensity W-light under, irradiate several minutes, in irradiation process, continuous Ubbelohde viscometer measures its viscosity, until stop UV-irradiation when its viscosity at 22 DEG C reaches in the scope of 2000cPs to 6000cPs, and pass into air block polyreaction, obtain slurry polymerization thing S1 to S4.

Wherein, for empty cell represents not containing respective substance in this comparative example or embodiment in form, lower same.

The parameter (consumption is weight part) of table 3, slurry polymerization thing

5, specific embodiment and the performance test results

1) comparative example C1 to C3 and embodiment 1 to embodiment 7

According to the formula of table 4, under lucifuge high-speed stirring, the above-mentioned slurry polymerization thing S1 of 100 weight parts is added in 1 quart of wide mouth glass bottle, and Penncolor 9B117, Irgacure 651 (0.04 weight part that in table, consumption adds before not comprising), HDDA etc., until all components dissolves all completely, gained solution clear; Then add expanded polymeric microspheres FN-80SDE (not being with metal level), compressible micrograde polymer particle (MA, MC), Aerosil R972 etc., fully stir; Finally add glass microballon K15, lucifuge stirring at low speed, to evenly, obtains the curable compositions of each embodiment and comparative example.

Between release that curable compositions is coated two transparent release films of CP Film T10 PET (Solutia company, Tennessee State, the U.S.) of thickness 0.051mm, control glued membrane at specific thickness, with wavelength 365nm, intensity 1.5mw/cm ²low intensity ultraviolet rayed 5 minutes to 10 minutes, make the complete polymerizing curable of curable compositions (i.e. monomer conversion reach or very close to 100%), obtain the adhesive tape of each embodiment and comparative example, test its properties according to the method described above, result is as shown in table 5.

The composition (consumption is weight part) of the curable compositions of table 4, comparative example C1 to C3 and embodiment 1 to embodiment 7

The performance of the adhesive tape of table 5, comparative example C1 to C3 and embodiment 1 to embodiment 7

2) embodiment 8 to embodiment 16

According to the formula of table 6, under lucifuge high-speed stirring, the above-mentioned slurry polymerization thing S2 of 100 weight parts is added in 1 quart of wide mouth glass bottle, and Irgacure 651 (0.04 weight part that in table, consumption adds before not comprising), HDDA, Triazine etc., until all components dissolves all completely, gained solution clear; Then add compressible micrograde polymer particle (MA, MD, ME, MG), Aerosil R972 etc., fully stir; Finally add glass microballon K15, lucifuge stirring at low speed, to evenly, obtains the curable compositions of each embodiment.Afterwards curable compositions is coated two the transparent release film of CP Film T10 PET (Solutia companies of thickness 0.051mm, Tennessee State, the U.S.) release between, control glued membrane at specific thickness, with wavelength 365nm, intensity 1.5mw/cm ²low intensity ultraviolet rayed 5 minutes to 10 minutes, make the complete polymerizing curable of curable compositions (i.e. monomer conversion reach or very close to 100%), obtain the adhesive tape of each embodiment, test its properties according to the method described above, result is as shown in table 7.

The composition (consumption is weight part) of the curable compositions of table 6, embodiment 8 to embodiment 16

The performance of the adhesive tape of table 7, embodiment 8 to embodiment 16

3) embodiment 17 to embodiment 23

According to the formula of table 8, under lucifuge high-speed stirring, the above-mentioned slurry polymerization thing S3 of 100 weight parts is added in 1 quart of wide mouth glass bottle, and Irgacure 651 (0.04 weight part that in table, consumption adds before not comprising), HDDA, PETA, Triazine, tackifying resin etc., until all components dissolves all completely, gained solution clear; Then add compressible micrograde polymer particle (MB, MF), Aerosil R972 etc., fully stir; Finally add glass microballon K15, lucifuge stirring at low speed, to evenly, obtains the curable compositions of each embodiment.Afterwards curable compositions is coated two the transparent release film of CP Film T10 PET (Solutia companies of thickness 0.051mm, Tennessee State, the U.S.) release between, control glued membrane at specific thickness, with wavelength 365nm, intensity 1.5mw/cm ²low intensity ultraviolet rayed 5 minutes to 10 minutes, make the complete polymerizing curable of curable compositions (i.e. monomer conversion reach or very close to 100%), obtain the adhesive tape of each embodiment, test its properties according to the method described above, result is as shown in table 9.

The composition (consumption is weight part) of the curable compositions of table 8, embodiment 17 to embodiment 23

The performance of the adhesive tape of table 9, embodiment 17 to embodiment 23

4) embodiment 24 to embodiment 27

According to the formula of table 10, under lucifuge high-speed stirring, the above-mentioned slurry polymerization thing S4 of 100 weight parts is added in 1 quart of wide mouth glass bottle, and Irgacure 651 (0.04 weight part that in table, consumption adds before not comprising), HDDA etc., until all components dissolves all completely, gained solution clear; Then add compressible micrograde polymer particle (MH, MI, MJ, MK), Aerosil R972 etc., fully stir; Finally add glass microballon K15, lucifuge stirring at low speed, to evenly, obtains the curable compositions of each embodiment.Afterwards curable compositions is coated two the transparent release film of CP Film T10 PET (Solutia companies of thickness 0.051mm, Tennessee State, the U.S.) release between, control glued membrane at specific thickness, with wavelength 365nm, intensity 1.5mw/cm ²low intensity ultraviolet rayed 5 minutes to 10 minutes, make the complete polymerizing curable of curable compositions (i.e. monomer conversion reach or very close to 100%), obtain the adhesive tape of each embodiment, test its properties according to the method described above, result is as shown in table 11.

The composition (consumption is weight part) of the curable compositions of table 10, embodiment 24 to embodiment 27

The performance of the adhesive tape of table 11, embodiment 24 to embodiment 27

5) embodiment 28 to embodiment 29

According to the formula of table 12, under lucifuge high-speed stirring, the above-mentioned slurry polymerization thing S2 of 100 weight parts is added in 1 quart of wide mouth glass bottle, and Irgacure 651 (0.04 weight part that in table, consumption adds before not comprising), HDDA etc., until all components dissolves all completely, gained solution clear; Then add compressible micrograde polymer particle (ML), Aerosil R972 etc., fully stir; Finally add glass microballon K15, lucifuge stirring at low speed, to evenly, obtains the curable compositions of each embodiment.

Different from the adhesive tape of each embodiment before, the adhesive tape prepared in the present embodiment take pressure sensitive adhesive as core, and arrange other binder layer afterwards again in its both sides, its concrete preparation method comprises:

Curable compositions is coated in substrate, control glued membrane at specific thickness, with wavelength 365nm, intensity 1.5mw/cm ²low intensity ultraviolet rayed 5 minutes to 10 minutes, make the complete polymerizing curable of curable compositions (i.e. monomer conversion reach or very close to 100%), obtain pressure sensitive adhesive core.

Respectively brush one deck silane coupling agent in core both sides afterwards, its composition comprises as follows:

Solute: the Macromelt 6240 (Henkel Corp., Dusseldorf, Germany) of 10 weight parts; Solvent: 47.5 parts by weight of isopropyl alcohol (Chemical Reagent Co., Ltd., Sinopharm Group, Shanghai, China), 47.5 weight part n-propyl alcohols (Chemical Reagent Co., Ltd., Sinopharm Group, Shanghai, China), the deionized water of 5 weight parts.

At room temperature place after 10 minutes and obtain the undercoat that thickness is 8.3 microns.

The laminating 50 microns of two-sided glued membrane 467MP (3M company, the Minnesota State, the U.S.) of difference on the undercoat of both sides, after using the manual pressing of rubber rollers, room temperature places one day, obtain adhesive tape, test its properties according to the method described above, result is as shown in table 13.

The composition (consumption is weight part) of the curable compositions of table 12, embodiment 28 to embodiment 29

The performance of the adhesive tape of table 13, embodiment 28 to embodiment 29

6, performance analysis

The test data of above each comparative example and embodiment is compared, is analyzed, can obtain drawing a conclusion:

(1) realize in the adhesive tape (wherein with the addition of the expanded polymeric microspheres not with metal level) of black at use black pigment, along with the intensification of color, every strength property of adhesive tape obviously reduces; Then can have the performances such as higher cohesive strength and peel adhesion when ensureing that color is darker at adhesive tape of the present invention (wherein with the addition of compressible micrograde polymer particle) simultaneously.

(2) in the relatively-stationary situation of other condition, the addition of compressible micrograde polymer particle is more, then adhesive tape color is more black; But meanwhile, every strength property of adhesive tape there is no reduction, is even also improved.This shows, compressible micrograde polymer particle, while making adhesive tape be black, not only can not reduce the intensity of adhesive tape, also can increase its intensity on the contrary.

(3) when using compressible micrograde polymer particle, other component (tackifying resin, glass microballon, expanded polymeric microspheres etc.) still can use, and shows that adding of compressible micrograde polymer particle can not cause detrimentally affect to the use of other component.

(4) in the relatively-stationary situation of other condition, in compressible micrograde polymer particle, the thickness of metal level is larger, then adhesive tape color is more black.This shows, the color of selection on product of metal layer thickness has important impact.

(5) if the add-on of compressible micrograde polymer particle exceedes the upper limit (polymerisable monomer of relative 100 weight parts is more than 7 weight parts) required in the present invention, then curable compositions can not solidify completely.This shows, the add-on of compressible micrograde polymer particle can not exceed the scope required in the present invention.

(6) adhesive tape of the present invention can directly using pressure sensitive adhesive simultaneously as core and tackiness agent, and also also can use additional binder layer with pressure sensitive adhesive as core, two kinds of forms are all feasible.If therefore need, the binder layer of different performance can be selected to give adhesive tape more diversified performance.

Be understandable that, the illustrative embodiments that above embodiment is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.

Claims (31)

1. a compressible micrograde polymer particle, it comprises:

Polymer particles, this polymer particles has the shell be made up of polymer materials and the cavity surrounded by described shell;

Cover the metal level on described shell outside surface.

2. compressible micrograde polymer particle according to claim 1, wherein,

Described polymer particles is spherical substantially.

3. compressible micrograde polymer particle according to claim 1, wherein,

The particle diameter of described polymer particles is between 10 microns to 100 microns;

The thickness of the shell of described polymer particles is between 2 microns to 15 microns.

4. compressible micrograde polymer particle according to claim 1, wherein,

Described polymer materials is thermoplastic polymer, and described cavity is filled with gas.

5. compressible micrograde polymer particle according to claim 4, wherein,

Described thermoplastic polymer is thermoplastic polypropylene acid resin, and described gas is alkane.

6. compressible micrograde polymer particle according to claim 1, wherein,

The material of described metal level is be selected from any one metal in tungsten, titanium, aluminium, chromium, niobium, zirconium or its alloy.

7. compressible micrograde polymer particle according to claim 1, wherein,

Described metal layer thickness is between 5 nanometer to 80 nanometers.

8. compressible micrograde polymer particle according to claim 7, wherein,

Described metal layer thickness is between 6 nanometer to 70 nanometers.

9. compressible micrograde polymer particle according to claim 8, wherein,

Described metal layer thickness is between 12 nanometer to 60 nanometers.

10. compressible micrograde polymer particle according to claim 9, wherein,

Described metal layer thickness is between 20 nanometer to 60 nanometers.

11. compressible micrograde polymer particles according to claim 1, wherein,

Described metal level is formed on described polymer particles outside surface by vacuum sputtering.

12. 1 kinds of curable compositions, it comprises:

Slurry polymerization thing, it comprises the mixture by the copolymerization of at least two kinds of polymerisable monomer parts, and described mixture comprises the described polymerisable monomer that polymerization does not occur and the multipolymer formed by described polymerisable monomer copolymerization;

Light trigger;

Compressible micrograde polymer particle, it comprises: polymer particles, and this polymer particles has the shell be made up of polymer materials and the cavity surrounded by described shell; Cover the metal level on described shell outside surface.

13. curable compositions according to claim 12, wherein, described polymerisable monomer comprises:

As the acrylic ester monomer of the first monomer;

As the non-ester unsaturated monomer with at least one ethylene linkage of second comonomer.

14. curable compositions according to claim 13, wherein,

Described first monomer is (methyl) acrylate monomer of non-tertiary alcohol;

Described second comonomer is the non-ester unsaturated monomer with at least one ethylene linkage of sour official energy.

15. curable compositions according to claim 12, wherein,

Described slurry polymerization thing the viscosity of 22 DEG C between 500cPs to 10000cPs.

16. curable compositions according to claim 12, wherein,

The weight-average molecular weight of described multipolymer is between 500000 dalton to 10000000 dalton;

Relative to the described polymerisable monomer occurring to be polymerized and the gross weight that the described polymerisable monomer be polymerized does not occur, there is the ratio of the weight of the described polymerisable monomer be polymerized between 1% to 30%.

17. curable compositions according to claim 12, wherein,

Relative to the described polymerisable monomer occurring to be polymerized and the gross weight that the described polymerisable monomer be polymerized does not occur, the ratio of the weight of described compressible micrograde polymer particle is between 0.1% to 7%.

18. curable compositions according to claim 17, wherein,

Relative to the described polymerisable monomer occurring to be polymerized and the gross weight that the described polymerisable monomer be polymerized does not occur, the ratio of the weight of described compressible micrograde polymer particle is between 1% to 7%.

19. curable compositions according to claim 18, wherein,

Relative to the described polymerisable monomer occurring to be polymerized and the gross weight that the described polymerisable monomer be polymerized does not occur, the ratio of the weight of described compressible micrograde polymer particle is between 1% to 6%.

20. curable compositions according to claim 12, wherein, also comprise:

Linking agent.

21. curable compositions according to claim 20, wherein,

Described linking agent comprises multifunctional (methyl) acrylate and/or triazines material.

22. curable compositions according to claim 12, wherein, also comprise:

Hydrophobicity aerosil.

The preparation method of 23. 1 kinds of curable compositions, it comprises:

Make the copolymerization of at least two kinds of polymerisable monomer generating portions, obtain slurry polymerization thing;

Light trigger and compressible micrograde polymer particle are mixed with described slurry polymerization thing; Wherein, described compressible micrograde polymer particle comprises: polymer particles, and this polymer particles has the shell be made up of polymer materials and the cavity surrounded by described shell; Cover the metal level on described shell outside surface.

24. 1 kinds of pressure sensitive adhesives, it is formed by curable compositions solidification, and described curable compositions comprises:

Slurry polymerization thing, it comprises the mixture by the copolymerization of at least two kinds of polymerisable monomer parts, and described mixture comprises the described polymerisable monomer that polymerization does not occur and the multipolymer formed by described polymerisable monomer copolymerization;

Light trigger;

Compressible micrograde polymer particle, it comprises: polymer particles, and this polymer particles has the shell be made up of polymer materials and the cavity surrounded by described shell; Cover the metal level on described shell outside surface.

25. 1 kinds of adhesive tapes, it comprises pressure sensitive adhesive, and described pressure sensitive adhesive is formed by curable compositions solidification, and described curable compositions comprises:

Slurry polymerization thing, it comprises the mixture by the copolymerization of at least two kinds of polymerisable monomer parts, and described mixture comprises the described polymerisable monomer that polymerization does not occur and the multipolymer formed by described polymerisable monomer copolymerization;

Light trigger;

Compressible micrograde polymer particle, it comprises: polymer particles, and this polymer particles has the shell be made up of polymer materials and the cavity surrounded by described shell; Cover the metal level on described shell outside surface.

26. adhesive tapes according to claim 25, wherein,

Described adhesive tape is made up of pressure sensitive adhesive;

Or,

Described adhesive tape comprises core and is located at the binder layer on described at least one surface of core, and described core is made up of described pressure sensitive adhesive.

27. adhesive tapes according to claim 25, wherein,

In the colour system represented according to L value a value b value, the colored L value of described glue is between 0 to 30.

28. adhesive tapes according to claim 27, wherein,

The colored L value of described glue is between 0 to 25.

29. adhesive tapes according to claim 28, wherein,

The colored L value of described glue is between 0 to 20.

30. adhesive tapes according to claim 25, wherein,

The thickness of the pressure sensitive adhesive of described adhesive tape is between 0.05 millimeter to 5 millimeters.

31. 1 kinds of compressible micrograde polymer particles are used for the purposes of pressure sensitive adhesive, wherein,

Described compressible micrograde polymer particle comprises: polymer particles, and this polymer particles has the shell be made up of polymer materials and the cavity surrounded by described shell; Cover the metal level on described shell outside surface;

Described pressure sensitive adhesive is polyacrylate(s) pressure sensitive adhesive.