CN100594224C - Pressure sensitive adhesion sheet and preparing method thereof - Google Patents

Pressure sensitive adhesion sheet and preparing method thereof Download PDF

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Publication number
CN100594224C
CN100594224C CN200710092351A CN200710092351A CN100594224C CN 100594224 C CN100594224 C CN 100594224C CN 200710092351 A CN200710092351 A CN 200710092351A CN 200710092351 A CN200710092351 A CN 200710092351A CN 100594224 C CN100594224 C CN 100594224C
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sensitive adhesive
latex
pressure sensitive
adhesive layer
water
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CN101033378A (en
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入江刚史
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Toyo Ink Mfg Co Ltd
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Toyo Ink Mfg Co Ltd
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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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention provides a pressure-sensitive adhesive sheet which is characterized in that the pressure-sensitive adhesive sheet includes a plastic base material except a foaming body and a pressure-sensitive adhesive layer laminated on at least one surface of the base material; the pressure-sensitive adhesive layer is formed by a latex type pressure sensitive adhesive with acrylic polymeras main component, the water-solubility component in the pressure sensitive adhesive layer is lower than 3 weight%; when the thickness of the pressure sensitive adhesive layer is 20 mum and 25 DEG C,the layer is dipped into water for 24 hours, and the brightness L<x> is lower than 40; when carrying through 180 DEG C peel off, the adhesive force is more than 6N/25mm.

Description

Pressure sensitive adhesion sheet and preparation method thereof
Technical field
The present invention relates to pressure sensitive adhesion sheet that comprises plastic sheet base material and pressure sensitive adhesive layer and preparation method thereof.Specifically, pressure-sensitive adhesive layer also is difficult for whiting, has pressure sensitive adhesion sheet of good anti-whiting performance and preparation method thereof in the immersion water even relate to.
Background technology
In order to form pressure sensitive adhesion sheet, adopt pressure sensitive adhesive.
Substantially the laminated such single face pressure sensitive adhesion sheet of (1) substrate sheets/pressure sensitive adhesive layer/stripping film that constitutes of pressure sensitive adhesion sheet, perhaps (2) stripping film/pressure sensitive adhesive layer/such double-sided pressure-sensitive adhesive sheet of substrate sheets/pressure sensitive adhesive layer/stripping film.In use, stripping film is peeled off, then pressure sensitive adhesive layer is adhered to by on the adherend.
Because pressure sensitive adhesion sheet is used for various purposes, so desired bounding force is also various.It is also various to adhere to the employed environment in back, and they are under the high humidity sometimes, are exposed to sometimes in cold water or the hot water.Under such occasion, just require pressure sensitive adhesive layer to have water tolerance.For example, be used under the adherent situation of optical material, because require through still having the moisture resistance properties of height after the long time, so require pressure sensitive adhesive layer can promptly can not whiten because of water produces gonorrhoea.
Pressure sensitive adhesive layer roughly is divided into solvent-borne type pressure sensitive adhesive and water based emulsion type pressure sensitive adhesive, and these two kinds of tackiness agents are as main ingredient mostly with acrylic polymers.
Usually, when formation had the pressure sensitive adhesive layer of excellent water resistance, the solvent-borne type pressure sensitive adhesive was more suitable for than water based emulsion type pressure sensitive adhesive.But, from the environment of preserving our planet (suppress discharge volatile compound) with improve viewpoints such as work situation and efficent use of resources,, also require to adopt aqueous pressure-sensitive adhesive replacement solvent-borne type pressure sensitive adhesive even in the field that requires enhanced water resistance.
But, under the situation that requires big bounding force, (for example,, peel off down, require under the situation of the above bounding force of 6N/25mm) at 180 degree for polyethylene board, adopt the solvent-borne type pressure sensitive adhesive that contains tackifying resin mostly.Tackifying resin is dissolved in the solvent.Therefore, under the occasion of solvent-type acrylic class pressure sensitive adhesive, tackifying resin is soluble in the solvent solution of acrylic polymers.As a result, because acrylic polymers and tackifying resin fully mix, so the dry coating of solvent-type acrylic class pressure sensitive adhesive, promptly pressure sensitive adhesive layer has the excellent transparency usually.
On the other hand, acrylic acid or the like water based emulsion type pressure sensitive adhesive be with the acrylic polymers latex as main ingredient, with water as dispersion medium.But tackifying resin is water insoluble.Therefore, when tackifying resin was directly mixed with the acrylic acid polymer emulsion adhesive, the water-soluble latex type of extremely difficult acquisition acrylic acid or the like pressure sensitive adhesive was even form tackiness agent, the also non-constant of its dispersion stabilization.
So,, attempted various methods for tackifying resin being imported in the acrylic acid or the like water based emulsion type pressure sensitive adhesive.
For example, proposed in advance tackifying resin carry out latexization, then it has been sneaked into the scheme of acrylic polymers latex.According to the method, can be that the solid tackifying resin is sneaked in the acrylic polymers latex with major part.
But if adopt this method, then not only the transparency is poor for the pressure sensitive adhesive layer that obtains after the pressure sensitive adhesive drying, and because the influence of water, gonorrhoea can take place in pressure sensitive adhesive layer.It is generally acknowledged that this is because in the drying process of pressure sensitive adhesive, polymer beads from the acrylic polymers latex is difficult to mix with tackifying resin, so tackifying resin has formed distinct area, can not form homogeneous phase, the result is exactly a pressure sensitive adhesive layer gonorrhoeaization not only, and also variation of water tolerance.
Among the following patent documentation 1-3 such method has been proposed, the latex that promptly contains free-radical polymerised unsaturated monomer, tackifying resin, tensio-active agent (preferred reaction surfacant) and water by preparation in advance, this latex of polymerization then, thus tackifying resin is imported latex type pressure sensitive adhesive.
For example, the embodiment 4 of Japanese Patent Application Publication 2000-313865 number (patent documentation 1) has put down in writing such method, obtain earlier to contain the latex of about 1.6 parts and water of free-radical polymerised unsaturated monomer 100 weight parts, 5 parts of tackifying resins, reactive surfactant, this latex of polymerization obtains latex type pressure sensitive adhesive then.But because the tensio-active agent that adopted is a reactive surfactant, and its amount is many, so the transparency and the water tolerance of the pressure sensitive adhesive layer that is obtained by such latex type pressure sensitive adhesive are just not enough.In addition, the amount of tackifying resin is fewer, so can not obtain to have the pressure sensitive adhesion sheet of following performance, promptly with respect to polyethylene board, peels off down at 180 degree, can demonstrate the above high adhesion of 6N/25mm.
The embodiment 1 and 2 of Japanese Patent Application Publication 2001-031708 number (patent documentation 2) has put down in writing such method, promptly obtain to contain the latex of free-radical polymerised unsaturated monomer 100 weight parts, 10 parts of tackifying resins, 1.5 parts of reactive surfactants and water earlier, then foregoing latex is splashed in the water that contains 1.5 parts of reactive surfactants, and carry out polymerization, obtain latex type pressure sensitive adhesive.But because the tensio-active agent that adopted is a reactive surfactant, and employed total amount is also many, so the transparency of the pressure sensitive adhesive layer that is obtained by such latex type pressure sensitive adhesive is not enough.
In addition, the embodiment 1 of Japanese Patent Application Publication 2001-348551 number (patent documentation 3) has put down in writing such method, obtain to contain the latex of free-radical polymerised unsaturated monomer 100 weight parts, 15 parts of tackifying resins, 2.5 parts of reactive surfactants and water earlier, this latex of polymerization obtains latex type pressure sensitive adhesive then.But because the tensio-active agent that is adopted is a reactive surfactant, and its amount is also many, so the pressure sensitive adhesive layer transparency that is obtained by such latex type pressure sensitive adhesive is still not enough.
Invent problem to be solved
The purpose of this invention is to provide the pressure sensitive adhesion sheet that contains plastic sheet base material and pressure sensitive adhesive layer, this pressure sensitive adhesion sheet has good water tolerance, also is difficult to the pressure sensitive adhesive layer that whitens in the water even have to immerse, and demonstrates high adhesion simultaneously.
The mode of dealing with problems
The present invention relates to pressure sensitive adhesion sheet, it is characterized in that: this pressure sensitive adhesion sheet comprises the plastic sheet base material except that foam and is laminated to pressure sensitive adhesive layer at least one face of aforementioned substrates; Aforesaid pressure sensitive adhesive layer is by forming the latex type aqueous pressure-sensitive adhesive of acrylic polymers as main ingredient, and the amount of contained water soluble ingredient is below the 3 weight % in this pressure sensitive adhesive layer; When the thickness of aforesaid pressure-sensitive adhesive layer is 20 μ m, in the time of 25 ℃, after in its immersion water 24 hours, lightness L *Be below 40; And for polyethylene board, carrying out 180 degree when peeling off, bounding force is more than the 6N/25mm.
The invention still further relates to pressure sensitive adhesion sheet, it is characterized in that: this pressure sensitive adhesion sheet comprises the plastic sheet base material except that foam and is laminated to pressure sensitive adhesive layer at least one face of aforementioned substrates; Aforementioned pressure sensitive adhesive layer is by forming the latex type aqueous pressure-sensitive adhesive of acrylic polymers as main ingredient, and contained water soluble ingredient amount is below the 3 weight % in this pressure-sensitive adhesive layer; Aforesaid latex type aqueous pressure-sensitive adhesive comprises the composition latex that contains acrylic polymers, this latex forms by containing the monomer combination emulsion polymerization, and the described monomer combination latex that contains comprises: can form second-order transition temperature and be (methyl) alkyl acrylate of the polymkeric substance below 0 ℃ as free-radical polymerised unsaturated monomer (A) 100 weight parts of main ingredient, contain tackifying resin (B) 6～30 weight parts, non-reacted tensio-active agent (C) 0.2～1.5 weight part and the water of the above rosin based tackifying resin of 60 weight %.
In addition, the invention still further relates to the preparation method of the pressure sensitive adhesion sheet that comprises following steps: the latex type aqueous pressure-sensitive adhesive that will contain the composition latex of acrylic polymers is applied at least one face of the plastic sheet base material except that foam, carry out drying then, latex particle from the composition latex that contains acrylic polymers is merged, form pressure sensitive adhesive layer, the composition latex that wherein contains acrylic polymers forms by containing the monomer combination emulsion polymerization, describedly contains monomeric latex and comprises that can to form second-order transition temperature be free-radical polymerised unsaturated monomer (A) 100 weight parts of (methyl) alkyl acrylate of the polymkeric substance below 0 ℃ as main ingredient, tackifying resin (B) 6～30 weight parts that contain the above rosin based tackifying resin of 60 weight %, (C) non-reacted tensio-active agent 0.2～1.5 weight part and water; The amount of contained water soluble ingredient is below the 3 weight % in the aforesaid pressure sensitive adhesive layer; When the thickness of aforementioned pressure sensitive adhesive layer is 20 μ m, under 25 ℃, after in its immersion water 24 hours, lightness L *Be below 40; For polyethylene board, when carrying out 180 degree when peeling off, its bounding force is more than the 6N/25mm.
The invention effect
Even immersing, pressure sensitive adhesion sheet provided by the invention also is difficult for whiting in the water, specifically, when the thickness of pressure sensitive adhesive layer is 20 μ m, in the water under it is immersed 25 ℃ after 24 hours, lightness L *Be below 40.In addition, pressure sensitive adhesion sheet of the present invention has good bounding force, specifically, for polyethylene board, carries out 180 and spends when peeling off, and bounding force shows as more than the 6N/25mm.
Embodiment
Pressure sensitive adhesion sheet of the present invention is that the pressure sensitive adhesive layer that will be formed as the latex type aqueous pressure-sensitive adhesive of main ingredient by acrylic polymers is laminated at least one face of the plastic sheet base material except that foam and forms.
Plastic sheet base material of the present invention (below, be abbreviated as " base material " or " flat substrates " sometimes) can be enumerated as various plastic sheet or plastics films with even shape.But, except the foam base material.
Various base materials also can will use with the multiple stratification form behind the multiple base material lamination except (individual layer) uses separately.In addition, also can use the base material of surface through lift-off processing.
Thickness for base material is not particularly limited, but preferred thickness is about 15～200 μ m usually, and more preferably thickness is about 25～80 μ m.
Operable various plastic sheet (various plastics film) for example is: PVA (PVOH) FILM, triacetylcellulose film, polyolefin resin film (polypropylene, polyethylene, poly-cyclenes, ethylene-vinyl acetate copolymer etc.), polyester resin film (polyethylene terephthalate) (below be written as " PET "), polybutylene terephthalate etc.), the polycarbonate resin film, the polynorbornene based resin film, the polyarylester based resin film, the acrylic resin film, the polyphenylene sulfide based resin film, the polystyrene resin film, vinyl-based resin film, polyamide-based resin film, the polyimide based resin film, redix film etc.
To be used under the condition of optical field by the pressure sensitive adhesion sheet of the present invention's preparation, preferred above-mentioned plastics film is the optics plastics film with good transparency, be under the condition of 100 μ m at thickness more specifically, transmittance is the optics plastics film more than 80%.
This optics except adopting the single thin film, also can adopt the film of multiple stratification with plastics film.
Single layer optical can be exemplified as polyester film, polycarbonate film, triacetylcellulose film, cyclenes film etc. with film.
The optical thin film of multiple stratification can be exemplified as light polarizing film, phase retardation film, elliptical polarized light film, antireflection film, brightness enhancement film etc.Light polarizing film for example can be exemplified as: the laminate structures that the two sides of adopting triacetyl cellulose to be clipped in the polyvinyl alcohol polarizer forms.Phase retardation film for example can be exemplified as: the structure that the polycarbonate laminate that extends is formed.Antireflection film for example can be exemplified as: the laminate structures that forms behind coating tetrafluoroethylene on the PET film.Brightness enhancement film for example can be exemplified as: the laminate structures that forms behind coating diffustivity particulate on the PET film.
Pressure sensitive adhesive layer is formed by latex type aqueous pressure-sensitive adhesive (following be abbreviated as sometimes " aqueous pressure-sensitive adhesive "), and it has good water tolerance and binding property.
The pressure sensitive adhesive layer that promptly constitutes pressure sensitive adhesion sheet of the present invention is by forming the latex type aqueous pressure-sensitive adhesive of acrylic polymers as main ingredient, and its contained water soluble ingredient amount is below the 3 weight %.
In addition, this pressure sensitive adhesive layer can also provide the so-called water tolerance (1) with following (1) and (2) and the pressure sensitive adhesion sheet of binding property (2):
(1) thickness at pressure sensitive adhesive layer is under the 20 μ m, after (25 ℃, 24 hours) in its immersion water, and lightness L *Be below 40;
(2) with respect to polyethylene board, when peeling off under 180 degree, bounding force is more than the 6N/25mm.
The acrylic polymers that constitutes latex type aqueous pressure-sensitive adhesive can use tensio-active agent and polymerization starter, make the free-radical polymerised unsaturated monomer of acrylic monomer by known emulsion polymer method, carry out polymerization and form as main ingredient.
Free-radical polymerised unsaturated monomer preferably is that (methyl) alkyl acrylate of 1～14 is as main ingredient with the carbonatoms of alkyl.This (methyl) alkyl acrylate can be exemplified as: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) decyl acrylate, the acrylate of the fatty alcohol of straight chain such as (methyl) vinylformic acid dodecane ester or branching and corresponding methacrylic ester etc.The carbonatoms of alkyl more preferably 1～10 in employed (methyl) alkyl acrylate, more preferably 1～8, especially preferably with 2-ethylhexyl acrylate as main ingredient.These materials can use separately, also can multiplely be used in combination.
In free-radical polymerised unsaturated monomer total amount is 100 weight %, and the content of above-mentioned (methyl) alkyl acrylate is preferably 70～99.9 weight %.
In free-radical polymerised unsaturated monomer total amount is 100 weight %, and free-radical polymerised unsaturated monomer preferably comprises the monomer that 0.1～20 weight % contains carboxyl, more preferably comprises 0.2～5 weight %, further preferably comprises 0.2～2 weight %.The monomer that contains carboxyl can be exemplified as: vinylformic acid, methacrylic acid, maleic anhydride, toxilic acid, methylene-succinic acid, Ba Dousuan etc.When containing the monomeric ratio less than 0.1 weight % of carboxyl, constitute formed acrylic polymers latex the dispersate particle (below, the dispersate particle is called latex particle.) dispersion state in water becomes unstable easily, and is unstable thereby polymerization also becomes easily.On the other hand, dry, then during ageing when the monomeric ratio that contains carboxyl is higher than 20 weight %, the bonding between the latex particle will be hindered, and when immersing it in water, pressure sensitive adhesive layer is whiting easily just.
As required, free-radical polymerised unsaturated monomer can use other monomer outside above-mentioned.This monomer can be exemplified as: (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) polyalkylene glycol acrylate ester etc. contain the monomer of alcohol hydroxyl group; Glycidyl acrylate, glycidyl methacrylate etc. contain the monomer of epoxy group(ing); (methyl) acrylamide monomers such as N-hydroxyalkyl (methyl) acrylamide, N-alkoxyalkyl (methyl) acrylamide, methylolation acrylamide, N-(1,1-dimethyl-3 oxygen-butyl) acrylamide, diacetone-acryloamide(DAA); Contain vinyl monomers such as the vinyl monomer of phosphate and vinyl acetate, vinylbenzene, divinyl; And contain monomer of acetoacetoxy groups ethyl-methyl acrylate, alkoxysilyl etc.Total amount in free-radical polymerised unsaturated monomer is 100 weight %, and these monomers can use with the ratio of 0～10 weight %, can also adopt one or more monomer.
According to above content, free-radical polymerised unsaturated monomer preferably adopts following monomeric mixture: (methyl) alkyl acrylate (main ingredient) 70～99.9 weight %, contain monomer 0.1～20 weight % of carboxyl and except that above-mentioned other monomer 0～10 weight % both.
Pressure sensitive adhesive layer forms by following steps usually, is about to liquid pressure sensitive adhesive and coats on the flat substrates such as plastic sheet, removes the liquid medium that comprises in the pressure sensitive adhesive by drying then.
Under the situation of solvent-borne type pressure sensitive adhesive,,, form pressure sensitive adhesive layer with the direct film forming of the polymkeric substance that is comprised by removing liquid medium.On the other hand, under the situation of latex type aqueous pressure-sensitive adhesive, when removing liquid medium, by after ageing process, make that dispersate latex particle experience is approaching, bonding, fusion, film forming process.
The amount that the present invention importantly constitutes the water soluble ingredient that is comprised in the pressure sensitive adhesive of pressure sensitive adhesion sheet is below the 3 weight %, is preferably below the 2.5 weight %.Surpass under the condition of 3 weight % in the amount of water soluble ingredient, when ageing, approaching, the bonding between the latex particle, merge and hindered.Thereby the pressure sensitive adhesive layer that contained water soluble ingredient is higher than 3 weight % just can not form fine and close membrane structure.As a result, sparse pressure sensitive adhesive layer poor water resistance whitened after in its immersion water 24 hours under 25 ℃, and when the thickness of pressure sensitive adhesive layer is 20 μ m, can not provide lightness L *It is the pressure sensitive adhesion sheet below 40.
Lightness L *Numeric representation by 0 to 100.L *The complete black of=0 expression, L *=100 expressions are pure white fully.Usually, L *Greater than 40 o'clock, under the situation of eye-observation, be recognized as " in vain " outdoor goods that it can not be used for the highly water-proof optics of requirement and be exposed to water.
In the present invention or later record, this lightness L *Be meant immerse pressure sensitive adhesion sheet in the water before, or 25 ℃ of values of being measured after immersing it in water, wherein this pressure sensitive adhesion sheet is laminated on the plastic sheet base material by the pressure sensitive adhesive layer that with thickness is 20 μ m and forms.In a word, it is meant and is provided with the pressure sensitive adhesion sheet (base material+pressure sensitive adhesive layer) that thickness is 20 μ m pressure sensitive adhesive layers, the lightness before and after (25 ℃, 24 hours) are handled in immersion.Be specifically soak handle before, or after handling and take out through immersion immediately by reflection method and the value that adopts multiple light courcess spectral photometric colour measuring meter to be measured.
Therefore, concerning the pressure sensitive adhesive layer that constitutes pressure sensitive adhesion sheet of the present invention, when importantly it being immersed in 25 ℃ the water 24 hours, even whiting, the pressure sensitive adhesive layer thickness is the L of the pressure sensitive adhesion sheet of 20 μ m *Also be below 40, more preferably L *Be below 35.Under the state before immersing it in water, the pressure sensitive adhesive layer thickness is the L of the pressure sensitive adhesion sheet of 20 μ m *Can not surpass 40.
Water-soluble substances in the various components that " water soluble ingredient " that comprises in the pressure sensitive adhesive layer is illustrated in the pressure sensitive adhesive layer to be comprised, wherein this pressure sensitive adhesive layer is by being applied to pressure sensitive adhesive base material and carrying out drying, forms after removing volatile constituent.
The example can be exemplified as: in the tensio-active agent that the letex polymerization that is used for obtaining acrylic polymers is adopted, itself do not have the water-soluble substances in the free-radical polymerised so-called non-reacted tensio-active agent; Be used for and the neutralizing agent of acrylic polymers latex in, in order not show the volatility of ammonia etc., residual material in formed pressure sensitive adhesive layer; In addition, in the preparation pressure sensitive adhesive, the water soluble ingredient that is comprised in defoamer, wetting agent, sanitas, the tackifier etc.
But, obtain except reactive surfactant, polymerization starter and the linking agent that the letex polymerization of acrylic polymers adopts in as described below being used for.
The bounding force of pressure sensitive adhesion sheet importantly, the bounding force of pressure sensitive adhesive layer just, for polyethylene board, when carrying out the peeling off of 180 degree, bounding force is more than the 6N/25mm, is preferably more than the 7N/25mm, more preferably more than the 8N/25mm.
In order to obtain pressure sensitive adhesion sheet of the present invention, the latex type aqueous pressure-sensitive adhesive that is adopted preferably comprises the composition latex (following also be abbreviated as " polymer emulsion ") that contains acrylic polymers, the composition latex that wherein contains acrylic polymers is to form by containing the monomer combination emulsion polymerization, and the described monomer combination latex that contains comprises: can form second-order transition temperature and be polymkeric substance below 0 ℃ with free-radical polymerised unsaturated monomer (A) 100 weight parts of (methyl) alkyl acrylate as main ingredient, tackifying resin (B) 6～30 weight parts that contain the above rosin based tackifying resin of 60 weight %, (C) non-reacted tensio-active agent 0.2～1.5 weight part and water.
To contain the free-radical polymerised unsaturated monomer (A) that uses in the monomer combination latex be foregoing various monomer forming this, and preferred employing can form the monomer that second-order transition temperature is the polymkeric substance below 0 ℃.
In addition, in order to form fine and close pressure sensitive adhesive layer, importantly when drying, and optional as required when carrying out ageing, promote the fusion between the latex particle.Therefore, in order to promote the fusion between the latex particle, preferably utilize intergranular crosslinked.
Intergranular crosslinked in order to form, above-mentioned free-radical polymerised unsaturated monomer (A) preferentially is used in combination and contains the monomer that can carry out the functional group of crosslinking reaction.Wherein, preferentially be used in combination the monomer that contains carboxyl or hydroxyl, and the monomer that can carry out the functional group of crosslinking reaction when containing film forming with them.These functional groups also can be the groups with self-crosslinking.
In addition, by using the described linking agent in back (D), also can form intergranular crosslinked.
Intergranular crosslinked in order to form, the monomer that is suitable for can be exemplified as: glycidyl acrylate, glycidyl methacrylate etc. contains the monomer of epoxy group(ing); (methyl) acrylamide monomer of N-hydroxyalkyl (methyl) acrylamide, N-alkoxyalkyl (methyl) acrylamide, methylolation acrylamide, diacetone-acryloamide(DAA) etc.; And the monomer that contains alkoxysilyl, acetoacetoxy groups ethyl-methyl olefin(e) acid ester.
Under the situation of the above-mentioned various free-radical polymerised unsaturated monomers of polymerization (A), the second-order transition temperature of resulting polymers (Tg) is preferably below 0 ℃, more preferably-10 ℃ below, more preferably-20 ℃ below.That is, in order to obtain required pressure-sensitive adhesive layer, the second-order transition temperature that preferably adopts resulting polymers (homopolymer) is the such free-radical polymerised unsaturated monomer below 0 ℃.
In other words, as the acrylic polymers of the main ingredient of aqueous pressure-sensitive adhesive, preferably adopting second-order transition temperature is material below 0 ℃.
With total amount 100 weight parts of free-radical polymerised unsaturated monomer (A) as benchmark, the resinoid tackifying resin of rosin (or fusible resin is provided) that comprises at least 60 weight % (B) preferably uses 6～30 weight parts, more preferably 8～25 weight parts, further preferred 10～20 weight parts.
When tackifying resin (B) less than 6 weight parts, be difficult to form the pressure sensitive adhesive layer that demonstrates adequate bonds power, be exactly with respect to polyethylene board specifically, be 180 when spending at degree of peeling off, bounding force is difficult for reaching more than the 6N/25mm.
On the other hand, when tackifying resin (B) surpassed 30 weight parts, the water tolerance of pressure-sensitive adhesive layer reduced, and was difficult to form make pressure sensitive adhesion sheet flood back its lightness L in water *It is the pressure sensitive adhesive layer below 40.In addition, if contained tackifying resin (B) is too much in the pressure-sensitive adhesive layer, then pressure-sensitive adhesive layer will become soft, was difficult to obtain firm bounding force.
Here, preferably tackifying resin (B) is sneaked in the monomer latex.Thereby tackifying resin (B) just has been added in the formed polymer beads, has obtained acrylic polymers and tackifying resin (B) and has formed incorporate latex particle, so can form the pressure sensitive adhesive layer with excellent water resistance.On the other hand, if take later tackifying resin (B) to be added into the method for formed polymer emulsion, though then can obtain binding property, but owing to only formed the mixture of the latex of the latex of acrylic polymers and tackifying resin (B), therefore the fusion of two kinds of latex particles is difficult to carry out, and probably can not obtain desirable water tolerance.
Total amount in free-radical polymerised unsaturated monomer (A) is 100 weight parts, tackifying resin (B) is even use 6～30 weight parts, when the rosin based resin in tackifying resin (B) during shared ratio less than 60 weight %, stage before then in its immersion water, the transparency of pressure sensitive adhesive layer is just poor, in addition, water tolerance is also bad, so if it is immersed bleach just easilier in water, opaque.From the transparency and water-proof angle,,, preferably use with other tackifying resin from the angle of economy though preferably only adopt the rosin based resin.
Other tackifying resin that uses with the rosin based resin can be exemplified as: terpenoid resin, fragrant same clan petroleum resin, aliphatic category petroleum resin etc.From the angle of bounding force, preferably use terpenoid resin simultaneously.
The rosin based resin can be exemplified as: natural rosin, rosin ester, hydrogenation rosin, hydrogenation rosin ester, polymerized rosin, polymerized rosin ester, non-homogenizing rosin, non-homogenizing rosin ester etc.
Terpenoid resin can be exemplified as: α-Pai Xishuzhi, beta-pinene resin, terpene phenolic resin, hydrogenation terpene phenolic resin etc.
Aromatic petroleum resin can be exemplified as: styrene oligomer, alpha-methyl styrene/styrol copolymer etc.
The monomer composition latex that importantly contains above-mentioned free-radical polymerised unsaturated monomer (A) and tackifying resin (B) further comprises non-reacted tensio-active agent (C) as emulsifying agent, rather than reactive surfactant.
Promptly, so long as with mixed solution emulsification simply in water medium of free-radical polymerised unsaturated monomer (A) and tackifying resin (B), just can adopt so-called reactive surfactant arbitrarily, or not have the non-reacted tensio-active agent of free-radical polymerised functional group with free-radical polymerised functional group.But,,,, preferably adopt non-reacted tensio-active agent (C) in view of following reason in order to obtain to have the pressure sensitive adhesive layer of excellent water resistance according to viewpoint of the present invention.
That is to say, when containing the monomer emulsion polymerization of free-radical polymerised unsaturated monomer (A) and tackifying resin (B), after investigating reactive surfactant and free-radical polymerised unsaturated monomer copolymerization, the reactive surfactant that loses degree of freedom is fixed on the latex particle near surface of the composition latex that contains acrylic polymers of generation.The latex particle of this polymer emulsion is made of as main ingredient rich more oil loving acrylic polymers and tackifying resin (B).Therefore, the latex type pressure sensitive adhesive that contains this polymer emulsion in drying, when forming pressure sensitive adhesive layer, can infer hydrophilic segment from the tensio-active agent that is fixed on the latex particle near surface, because its wetting ability, with account for the most lipophilicity of latex particle and partly do not have avidity, so hindered fusion between the latex particle of polymer emulsion.The result is the pressure sensitive adhesive that is difficult to have from the pressure sensitive adhesive acquisition that contains the polymer emulsion that adopts the reactive surfactant acquisition excellent water resistance.
In contrast, under the situation that adopts non-reacted tensio-active agent (C), even tensio-active agent is present near the latex particle of polymer emulsion, owing to it is not fixed, so in the process of drying and forming-film, can in film, move.That is to say, because non-reacted tensio-active agent (C) does not hinder the fusion that is rich between the oil loving latex particle, so the pressure sensitive adhesive that contains polymer emulsion that adopts non-reacted tensio-active agent (C) to obtain can form the pressure sensitive adhesive layer of density homogeneous.Pressure sensitive adhesive layer is owing to the density homogeneous, so have good water tolerance.
In addition, need not to give an example, before, on the water tolerance that improves pressure sensitive adhesive layer, it is generally acknowledged that the most resultful is exactly to adopt reactive surfactant as emulsifying agent with special patent documentation etc.Therefore, opinion of the present invention is to adopt reactive surfactant bring adverse influence can for the water tolerance of pressure sensitive adhesive layer, and this opinion is still not epoch-making, but also extremely important.
Non-reacted tensio-active agent (C) can adopt any kind in ionic or the nonionic, and it can independently separately use, and also can both use together.
The material of nonionic can also be exemplified as: polyoxyethylene glycerol ether fatty acid ester, polyoxyethylene hardened castor oil fatty acid ester, polyoxyethylene trimethylolpropane fatty acid ester, amino acid derivative, polyglycerol fatty acid ester, silicone based tensio-active agent etc. except encircled ethers such as phenyl ether by the polyoxyalkylene alkyl of Voranol EP 2001 representative and polyoxyalkylene more in the non-reacted tensio-active agent (C).
As the ionic substance in the non-reacted tensio-active agent (C), can use by sulfuric ester that forms behind the above-mentioned nonionic surfactant anionization or its esters isoiony tensio-active agent.
The usage quantity of non-reacted tensio-active agent (C) is 100 in the total amount of free-radical polymerised unsaturated monomer (A), is preferably 0.2～1.5 weight part, more preferably 0.5～1 weight part.Under non-reacted tensio-active agent (C) less than 0.2 weight part condition, the dispersion stabilization of monomer latex is relatively poor, and the layer that comprises free-radical polymerised unsaturated monomer (A) and tackifying resin (B) becomes with water layer and is easy to separate.And if the monomer latex of polymerization dispersion stabilization difference, then polymerization also becomes unstable, produces more condensation product.
On the other hand, though tensio-active agent is not fixed on the near surface of latex particle, if but non-reacted tensio-active agent (C) surpasses 1.5 weight parts, then when drying contains the composition latex of resulting acrylic polymers, excessive non-reacted tensio-active agent (C) will hinder the fusion between the latex particle, in stage before making in its immersion water, the transparency of pressure sensitive adhesive layer will reduce, and water tolerance is also tended to reduce in addition.
In preparation process,, the part of employed tensio-active agent can be added to the polymerization container in advance in order to control the latex particle particle diameter of the polymer emulsion that makes.
In the monomer latex, be benchmark with 100 weight part free radical polymerization monomers (A), comprise the tackifying resin (B) of specified quantitative, the non-reacted tensio-active agent (C) of specified quantitative, and water.Water content does not herein have particular determination, 40～250 weight parts normally, and it is a benchmark with 100 weight parts (A) free radical polymerization monomer.
As containing the monomer combination latex, 50% particle diameter of preferred latex particle is below the 2 μ m, more preferably 0.5～1.7 μ m, more preferably 0.8～1.5 μ m.Can control the latex particle particle diameter of monomer latex by controlling agitation condition etc.
In addition, so-called among the present invention " 50% particle diameter " is meant with the volume to be the median particle diameter of benchmark.
The transparency and water-proof viewpoint before immersing formed pressure-sensitive adhesive layer the water in the stage, the latex particle particle diameter of preferred polymers latex is the smaller the better.But on the other hand, if 50% particle diameter of the latex particle of monomer latex is too small, then the stability of monomer latex is tended to reduce, and polymerization stability also tends to reduce.
Usually, in order to ensure the dispersion stabilization of less latex particle, need the tensio-active agent of more amount.If, increase employed non-reacted tensio-active agent (C) with respect to free radical polymerization monomer (A) and tackifying resin (B), then can improve the stability of the less monomer latex of grain diameter, also can improve the stability of the polymer emulsion of generation.But if the amount of non-reacted tensio-active agent (C) is excessive, then the transparency of formed pressure sensitive adhesive layer reduces.
On the other hand, the monomer latex 50% particle diameter of latex particle surpass under the situation of 2 μ m, its polymerization is formed polymer emulsion, and the pressure sensitive adhesive layer that is made by the aqueous pressure-sensitive adhesive that comprises this polymer emulsion is transparency variation just in the stage before in immersing water.
It is generally acknowledged at the composition (monomer latex) that contains free radical polymerization monomer (A) and tackifying resin (B) in water under the polymeric situation, free radical polymerization monomer (A) is different with the velocity of diffusion of tackifying resin (B) in water, therefore free radical polymerization monomer (A) is preferential forms polymer emulsion separately, and tackifying resin (B) occurs residual easily.
Under the situation of polymerization latex particulate 50% particle diameter above the bigger monomer latex of 2 μ m, this tendency has also strengthened all the more, has formed the state that approaches from the simple mixtures of the latex of the acrylic polymers latex of free radical polymerization monomer (A) and tackifying resin (B).Under these circumstances, because the fusion between two kinds of latex particles is difficult to carry out, therefore formed pressure sensitive adhesive layer transparency variation just in the stage before in immersing water is if immerse in the water then tend to the whiting, opaque that becomes at once.
Polymerization contains the method that the monomer combination latex forms the composition latex contain acrylic polymers and for example can carry out according to following content.
At first, with free radical polymerization monomer (A) and tackifying resin (B) thorough mixing, preferably tackifying resin (B) fully is dissolved in the free radical polymerization monomer (A), then non-reacted tensio-active agent (C) and water is joined in this mixture, mix., adopt decollators such as ultrasonic emulsator or intimate mixing device as required herein, 50% particle diameter that preferably will be able to obtain latex particle is the following monomer latexes of 2 μ m.
Then, the monomer latex of part or all of gained can be added in the dropper, (1) in reactor, adds entry with heating and whipping appts, above-mentioned monomer latex splashed into carry out polymerization in this water, or (2) add entry and above-mentioned partial monosomy latex in the reactor with heating and whipping appts, splash into remaining monomer latex by dropper then, carry out polymerization, or (3) add entry and non-reacted tensio-active agent in the reaction vessel with heating and whipping appts, then above-mentioned monomer latex is splashed in the aqueous solution of this tensio-active agent, carry out polymerization.
Purpose is to obtain to contain the polyreaction of the composition latex of acrylic polymers, is under 40 ℃～90 ℃ in temperature range usually, carries out 2～6 hours.
In as above-mentioned (3) illustrational method, the amount that can sneak into the non-reacted tensio-active agent in the water in the reaction vessel is preferably the amount of the transparency that does not reduce formed pressure sensitive adhesive, when it adds together with the amount that is used to form the non-reacted tensio-active agent of monomer latex, be preferably 0.2～1.5 weight part, it is that 100 weight parts are benchmark with free radical polymerization monomer (A).
Preferably adopt polymerization starter during polymerization.This polymerization starter can use water-soluble arbitrarily or non-water-soluble material, preferably uses water-soluble polymerization initiator.
Usually the material that adopts can be water miscible thermolysis type polymerization starters such as persulphates such as Potassium Persulphate, ammonium persulphate, or azo cationoid salt or hydroxyl affixture, or redox initiator.Redox initiator can adopt the combination of reductive agents such as superoxide such as tertbutyl peroxide, benzoyl peroxide, isopropyl benzene hydroperoxide and rongalite, sodium metabisulphite, or the combination of Sodium Persulfate, ammonium persulphate and rongalite, Sulfothiorine etc., the combination of hydrogen peroxide and xitix etc.
The usage quantity of polymerization starter is 100 weight parts in (A) free-radical polymerised unsaturated monomer, is preferably 0.02～3 weight part, more preferably 0.1～1 weight part.
As the addition manner of polymerization starter, can be all to add to reaction vessel in advance, begin reaction then; Or in advance a part is wherein added to reaction vessel, then the remainder gradation is added or splashed into; Maybe whole gradation can be added or splash into.Gradation add or situation about splashing under, can use the polymerization starter that is in monomer latex blended state.
In addition, even polymerization starter is water miscible when adding, but when polymerization, because initiator itself is introduced in the polymkeric substance, so that it has been lost is water-soluble.Therefore, polymerization starter of the present invention is excluded outside " water soluble ingredient that contains in the pressure sensitive adhesive layer ".
In addition, for molecular weight and the molecular weight distribution of controlling the latex particle that contains the acrylic polymer compositions latex, can adopt following material as chain-transfer agent, this material is the alkyl ester of thio-alcohol, thioglycol class, β-Qiu Jibingsuan class.Using under the situation of chain-transfer agent, be 100 weight parts in free-radical polymerised unsaturated monomer (A), preferably its addition in the scope of 0～0.1 weight part to regulate the molecular weight of the acrylic polymers that is generated.
The polymer emulsion that obtains after the polymerization, volume in whole discrete particles is 100%, the preferred 0.05 μ m shared ratio of small size particle above and less than 0.4 μ m is 60～98 volume %, 0.4 the following shared ratio of large-size particles of the above 5 μ m of μ m is 40～2 volume %, the shared ratio of more preferably above-mentioned small size particle is 75～90 volume %, and the shared ratio of above-mentioned large-size particles is 25～10 volume %.If 0.05 μ m is above and the shared ratio less than 60 volume % of small size particle of less than 0.4 μ m, be that the following shared ratio 40 volume % of large-size particles of the above 5 μ m of corresponding 0.4 μ m want many, the transparency of so formed pressure sensitive adhesive layer is just tended to reduce.On the other hand, if the shared ratio of small size particle surpasses 98 volume %, the particulate filling ratio reduces when then dry, and then the amalgamation between the latex particle and also reduce with the binding property of base material, so the water tolerance of resulting pressure sensitive adhesive layer and binding property are just tended to reduce.
For the latex type aqueous pressure-sensitive adhesive that has comprised the composition latex that contains acrylic polymers by obtaining with upper type, after it is applied to the plastic sheet base material, carry out drying, but preferably in its drying process, or in the ageing process that carries out as required, it is crosslinked that latex particle is carried out between particle mutually.
For this reason, can preferentially adopt the method for for example following (1) and (2).
(1) selects the kind of the functional group in the free-radical polymerised unsaturated monomer (A), after making that free-radical polymerised unsaturated monomer (A) carries out radical polymerization, from the reaction that can in drying process or the ageing process that carries out as required, be cross-linked with each other of the functional group of aforementioned monomer (A).
For example, if adopt a kind of as in (A) free-radical polymerised unsaturated monomer of monomer with acetoacetoxy groups, then in drying process, constitute between the acrylic polymers of latex particle and can carry out self-crosslinking.
(2) make comprise in the latex type aqueous pressure-sensitive adhesive (or polymer emulsion) can with the linking agent (D) of aforementioned functional group reactions from monomer (A).
Linking agent (D) can adopt in drying process and during ageing can with the compound from the functional group reactions of free-radical polymerised unsaturated monomer (A) in the polymer emulsion, wherein this functional group for example is: hydroxyl, carboxyl, epoxy group(ing) etc.
Such linking agent (D) can be enumerated, for example hydrazide compound, semicarbazide derivative, isocyanate ester compound, carbodiimide compounds, aziridine cpd, can form the metal species compound of complexing etc.
The consumption of linking agent (D) is 100 weight parts to be contained in the acrylic polymers in the polymer emulsion and the total amount of tackifying resin (B), is preferably below 10 weight parts, more preferably below 5 weight parts, further below preferred 3 weight parts.
It is generally acknowledged in drying process and ageing process fusion between the latex particle and intergranular crosslinked being at war with.Therefore, consider that then crosslinked part just becomes a kind of obstacle with respect to the fusion between the latex particle if carry out crosslinked between the particle when almost not merging between latex particle.Thereby preferred linking agent (D) can not be excessive.
In addition, even be in water-soluble state in the pressure sensitive adhesive of linking agent (D) before dry, but in dry and ageing process, react owing to linking agent (D) with from the functional group of the free-radical polymerised unsaturated monomer (A) in the polymer emulsion, it loses water-soluble.For this reason, the linking agent among the present invention (D) is excluded outside " water soluble ingredient that pressure sensitive adhesive contains ".
In latex type pressure sensitive adhesive,, can also comprise various additives arbitrarily except the composition latex that comprises acrylic polymers and as required the blended linking agent (D).Concrete adducible example is oil-soluble ingredient such as water soluble ingredient such as wetting agent (anti-repel tensio-active agent etc.), water insoluble defoamer (tensio-active agent of low HLB), neutralizing agent, softening agent, tackifier, tinting material, sanitas, rust-preventive agent and solvent, tinting material, water-resisting agent.
Wetting agent is to reduce the high tensio-active agent of the capillary ability of aqueous pressure-sensitive adhesive, and it is the composition that contains usually when coating aqueous pressure-sensitive adhesive on the stripping film of WATER REPELLENT.
Wetting agent can adopt acetylenediol class tensio-active agent, dioctyl sodium sulphosuccinate, silicone based tensio-active agent etc. usually.
Because aqueous pressure-sensitive adhesive bubbles easily, in order to obtain the pressure sensitive adhesive layer of homogeneous, sneaks into defoamer usually as additive.
Defoamer is the composition that is mixed by mineral compound such as mineral oil, tensio-active agent, hydrophobic silica etc., the most of lower nonionic surfactant of HLB that adopts of tensio-active agent.
In addition, in order to improve the stability of polymer emulsion, preferably adopt the acidic-groups such as carboxyl that had with latex particle in the neutralizing agent.
Neutralizing agent can be exemplified as ammoniacal liquor, sodium hydroxide, amine etc.
In addition, because pressure sensitive adhesive comprises water, so breeding easily such as bacterium is also rotted easily.Therefore, preferably in aqueous pressure-sensitive adhesive, sneak into sanitas.
Waterborne-type preservation can be exemplified as isothiazoline derivative, Zephiran chloride, Solamin, clorox, povidone-iodine, pyridyl thiol derivative, hydrogen peroxide, ethanol etc.
In addition, preferably adopt the intimate mixing device that these various water-soluble additive components are sneaked in the polymer emulsion well.
Among the present invention, the water soluble ingredient amount that is comprised in the resulting by the way pressure sensitive adhesive is necessary for below the 3 weight %.Therefore, for the water soluble ingredient in the above-mentioned various additives, preferentially control its combined amount.
Promptly, it originally is exactly water-soluble substances that water-soluble additive (E) is defined as, when monomer emulsion polymerization and aqueous pressure-sensitive adhesive are dry, the reactivity that does not have latex particle with monomer latex or polymer emulsion etc., and material with non-volatility, water-soluble non-reacted tensio-active agent in water-soluble additive (E) and the polymer emulsion altogether, dry weight at aqueous pressure-sensitive adhesive, be preferably to be controlled in below the 3 weight % among the total amount 100 weight % of non-volatility component, more preferably below the 2.5 weight %.If surpass 3 weight %, then be difficult to obtain to have the pressure sensitive adhesive of excellent water resistance.
In addition, can introduce the structure of polymer emulsion,, therefore be come outside the water-soluble additive (E) so lose activity owing to be used for reactive surfactant, polymerization starter and institute's blended linking agent of letex polymerization.
Pressure sensitive adhesion sheet of the present invention can preferentially adopt so-called transfer printing to obtain, this transfer printing is for to coat stripping film with above-mentioned latex type aqueous pressure-sensitive adhesive, carry out drying and be provided with after the pressure sensitive adhesive layer, plastic sheet-like base material outside pressure-sensitive adhesive layer and the foam is fit together, pressure sensitive adhesive layer is transferred on the flat substrates.After fitting to pressure sensitive adhesive layer and flat substrates together, preferably it is carried out ageing as required.
The method that aqueous pressure-sensitive adhesive is applied to stripping film is not particularly limited, can adopts the known apparatus for coating of prior art such as print roll coating devices such as comma spreader, Scraper applicator, intaglio plate spreader, seam die head spreader, labial lamina spreader, curtain formula spreader.
Drying was in most cases carried out under 50～120 ℃ 30 seconds～5 minutes usually, especially carried out tens of seconds about 100 ℃, but was not limited thereto, so long as the condition that the volatile constituent in the formed layer is fully removed can be got final product.
The dry thickness of formed pressure sensitive adhesive layer is preferably 5～70 μ m, more preferably 10～60 μ m.
In pressure sensitive adhesion sheet of the present invention, importantly form the abundant fusion between the latex particle of pressure sensitive adhesive layer.Specifically, importantly to make from the latex particle of the composition latex that contains acrylic polymers and merge, the lightness L of the pressure sensitive adhesion sheet after in the promptly above-mentioned immersion water to following degree *Be below 40.
The drying of latex type aqueous pressure-sensitive adhesive is for example being carried out tens of seconds about 100 ℃, if the inadequate words of the fusion with this understanding between the latex particle are preferably carried out ageing again with dried pressure sensitive adhesion sheet (according to a kind of precursor of pressure sensitive adhesion sheet of the present invention).Make by ageing and to merge between the latex particle that the shape of granular polymeric latex particle is through breaking the formation homogeneous phase, therefore can obtain to immerse lightness L behind the water *It is the pressure sensitive adhesion sheet of the present invention below 40.
For example, this ageing can carried out under 5～70 ℃ about 1～30 day, more particularly for example preferred 25 ℃ following 7 days, or 40 ℃ following about 3 days.
The pressure sensitive adhesion sheet that is obtained is owing to have the good transparency and water tolerance, so can be used for goods commonly used such as laminated film, label, tape, window film, opticses such as wrapping material and Polarizer etc. require the purposes widely of enhanced water resistance and bounding force.
This pressure sensitive adhesion sheet comprises plastic sheet base material and pressure sensitive adhesive layer, can also comprise stripping film or other sheet or layer arbitrarily.
Embodiment
Below, specific embodiments of the invention are described with comparative example, but the present invention is not subjected to the qualification of following embodiment.In addition, in following embodiment and the comparative example, " part " and " % " represents " weight part " and " weight % " respectively.In addition, the repeat number of the oxyethane in the polyoxyethylene structure is counted " EO number ".
Embodiment 1
Will be as 50.5 parts of the 2-EHAs of free radical polymerization monomer, 40.3 parts of butyl acrylates, 5 parts of ethyl propenoates, 3 parts of methyl methacrylates, 1 part in vinylformic acid, 0.2 part of acetoacetoxy groups ethyl-methyl acrylate, with as tackifying resin rosin resinoid " ス one パ one エ ス テ Le A-125 " (waste river chemistry (strain) production) 10 parts, " YSL rosin PX1250 " (ヤ ス Ha ラ ケ ミ カ Le (strain) production) as terpenoid resin mixes for 5 parts, tackifying resin is dissolved in the free radical polymerization monomer, obtains the mixture of the two.
(carbonatoms of alkyl is 12 with water-soluble non-reacted surfactant polyoxyethylene sulfated alkyl ether, the EO number is 18) 1 part and deionized water add in this mixture for 50 parts, adopt the intimate mixing machine to stir then, obtain 50% particle diameter and be 5 μ m following contain the monomer composition latex.As forming the polymkeric substance that obtains, be-57.1 ℃ by the second-order transition temperature of trying to achieve in theory by above-mentioned free radical polymerization monomer.
Contain the monomer combination latex dropping liquid container of packing into what obtain.
With the carbonatoms of 49 parts of deionized waters and 0.1 part of alkyl be 12, the EO number be 18 polyoxyethylene alkyl ether sulfate salt add to be equipped with heating unit, agitator, reflux cooling device, thermometer, nitrogen ingress pipe and dropping liquid container polymerization with in the container, under nitrogen atmosphere, stir then, temperature is 78 ℃ in being warming up to, and the Potassium Persulphate that adds 0.105 part 5% again is as solid state component.After 5 minutes, contain the monomer combination latex and 5% ammonium persulfate aqueous solution (counting 0.315 part with solid substance) dripped 4 hours respectively from the dropping liquid container, carry out polymerization above-mentioned.
Splash into finish after, kept 30 minutes at 80 ℃, then interior temperature is set at 60～65 ℃ through 30 minutes, with 0.1 part of tertbutyl peroxide and 0.12 part of rongalite every 3 addings of 10 minutes branches.Further stir, make reaction carry out 1 hour after, adopt ammoniacal liquor to neutralize, adopt 175 purpose nylon filter cloths to filter, obtain to comprise the acrylic composition latex of acrylic polymers and tackifying resin.The non-volatility composition of this latex is 50.1%, and viscosity is 120mPas.
, adopt BL type viscometer herein, under the condition of 25 ℃ of #4 rotor/60rpm, measure viscosity (following all identical).The non-volatility composition can be by in electric furnace, and the weight ratio of the weight before the weight/drying of 150 ℃ of following dryings after 20 minutes is tried to achieve.
The maximum value that the polymer emulsion that is obtained has separately is that particle diameter is 0.190 μ m and 3.276 μ m, has small particle size composition (peak value) and big particle diameter composition (peak value), and 50% particle diameter is 0.188 μ m.Having the latex particle that is comprised in the small particle size composition (peak value) of maximum value at particle diameter 0.190 μ m place is that particle diameter is the small size particle below the 0.4 μ m more than the 0.05 μ m, its ratio that contains is 85 volume %, wherein with the cumulative volume of the latex particle of resulting polymer emulsion as 100 volume %.The remaining particle that accounts for 15 volume % is that have the particle diameter that contains in the big particle diameter composition (peak value) of maximum value at 3.276 μ m places be the large-size particles below the 5 μ m more than the 0.4 μ m.
Adopt day " the マ イ Network ロ ト ラ Star Network " of machine dress (strain) manufacturing to measure the particle diameter of monomer latex and polymeric latex particle herein.
0.1 part of defoamer (50% is water soluble ingredient), 0.1 portion of the water soluble ingredient dioctyl sodium sulphosuccinate as wetting agent, 0.3 portion of sanitas (5% is water soluble ingredient) are added in the above-mentioned 100 parts polymer emulsion, add 1 part of tackifier (30% is water soluble ingredient) again, adopt the intimate mixing machine to carry out thorough mixing then, obtaining viscosity is the latex type aqueous pressure-sensitive adhesive of 5000mPas.
Adopt scraper that the latex type aqueous pressure-sensitive adhesive that obtains is coated the surface on the stripping film of lift-off processing, then 100 ℃ dry 75 seconds down, obtaining desciccator diaphragm thickness is the pressure-sensitive adhesive layer of 20 μ m.Then, be that the PET of 50 μ m is film adhered on pressure sensitive adhesive layer with thickness, 40 ℃ of following ageings three days, obtain pressure sensitive adhesive layer.The amount of contained water soluble ingredient is 1.86% in the pressure sensitive adhesive layer.
＜water tolerance (anti-whiting) is estimated 〉
Before immersing in the water: peel off the stripping film of pressure sensitive adhesion sheet, adopt multiple light courcess spectral photometric colour measuring meter (ス が Try Omen Machine (strain) manufacturing), measure the L of pressure sensitive adhesion sheet according to reflection method *
After immersing in the water: peel off the stripping film of pressure sensitive adhesion sheet, in the water with 25 ℃ of its immersions, place after 24 hours and take out, adopt multiple light courcess spectral photometric colour measuring meter (ス が Try Omen Machine (strain) manufacturing) at once, measure the L of pressure sensitive adhesion sheet according to reflection method *
The mensuration of＜bounding force 〉
Pressure sensitive adhesion sheet is cut into the wide short strip shape of 25mm that is, peel off stripping film then, be attached on the polyethylene board, adopt the roller of 2kg to make a round trip, obtain test sample.The test sample that obtains placed 24 hours in 23 ℃ atmosphere after, in 23 ℃ atmosphere,, peel off, measure the bond strength of this moment along 180 ℃ direction with the speed that 300mm/ divides.
Embodiment 2
Remove the aging condition among the embodiment 1 is changed into outside 25 ℃/7 days, carry out the experiment identical with embodiment 1.
Embodiment 3
Except 50% particle diameter that makes the monomer latex is 1.2 μ m, carry out the polymerization identical with embodiment 1, obtain polymer emulsion.Resulting polymer emulsion has maximum value respectively at particle diameter 0.203 μ m and 1.244 μ m places, and it has small particle size composition (peak value) and big particle diameter composition (peak value), and 50% particle diameter is 0.182 μ m.
Having the latex particle that is comprised in the small particle size composition (peak value) of maximum value at particle diameter 0.203 μ m place is that particle diameter is the small size particle below the 0.4 μ m more than the 0.05 μ m, it contains proportional is 88 volume %, wherein with the cumulative volume of the latex particle of resulting polymer emulsion as 100 volume %.The remaining particle that accounts for 12 volume % is to have at particle diameter 1.244 μ m places that contained particle diameter is the large-size particles below the 5 μ m more than the 0.4 μ m in the big particle diameter composition (peak value) of maximum value.
Adopt resulting polymer emulsion, carry out the experiment identical with embodiment 1.
Embodiment 4
Except tackifying resin being changed into 5 parts of rosin based resins " ス one パ one エ ス テ Le A-125 " (waste river chemistry (strain) production), 10 parts of terpenoid resins " YSL rosin PX1250 " (ヤ ス Ha ラ ケ ミ カ Le (strain) production), by the mode identical with embodiment 1, obtaining 50% particle diameter is the monomer latex of 1.2 μ m, carry out polymerization equally, filter, obtaining the non-volatility composition is 50.3%, and viscosity is the polymer emulsion of 120mPas.After this, carry out the experiment identical with embodiment 1.
Comparative example 1
In embodiment 1, except not carrying out the ageing, carry out the experiment identical with embodiment 1.
Comparative example 2
0.1 part of defoamer (50% is water soluble ingredient), 1 portion of the water soluble ingredient dioctyl sodium sulphosuccinate as wetting agent, 0.3 portion of sanitas (5% is water soluble ingredient) are added in 100 parts the polymer emulsion that obtains by embodiment 1, add 1 part of tackifier (30% is water soluble ingredient) again, obtain latex type aqueous pressure-sensitive adhesive.
After this carry out the experiment identical with embodiment 1.
Comparative example 3
Will be as 1 part in 3 parts of 5 parts of 40.3 parts of 50.5 parts of 2-EHAs, butyl acrylates, ethyl propenoates, methyl methacrylates, vinylformic acid, 0.2 part of the acetoacetoxy groups ethyl-methyl acrylate of free radical polymerization monomer, with as tackifying resin rosin resinoid " ス one パ one エ ス テ Le A-125 " (waste river chemistry (strain) production) 10 parts, mix for 5 parts as " YSL rosin PX1250 " (ヤ ス Ha ラ ケ ミ カ Le (strain) production) of terpenoid resin, dissolving and obtain the two mixture.To add in this mixture for 50 parts as 1 part of the ammonium salt and the deionized water of polyoxyethylene-1-(allyloxy methyl) alkyl ether sulphate of reactive surfactant, adopt the intimate mixing machine to stir then, obtaining to contain 50% particle diameter is the following monomer latexes of 5 μ m.
With the monomer latex that the obtains dropping liquid container of packing into.
With the carbonatoms of 49 parts of deionized waters and 0.1 part of alkyl be 12, the EO number be 18 polyoxyethylene alkyl ether sulfate salt add to be equipped with heating unit, agitator, reflux cooling device, thermometer, nitrogen ingress pipe and dropping liquid container polymerization with in the container, under nitrogen atmosphere, stir then, temperature is 78 ℃ in being warming up to, and adds to count 0.105 part 5% ammonium persulphate with solid substance again.After 5 minutes, the ammonium persulfate aqueous solution (counting 0.315 part with solid substance) of above-mentioned latex and 5% was dripped from the dropping liquid container 4 hours respectively, carry out polymerization.Splash into finish after, kept 30 minutes at 80 ℃, then interior temperature is set at 60～65 ℃ through 30 minutes, with 0.1 part of tertbutyl peroxide and 0.12 part of rongalite every 3 addings of 10 minutes branches.Stir again, make reaction carry out 1 hour after, adopt ammoniacal liquor to neutralize, adopt 175 purpose nylon filter cloths to filter, obtain to comprise the latex of acrylic polymers, wherein the second-order transition temperature of acrylic polymers (calculated value) is-57.1 ℃.The non-volatility composition of this polymer emulsion is 50.1%, and viscosity is 120mPas.
1 part of tackifier (30% is water soluble ingredient) are added in 100 parts of polymer emulsiones that obtained, and are 5000mPas with its tackify, obtain latex type pressure sensitive adhesive.Adopt intimate mixing mechanism to be equipped with this pressure sensitive adhesive.
Carry out the experiment identical afterwards with embodiment 1.Contained water soluble ingredient is 0.6% in the pressure sensitive adhesive layer.
Comparative example 4
Except tackifying resin being changed into 3.3 parts of rosin based resins " ス one パ one エ ス テ Le A-125 " (waste river chemistry (strain) production), 1.7 parts of terpenoid resins " YSL rosin PX1250 " (ヤ ス Ha ラ ケ ミ カ Le (strain) production), (carbonatoms is 12 to the water-soluble non-reacted surfactant polyoxyethylene sulfated alkyl ether that embodiment 1 is adopted, the EO number is 18) change into outside 1.5 parts, carry out the experiment identical with embodiment 1.
Comparative example 5
(carbonatoms is 12 except non-reacted surfactant polyoxyethylene sulfated alkyl ether that comparative example 4 is adopted, the EO number is 18) replace with outside the ammonium salt of reactive surfactant polyoxyethylene-1-(allyloxy methyl) alkyl ether sulphate, carry out the experiment identical with comparative example 4.
Comparative example 6
Except tackifying resin being changed into 25 parts of rosin based resins " ス one パ one エ ス テ Le A-125 " (waste river chemistry (strain) production), 15 parts of terpenoid resins " YSL rosin PX1250 " (ヤ ス Ha ラ ケ ミ カ Le (strain) production), carry out the experiment identical with embodiment 1.
Comparative example 7
Except being changed into, tackifying resin do not use terpenoid resin, and adopt 15 parts of rosin based resins " ス one パ one エ ス テ Le A-125 " (waste river chemistry (strain) production), (carbonatoms is 12 to adopt the water-soluble non-reacted surfactant polyoxyethylene sulfated alkyl ether that the ammonium salt of 2.5 parts of polyoxyethylene-1-as reactive surfactant (allyloxy methyl) alkyl ether sulphate replaces embodiment 1 to adopt, the EO number is 18) outside, carry out the experiment identical with embodiment 1.
Comparative example 8
Tackifying resin is not sneaked in the monomer latex, (carbonatoms is 12 to adopt the free radical polymerization monomer mixture identical with embodiment 1 and 1 part of water-soluble non-reacted surfactant polyoxyethylene sulfated alkyl ether, the EO number is 18), obtain containing the monomer composition latex that 50% particle diameter is 1.2 μ m.Below operate in the same manner with embodiment 1, obtaining the non-volatility composition is 50.2%, viscosity is 110mPas, and does not contain the polymer emulsion of tackifying resin.
The particle size distribution of resulting polymer emulsion is, the particle that has maximum value at particle diameter 0.180 μ m place is 100 volume %, and its particle diameter is that 0.05 μ m is above and less than 0.4 μ m.In addition, the particle diameter of polymer emulsion 50% is 0.185 μ m.
Then, be benchmark with the solid ingredient of 100 parts of resulting polymer emulsiones, adding the softening temperature of counting 15 parts latexization with solid substance is 150 ℃, median size is the rosin based tackifying resin of 0.52 μ m, mixes.After the mixing, obtain size distribution by the mode identical with embodiment 1.
After this, be benchmark with the mixture of the latex of 100 parts of polymer emulsiones that do not contain tackifying resin and tackifying resin, carry out the experiment identical with embodiment 1.
Above gained the results are shown in table 1.
Figure C20071009235100271

Claims (5)

1. pressure sensitive adhesion sheet is characterized in that: this pressure sensitive adhesion sheet comprises the plastic sheet base material except that foam and is laminated to the aforementioned substrates pressure sensitive adhesive layer on the one side at least; Aforementioned pressure sensitive adhesive layer is by forming the latex type aqueous pressure-sensitive adhesive of acrylic polymers as main ingredient, and contained water soluble ingredient amount is below the 3 weight % in this pressure-sensitive adhesive layer; Aforesaid latex type aqueous pressure-sensitive adhesive comprises the composition latex that contains acrylic polymers, this latex forms by containing the monomer combination emulsion polymerization, and the described monomer combination latex that contains comprises: can form second-order transition temperature and be (methyl) alkyl acrylate of the polymkeric substance below 0 ℃ as free-radical polymerised unsaturated monomer (A) 100 weight parts of main ingredient, contain tackifying resin (B) 6～30 weight parts, non-reacted tensio-active agent (C) 0.2～1.5 weight part and the water of the above rosin based tackifying resin of 60 weight %; The aforementioned composition latex that contains acrylic polymers, volume in whole discrete particles is 100%, 0.05 the μ m shared ratio of small size particle above and less than 0.4 μ m is 60～98 volume %, the following shared ratio of large-size particles of the above 5 μ m of 0.4 μ m is 40～2 volume %.
2. the described pressure sensitive adhesion sheet of claim 1 wherein, when the thickness of aforesaid pressure-sensitive adhesive layer is 20 μ m, in the time of 25 ℃, immerses it in water after 24 hours, and lightness L* is below 40; For polyethylene board, carry out 180 and spend when peeling off, bounding force is more than the 6N/25mm.
3. claim 1 or 2 described pressure sensitive adhesion sheets contain the linking agent (D) that can react with the functional group in the above-mentioned composition latex that contains acrylic polymers in the wherein above-mentioned latex type aqueous pressure-sensitive adhesive.
4. the preparation method of pressure sensitive adhesion sheet, it comprises latex type aqueous pressure-sensitive adhesive is applied at least one face of the plastic sheet base material except that foam, carry out drying then, thereby will merge from the latex particle of the composition latex that contains acrylic polymers, form the step of pressure sensitive adhesive layer; Above-mentioned latex type aqueous pressure-sensitive adhesive comprises the composition latex that contains acrylic polymers, this latex forms by containing the monomer combination emulsion polymerization, and the described monomer combination latex that contains comprises: can form second-order transition temperature and be (methyl) alkyl acrylate of the polymkeric substance below 0 ℃ as free-radical polymerised unsaturated monomer (A) 100 weight parts of main ingredient, contain tackifying resin (B) 6～30 weight parts, non-reacted tensio-active agent (C) 0.2～1.5 weight part and the water of the above rosin based tackifying resin of 60 weight %; The amount of contained water soluble ingredient is below the 3 weight % in the aforesaid pressure sensitive adhesive layer; The aforementioned composition latex that contains acrylic polymers, volume in whole discrete particles is 100%, 0.05 the μ m shared ratio of small size particle above and less than 0.4 μ m is 60～98 volume %, the following shared ratio of large-size particles of the above 5 μ m of 0.4 μ m is 40～2 volume %.
5. the manufacture method of the described pressure sensitive adhesion sheet of claim 4 wherein, when the thickness of aforesaid pressure-sensitive adhesive layer is 20 μ m, in the time of 25 ℃, immerses it in water after 24 hours, and lightness L* is below 40; For polyethylene board, carry out 180 and spend when peeling off, bounding force is more than the 6N/25mm.
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