CN104870588B - The contact adhesive prepared by degradable monomer and polymer - Google Patents

The contact adhesive prepared by degradable monomer and polymer Download PDF

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CN104870588B
CN104870588B CN201380066683.4A CN201380066683A CN104870588B CN 104870588 B CN104870588 B CN 104870588B CN 201380066683 A CN201380066683 A CN 201380066683A CN 104870588 B CN104870588 B CN 104870588B
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methyl
monomer
weight
formula
contact adhesive
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CN104870588A (en
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K·M·莱万多夫斯基
C·E·利普斯科姆
J·E·贾诺斯基
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3M Innovative Properties Co
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3M Innovative Properties Co
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Abstract

The invention provides, under the conditions of typical use, there is good performance characteristic and the contact adhesive can the most easily degraded and/or remove later.More specifically; described contact adhesive contain copolymerization based on (methyl) acrylic acid elastomeric material; it is prepared by the polymerizable material containing (methyl) acrylate monomer, and described (methyl) acrylate monomer both had (methyl) acryl group and also has the ester bond of the part not being (methyl) acryl group.

Description

The contact adhesive prepared by degradable monomer and polymer
The cross reference of related application
Patent application claims is in the U.S. Provisional Patent Application of December in 2012 submission on the 19th The rights and interests of 61/739136, the disclosure of this temporary patent application is incorporated by reference in its entirety herein.
Technical field
The present invention describes contact adhesive and the goods containing described contact adhesive.
Background technology
Contact adhesive (PSA) adhesive tape is the most omnipresent in family's live and work place.? In one of its simplest structure, pressure sensitive adhesive tape comprises backing layer and is attached to the bonding of described backing layer Oxidant layer.According to pressure sensitive adhesive tape association, it is known that contact adhesive has and includes following character: (1) is strong And lasting adhesion strength；(2) can adhere to the pressure less than finger pressure；(3) have enough be fixed on viscous Ability on attached body；And (4) enough cohesive strength is to make it be cleanly removed from adherend.? Find that the material played one's part to the full as PSA includes being designed and formulated to show required viscoelastic special Property polymer, described viscous-elastic behaviour realizes desired adhesion strength, peel adhesion and shearing keep The balance of power.PSA is characterised by the most tacky under room temperature (such as, 20 DEG C to 25 DEG C) 's.Only viscosity or adhere to the material on surface and do not constitute contact adhesive；Term contact adhesive is contained Lid has the material of extra viscoelastic properties.
The important contact adhesive of one class is those with elastomeric material based on methacrylic acid. Have been described in following patent documentation based on (methyl) acrylic acid elastomeric material: European patent Shen Please 2072594 A1 (Kondou et al.), United States Patent (USP) 5,648,425 (Everaerts et al.), United States Patent (USP) 6,777,079 B2 (Zhou et al.) and U.S. Patent Application Publication 2011/04486 A1 (Ma et al.).
It is ordinarily selected to provide steady under average operating based on (methyl) acrylic acid elastomeric material Fixed contact adhesive.In some applications, for example, it is desirable to contact adhesive is in the highest temperature Keep stable under degree and/or higher damp condition.But, in other applications, it is desirable to pressure-sensitive adhesion Agent can easily remove at the end of its service life.For example, it may be desired to remove bonding after a procedure Agent label or the purpose for recycling separate the part and assembly adhered to.
Summary of the invention
The present invention describes has good performance characteristic and later can be at alkali under the conditions of typical use The contact adhesive easily degraded under the conditions of property and/or remove.More specifically, described pressure-sensitive adhesion Agent contain copolymerization based on (methyl) acrylic acid elastomeric material, it is by containing (methyl) acrylate list Prepared by the polymerizable material of body, described (methyl) acrylate monomer both had (methyl) acryloxy base Group (CH2=CHR3-(CO)-O-) also there is the not ester of a part for (methyl) acryloxy group Key (-O-(CO)-).
At first aspect, it is provided that a kind of contact adhesive, its contain copolymerization based on (methyl) third The elastomeric material of olefin(e) acid.Described comprise polymerizable material based on (methyl) acrylic acid elastomeric material Product, described polymerizable material contains the monomer of (a) first formula (I)
R1-O-(CO)-Y-O-(CO)-C(R3)=CH2
(I)
(b) there is the second comonomer of ethylenic unsaturated group.In formula (I), group R1For alkane Base, aryl or combinations thereof.Group Y is formula C of side chain or straight chainn(R2)2nAlkylidene, its Middle group R2For hydrogen or alkyl and wherein variable n be the integer in the range of 1 to 12.Group R3For hydrogen or methyl.
At second aspect, it is provided that a kind of contact adhesive, its contain copolymerization based on (methyl) third The elastomeric material of olefin(e) acid.Described comprise multiple formula based on (methyl) acrylic acid elastomeric material (XX) first module
Second unit with multiple formulas (XXI).
In formula (XX), group R1For alkyl, aryl or combinations thereof.Group Y is side chain or straight Formula C of chainn(R2)2nAlkylidene, wherein group R2For hydrogen or alkyl and wherein variable n be 1 Integer in the range of 12.The unit of the second formula (XXI) derived from second comonomer, described second Monomer is to have the crosslinkers monomers of at least two ethylenic unsaturated group, have single ethylenic not The non-polar monomer of saturated group or there is the polar monomer of single ethylenic unsaturated group.Group Q Vinyl groups (CH is deducted equal to second comonomer2=CHR3-).At formula (XX) and (XXI) In, group R3For hydrogen or methyl and asterisk (*) represent in copolymerization based on (methyl) acrylic acid bullet Each unit in elastomer material is connected to the position of another unit.
In the 3rd aspect, it is provided that a kind of goods, it comprises pressure sensitive adhesive layer and is positioned adjacent to The substrate of pressure sensitive adhesive layer.Described pressure sensitive adhesive layer contains above in first aspect or second aspect Defined based on (methyl) acrylic acid elastomeric material.
Detailed description of the invention
The present invention describes has good performance characteristic and later can be at alkali under the conditions of typical use The contact adhesive easily degraded under the conditions of property and/or remove.These contact adhesives are particularly well-suited to The substrate that wherein binding agent is adhered to is subsequently recycled utilization or unsticking for answering in another goods With.That is, the contact adhesive of described viscosity can remove from substrate easily.
More particularly, described contact adhesive contain copolymerization based on (methyl) acrylic acid elastomer material Material.As used herein, term " (methyl) acrylic acid " refers to the material using at least one monomer to prepare, Described monomer has (methyl) acryl group, and it is formula CH2=CHR3-(CO)-group, wherein R3For hydrogen or methyl, and group (CO)-refer to carbonyl group.Term (methyl) acryloyl group refers to methyl-prop Enoyl-group, acryl group or the two.Generally, described based on (methyl) acrylic acid for being formed Elastomeric material monomer at least 50 moles of % there is (methyl) acryl group.
Described is copolymer based on (methyl) acrylic acid elastomeric material, and described copolymer comprises and can gather The product of condensation material, described polymerizable material contains the monomer of (a) first formula (I)
R1-O-(CO)-Y-O-(CO)-C(R3)=CH2
(I)
(b) there is the second comonomer of ethylenic unsaturated group.As used herein, term " polymerizable material Material " refer to that having polymerizable groups such as may occur from by the change of the ethylenic unsaturated group of base polyreaction Compound.Being included in contact adhesive is by least two based on (methyl) acrylic acid elastomeric material (methyl) acrylic copolymer prepared by different monomers (that is, having the compound of polymerizable groups).
Group R for the first monomer, in formula (I)1For alkyl, aryl or their group Close.Suitably alkyl group can be straight chain, side chain, ring-type or combinations thereof.Alkyl base Group usually has at most 20 carbon atoms, at most 18 carbon atoms, at most 16 carbon atoms, at most 12 carbon atoms, at most 10 carbon atoms, at most 6 carbon atoms or at most 4 carbon atoms.Example As, linear alkyl groups can have 1 to 20 carbon atom, and branched alkyl group can have 3 to 20 Carbon atom, cyclic alkyl radical can have 3 to 20 carbon atoms or 6 to 20 carbon atoms.Suitably It is former that aromatic yl group usually has 6 to 20 carbon atoms, 6 to 12 carbon atoms or 6 to 10 carbon Son.Aromatic yl group is usually phenyl.
During the combination of aryl and alkyl as referred to herein used, group R1Can be aromatic alkyl group or alkane Aromatic yl group.Term " aralkyl " refers to the univalent perssad by the alkyl group replaced by aromatic yl group (such as, benzyl group).Term " alkaryl " refers to by the aryl replaced by alkyl group Valency group (such as, tolyl group).Except as otherwise noted, otherwise for two kinds of groups, Moieties usually there is 1 to 10 carbon atom, 1 to 6 carbon atom or 1 to 4 carbon atom and Aryl moiety usually have 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms or 6 to 10 carbon atoms.In some groups, aryl moiety is phenyl and alkane Base section has 1 to 10 carbon atom, 1 to 6 carbon atom or 1 to 4 carbon atom.
Group R in formula (I)3For hydrogen or methyl.That is, R is worked as3During for hydrogen, described first monomer is Acrylate, and work as R3During for methyl, described first monomer is methacrylate.Implement in many In example, R3For hydrogen.
Formula-the C that group Y is side chain or straight chain in formula (I)n(R2)2n-alkylidene, wherein group R2For hydrogen or alkyl and wherein variable n be the integer in the range of 1 to 12.In other words, Y It can be the alkylidene with 1 to 12 carbon atom.As used herein, term " alkylidene " refers to alkane Bivalent group.Group Y can be to have at most 10 carbon atoms, at most 8 carbon atoms, at most The alkylidene of 6 carbon atoms or at most 4 carbon atoms.In certain embodiments, Y has 1 to 10 Individual carbon atom, 2 to 10 carbon atoms, 3 to 10 carbon atoms, 1 to 8 carbon atom, 1 to 6 Carbon atom or 1 to 4 carbon atom.Work as R2During for alkyl, this group can be straight or branched also Can have at most 11 carbon atoms, at most 10 carbon atoms, at most 6 carbon atoms or at most 4 carbon Atom.Such as, R2Can be have 1 to 10 carbon atom, 2 to 10 carbon atoms, 3 to 10 Carbon atom, 1 to 6 carbon atom or the alkyl of 1 to 4 carbon atom.
In certain embodiments, group Y has formula CnH2n-, wherein n is as mentioned above 1 to 12 In the range of the variable of integer.This type of monomer has formula (Ia), and it is the subset of formula (I).
R1-O-(CO)-CnH2n-O-(CO)-C(R3)=CH2
(Ia)
In formula (Ia), n can be in the range of 1 to 10, in the range of 1 to 8,1 to 6 In the range of or integer in the range of 1 to 4.Some object lessons of Y include CH2-, wherein N is equal to 1, as in the monomer at formula (Ib), formula (Ib) be formula (I) and (Ia) the two Subset.
R1-O-(CO)-CH2-O-(CO)-C(R3)=CH2
(Ib)
Some of formula (Ib) more specifically examples are alkyl acryl ethoxy-ethanol acid esters such as butyl propyleneglycol acyl-oxygen Base ethyl glycolate (R1For butyl), n-octyl group acryloxy ethyl glycolate (R1For n-octyl group) With 2-ethylhexyl acryloxy ethyl glycolate (R1For 2-ethylhexyl).At these alkyl In acyloxy ethyl glycolate, R3For hydrogen.The monomer of other exemplary formula (Ia) includes wherein R1For second Base, Y are pentylidene (C5H10-) ethyl-6-acryloxy-alkyl caproate.
In other embodiments, the group Y in formula (I) has formula-CnHp(R2a)q-, wherein p is In the integer of at least zero, q is the integer equal at least about 1, and (p+q) sum is equal to 2n.Institute Stating monomer and have formula (Ic), it is the subset of formula (I).
R1-O-(CO)-CnHp(R2a)q-O-(CO)-C(R3)=CH2
(Ic)
Variable n is identical with the definition above for formula (Ia).In formula (Ic), group R2aFor have to Many 11 carbon atoms, at most 10 carbon atoms, at most 6 carbon atoms or at most 4 carbon atoms straight Chain or branched alkyl.Such as, R2aCan be have 1 to 10 carbon atom, 2 to 10 carbon atoms, 3 To 10 carbon atoms, 1 to 6 carbon atom or the alkyl of 1 to 4 carbon atom.Some of Y are concrete Example includes-CHR2a-(p is equal to 1, and q is equal to 1, and n is equal to 1), such as the list at formula (Id) As in body, and-C (R2a)2-(wherein p is equal to zero, and q is equal to 2, and n is equal to 1), as in formula (Ie) as in monomer.
R1-O-(CO)-CHR2a-O-(CO)-C(R3)=CH2
(Id)
R1-O-(CO)-C(R2a)2-O-(CO)-C(R3)=CH2
(Ie)
Formula (1d) and (Ie) are the subset of formula (Ic).Some object lessons of formula (Id) include alkyl Acryloxy lactate such as ethyl propylene acyloxy lactate (R1For ethyl), n-octyl group acryloyl Epoxide lactate (R1For n-octyl group), 2-octyl group acryloxy lactate (R1For 2-octyl group), 2-ethylhexyl acryloxy lactate (R1For 2-ethylhexyl) and 1-hexyl acryloxy breast Acid esters (R1For 1-hexyl).In these alkyl acyloxy lactates, R3For hydrogen, R2aFor first Base.Other object lesson of formula (Id) includes 1-butyl-2-acryloxy alkyl caproate (R1For 1-fourth Base, R2aFor butyl, R3For hydrogen).Some object lessons of the monomer of formula (Ie) include ethyl-2-third Alkene acyloxy-2 Methylpropionic acid ester (R1For ethyl, each R2aFor methyl, R3For hydrogen).Formula (Ic) some object lessons of monomer include wherein R1For 1-butyl ,-CnHp(R2a)q-it is CH2CH(CH3)-1-butyl-3-acryloxy-butyrate.That is, n is equal to 2, and p is equal to 3, q Equal to 1, R2aFor methyl.
The monomer of some concrete the first formulas (I) includes following compound:
CH3CH2CH2CH2-O-(CO)-CH2-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH2CH2CH2CH2-O-(CO)-CH2-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH(CH2CH3)CH2-O-(CO)-CH2-O-(CO)-CH2=CH2、 CH3CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2-O-(CO)-C(CH3)2-O-(CO)-CH2=CH2、 CH3CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH2CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH(CH2CH3)CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH2CH2CH(CH3)-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2-O-(CO)-CH2CH2CH2CH2CH2-O-(CO)-CH2=CH2、 CH3CH2CH2CH2-O-(CO)-CH2CH(CH3)-O-(CO)-CH2=CH2With CH3CH2CH2CH2-O-(CO)-CH(CH2CH2CH2CH3)-O-(CO)-CH2=CH2.Real at some Executing in example, the first monomer of formula (I) includes CH3CH2CH2CH2-O-(CO)-CH2-O-(CO)- CH2=CH2Or CH3CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2。
The monomer of formula (I) can use any suitable method to prepare.Reaction scheme A illustrates one Plant the method preparing described monomer.
Reaction scheme A
The hydroxy ester that can make formula (II) is reacted to form in the presence of alkali such as triethylamine with (methyl) acryloyl chloride The monomer of formula (I).The hydroxy ester of some formulas (II) is commercially available, the most various alkyl glycolates Ester, various lactic acid alkyl ester, ethyl-2-hydroxy-isobutyric acid ester, ethyl-6 hydroxycaproic acid ester, ethyl- 3-hydroxybutyrate ester and methyl-2,2-dimethyl-3-hydroxy propionate.
The hydroxy ester of other formula (II) can be prepared as shown in reaction scheme B, wherein makes formula (IV) The hydroxy acid of alcohol and formula (V) react.The hydroxy acid of exemplary formula (V) includes Pfansteihl and D- Lactic acid, glycolic, 3-hydracrylic acid, 3-hydroxybutyrate, 4 hydroxybutyric acid, 4-hydroxypentanoic acid, 3-hydroxyl Base valeric acid, 5-hydroxypentanoic acid, 3-hydroxycaproic acid, 6 hydroxycaproic acid, 3-hydroxyheptanoic acid, 3-hydroxyl are pungent Acid, 2-hydroxy-iso-butyric acid and 10-hydroxydecanoic acid.
Reaction scheme B
Alternately, reaction scheme C can be used to form the monomer of formula (I).Side at this In method, the alcohol of formula (IV) and the halogenated acid of formula (VI) is made to be reacted to form in the halo of formula (VII) Mesosome.Then described halogenated intermediates is made to be reacted to form formula with (methyl) acrylic acid of formula (VIII) (I) monomer.Example halogenated acid is usually chloroacid or bromo-acid such as monoxone, bromoacetic acid, 2-chlorine Propanoic acid, 2 bromopropionic acid, 3-chloropropionic acid, 4-chloro-butyric acid, 2-bromo-butyric acid, 2-bromocaproic acid and 2-bromine valeric acid.
Reaction scheme C
In a further alternative, reaction scheme D can be used to form the monomer of formula (I).At this In method, make the alcohol of formula (IV) lactone reaction with formula (IX) to form the hydroxy ester of formula (II). Then the hydroxy ester that can make formula (II) is reacted to form the list of formula (I) as in reaction scheme A Body.The lactone of exemplary formula (IX) include β-lactone, beta-butyrolactone, gamma-butyrolacton, Alpha-Methyl-ν- In butyrolactone, ν-valerolactone, ν-caprolactone, ν-caprylolactone, ν-decalactone, ν-undecalactone, e-are own Ester and oxa-ring 12-2-ketone.
Reaction scheme D
Can use any suitable amount the first formula (I) monomer to prepare described copolymerization based on (methyl) Acrylic acid elastomeric material.In certain embodiments, it is used for being formed the polymerizable of described elastomeric material In material, at least 10 weight % are the first monomer of formula (I).Polymerizable material can comprise at least 20 weights The list of first formula (I) of amount %, at least 30 weight %, at least 40 weight % or at least 50 weight % Body.Polymerizable material may comprise up to 99 weight % or the highest (such as, at most 99.5 weight Amount %), at most 98 weight %, at most 95 weight %, at most 90 weight %, at most 80 weight %, At most 70 weight % or described first monomer of at most 60 weight %.In certain embodiments, polymerizable Material comprises 10 to 99.5 weight %, 20 to 99 weight %, 20 to 95 weight %, 20 to 90 weights Amount %, 20 to 80 weight %, 20 to 70 weight %, 30 to 90 weight %, 40 to 90 weight % or Described first monomer of 50 to 90 weight %.Described amount is based on the gross weight of polymerizable material.
Be exposed to by recycle polyester material generally met with alkaline condition time, use polymerizable Prepared by the monomer of the formula (I) in material tends to dropping based on (methyl) acrylic acid elastomeric material Solve.That is, little constantly, in polymeric material when being exposed to the pH aqueous solution 24 more than 7 at 80 DEG C Ester bond from the monomer of formula (I) tends to ester hydrolysis reaction.Exemplary alkaline aqueous solution comprises Alkali (such as, sodium hydroxide, potassium hydroxide or the tetraalkylphosphonium hydroxide of 2 weight % being dissolved in water Ammonium).The monomer of the formula (I) of higher amount will cause existing based on (methyl) acrylic acid elastomeric material More degradeds under the conditions of alkalescence.
It is used for forming polymerizable material based on (methyl) acrylic acid elastomeric material to comprise there is ethylenic The second comonomer of unsaturated group.Ethylenic unsaturated group can be vinyl (that is, CH2=CHR3-base Group) or (methyl) acryl group (that is, CH2=CHR3-(CO)-), but usually from (methyl) propylene Carboxyl groups.Described second comonomer can be to have the non-polar monomer of single ethylenic unsaturated group, tool There is the polar monomer of single ethylenic unsaturated group, there is the friendship of at least two ethylenic unsaturated group Connection agent monomer or their mixture.The amount of second comonomer and second comonomer is ordinarily selected to provide vitrification Transition temperature (Tg) not higher than 10 DEG C based on (methyl) acrylic acid elastomeric material.Such as, described TgUsually not higher than 0 DEG C, not higher than-10 DEG C, not higher than-20 DEG C or not higher than-30 DEG C.Glass transition Temperature can use differential scanning calorimeter to measure as described in EXAMPLEPART.
Some conventional non-polar monomers with single ethylenic unsaturated group include (methyl) propylene Acid esters such as (methyl) alkyl acrylate, (methyl) benzyl acrylate, aryl substituted (methyl) propylene Acid alkyl ester, aryloxy group substituted (methyl) alkyl acrylate, (methyl) acrylic acid alkenyl esters etc..Remove Present in (methyl) acryloxy group outside ester bond, these monomers do not have other ester bond.With formula (I) monomer is different, when being exposed to alkalescence condition such as dissolved in 2 weights in water at a temperature of 80 DEG C When measuring the alkali of %, in 24 hours the most there is not ester hydrolysis reaction in these monomers.The first formula (I) can be used Monomer prepare from the combination of these nonpolar second comonomer any have different ester hydrolysis tendency and There is different degradeds and/or the copolymer of tendency removed from substrate.Namely be based on (methyl) acrylic acid The ester hydrolysis rate of elastomeric material tend to nonpolar (methyl) acrylate as second comonomer Amount increase and reduce.
Suitably usually to have 1 to 32 carbon atom, 1 to 20 carbon former for (methyl) alkyl acrylate Son, 1 to 18 carbon atom, 1 to 12 carbon atom, 1 to 10 carbon atom, 1 to 6 carbon are former Son or 1 to 4 carbon atom.Example (methyl) alkyl acrylate includes but not limited to (methyl) acrylic acid Methyl ester, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (first Base) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) propylene Acid n-pentyl ester, (methyl) isoamyl acrylate (that is, (methyl) isoamyl acrylate), (methyl) propylene Acid 3-pentyl ester, (methyl) acrylic acid 2-methyl-1-butene ester, (methyl) acrylic acid 3-methyl isophthalic acid-butyl ester, (first Base) the most own ester of acrylic acid, (methyl) Isohexyl acrylate., (methyl) acrylic acid 2-methyl-1-pentene ester, (first Base) acrylic acid 3-methyl-1-pentene ester, (methyl) acrylic acid 4-methyl-2-pentyl ester, (methyl) acrylic acid 2-second Base-1-butyl ester, (methyl) acrylic acid 2-methyl isophthalic acid-own ester, (methyl) acrylic acid 3,5,5-trimethyl-1-are own Ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 3,3,5-3-methyl cyclohexanol ester, (methyl) acrylic acid 3-heptyl ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid 2-is pungent Ester, (methyl) acrylic acid 2-own ester of ethyl-1-, (methyl) isobornyl acrylate, (methyl) acrylic acid are just The last of the ten Heavenly stems ester, (methyl) isodecyl acrylate, (methyl) acrylic acid 2-Propylheptyl, the different nonyl of (methyl) acrylic acid Ester, (methyl) acrylic acid dodecyl ester (that is, (methyl) lauryl acrylate), (methyl) propylene Acid n-tridecane base ester, (methyl) acrylic acid isotridecyl ester, stearyl methacrylate, (first Base) acrylic acid 3,7-dimethyl-monooctyl ester, (methyl) acrylic acid 1-stearyl, (methyl) acrylic acid 17- Methyl isophthalic acid-heptadecyl ester and (methyl) acrylic acid 1-myristyl ester.Some exemplary (methyl) propylene Acid branched alkyl ester is (methyl) acrylate of the Guerbet alcohol with 12 to 32 carbon atoms, as Described in the open WO 2011/119363 (Clapper et al.) of PCT Patent Application.
Suitably (methyl) benzyl acrylate usually has containing 6 to 20 carbon atoms or 6 to 12 carbon The aromatic yl group of atom.Suitably aryl replacement (methyl) alkyl acrylate usually has containing 1 to 10 Individual carbon atom or the alkyl group of 1 to 6 carbon atom and containing 6 to 20 carbon atoms or 6 to 12 carbon The aromatic yl group of atom.Suitably aryloxy group replace (methyl) alkyl acrylate usually have containing 1 to 10 carbon atoms or the alkyl group of 1 to 6 carbon atom and containing 6 to 20 carbon atoms or 6 to 12 The aryloxy group of individual carbon atom.As used herein, term " aryl " refers to comprise at least one aromatics The monoradical of carbocyclic ring.Aromatic yl group can comprise other ring structure condensing or being bonded to aromatic carbocyclic. Other ring structure any can be saturated, part is undersaturated or undersaturated.It is as used herein, Term " aryloxy group " refers to the monoradical of formula-OAr, and wherein Ar is aryl base as defined above Group.Aryl replaces (methyl) alkyl acrylate or the example of aryloxy group replacement (methyl) alkyl acrylate Including (methyl) acrylic acid own ester of 2-biphenyl, (methyl) benzyl acrylate and (methyl) acrylic acid 2-phenoxy group Ethyl ester.A kind of example (methyl) benzyl acrylate is (methyl) phenyl acrylate.
If it does, any one in nonpolar (methyl) acrylate can be deposited with any suitable amount ?.Gross weight meter based on polymeric material, this type of monomer can at most 80 weight %, at most 70 weights The amount of amount %, at most 60 weight % or at most 50 weight % exists.Such as, nonpolar (methyl) propylene Acid esters can in the range of 0 to 80 weight %, in the range of 0.5 to 80 weight %, 0 to In the range of 70 weight %, in the range of 1 to 70 weight %, in the scope of 0 to 60 weight % Interior, in the range of 1 to 60 weight %, in 0 to 50 weight %, the scope of 1 to 50 weight % Interior, in the range of 0 to 40 weight %, in the range of 1 to 40 weight %, at 0 to 30 weight Amount % in the range of, in the range of 1 to 30 weight %, in the range of 0 to 20 weight % or Amount in the range of 1 to 20 weight % exists.
Described polymerizable material usually comprises one or more optional polar monomers as second comonomer. Term used herein " polar monomer " refers to have single ethylenic unsaturated group and polar group Monomer.Polar group usually includes oh group, acidic-group, primary amido groups, secondary acylamino- Group, tertiary amido groups, amino group or ether group are (that is, containing at least one formula-R-O-R-'s The group of alkylidene-epoxide-alkylidene group, each of which R is to have the Asia of 1 to 4 carbon atom Alkyl).Polar group can form in salt.Such as, acidic-group can form in anion can There is cation counterbalancing ion.In many examples, cation counterbalancing ion is alkali metal ion (such as, sodium, potassium or lithium ion), alkaline-earth metal ions (such as, calcium, magnesium or strontium ion), Ammonium ion or the ammonium ion replaced by one or more alkyl or aryl groups.In other example, Various acylamino-s or amino group can forms in cation can have anionic counter-ion.At this In a little embodiments, anionic counter-ion usually from halogenide, acetate, formate, sulfate radical, Phosphate radical etc..
The monomer of the first formula (I) can be used to prepare with the combination of these polarity second comonomer any have Different ester hydrolysis is inclined to and has different degradeds and/or remove the copolymer of tendency from substrate.Polarity The interpolation of second comonomer tends to improving water-wet behavior based on (methyl) acrylic acid elastomeric material.Ester water Solve speed to tend to increasing with the raising of water-wet behavior.
The exemplary polar monomer with oh group includes but not limited to (methyl) acrylic acid hydroxy alkyl Ester (such as, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid- 3-hydroxypropyl acrylate and (methyl) acrylic acid-4-hydroxy butyl ester), hydroxyalkyl (methyl) acrylamide (such as, 2-hydroxyl Ethyl (methyl) acrylamide or 3-hydroxypropyl (methyl) acrylamide), (methyl) propylene of ethoxylation Acid hydroxyl ethyl ester is (for example, it is possible to trade name CD570, CD571 and CD572 are from Pennsylvania, United States The list that the Sartomer (Sartomer) of state Exton (Exton, PA, USA) is commercially available Body) and aryloxy group substituted (methyl) acrylic acid hydroxy alkyl ester (such as, (methyl) acrylic acid 2-hydroxyl-2- Phenoxy-propyl).
The exemplary polar monomer with acidic-group can be such as carboxylic acid monomer, phosphonate monomers, sulphur Acid monomers, their salt or combinations thereof.Exemplary acid monomer includes but not limited to (methyl) third Olefin(e) acid, itaconic acid, fumaric acid .beta.-methylacrylic acid, citraconic acid, maleic acid, oleic acid, propenoic acid beta-carboxylic second Ester, 2-(methyl) acrylamido ethyl sulfonic acid, 2-(methyl) acrylamido-2-methyl propane sulfonic acid, ethylene Base sulfonic acid etc..In many examples, polar monomer is (methyl) acrylic acid.
The exemplary polar monomer with primary amido groups includes (methyl) acrylamide.Exemplary The polar monomer with secondary amido groups include but not limited to N-alkyl (methyl) acrylamide such as N- Methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-isopropyl (methyl) acrylamide, N-t-octyl (methyl) acrylamide and N-octyl group (methyl) acrylamide.Exemplary has tertiary acylamino- The polar monomer of group include but not limited to N-caprolactam, NVP, (methyl) acryloyl morpholine and N, N-dialkyl group (methyl) acrylamide such as N, N-dimethyl (methyl) propylene Amide, N, N-diethyl (methyl) acrylamide, N, N-dipropyl (methyl) acrylamide and N, N-bis-fourth Base (methyl) acrylamide.
The polar monomer with amino group includes various (methyl) acrylic acid N, N-dialkyl aminoalkyl Ester and N, N-dialkyl aminoalkyl (methyl) acrylamide.Example includes but not limited to (methyl) acrylic acid N, N-dimethylamino ethyl ester, N, N-dimethyl aminoethyl (methyl) acrylamide, (methyl) acrylic acid N, N-dimethylamino propyl ester, N, N-dimethylaminopropyl (methyl) acrylamide, (methyl) acrylic acid N, N-diethylamino ethyl ester, N, N-diethylamino ethyl (methyl) acrylamide, (methyl) acrylic acid N, N-diethylamino propyl ester and N, N-diethyl amino propyl (methyl) acrylamide.
The exemplary polar monomer with ether group includes but not limited to (methyl) propylene of alkoxylate Acid alkyl ester, such as (methyl) ethoxyethoxy ethyl acrylate, (methyl) acrylic acid 2-methoxy acrylate (methyl) acrylic acid 2-ethoxy ethyl ester；And poly-(alkylene oxide) (methyl) acrylate, such as poly-(epoxy Ethane) (methyl) acrylate and poly-(expoxy propane) (methyl) acrylate.Poly-(alkylene oxide) acrylate The most poly-(aklylene glycol) (methyl) acrylate.These monomers can have any suitable end Base, such as hydroxyl or alkoxyl.Such as, when end group is methoxy group, monomer is referred to alternatively as methoxy Base PEG (methyl) acrylate.
Various polarity monomer can be added to increase contact adhesive to adjacent layer such as backing layer or other class The adhesiveness of the substrate of type, strengthens cohesive strength based on (methyl) acrylic acid elastomeric material, or on State both.Any polar monomer or their salt all can exist with any suitable amount.If it does, Based on being used for being formed the gross weight of described polymerizable material based on (methyl) acrylic acid elastomeric material Meter, polar monomer generally uses with the amount of at most 20 weight %.This amount can be up to 15 weight %, extremely Many 10 weight % or at most 5 weight %.Such as, polar monomer can 0 to 20 weight %, 0.5 to 20 weight %, 1 to 20 weight %, 0 to 15 weight %, 0.5 to 15 weight %, 1 to 15 weight Amount %, 0 to 10 weight %, 0.5 to 10 weight %, 1 to 10 weight %, 0 to 5 weight %, 0.5 Amount to 5 weight % or 1 to 5 weight % exists.
It is used for forming described polymerizable material based on (methyl) acrylic acid elastomeric material can also comprise One or more other vinyl monomer such as vinyl esters (such as, vinylacetate and vinyl propionates Ester)；Polyvinylether；Styrene or the substituted styrene of their derivant such as alkyl are (such as, α-methyl styrene)；Olefinic type monomers (such as, ethylene, propylene or butylene)；Vinyl halides Thing；Or their mixture.Depending on specific structure, these monomers can be polarity or non-pole Property.If it does, these monomers can exist with any suitable amount.In certain embodiments, base In the gross weight meter of polymerizable material, vinyl monomer exists with the amount of at most 5 weight %.Such as, second Alkenyl monomer can at most 4 weight %, at most 3 weight %, at most 2 weight % or at most 1 weight % Amount use.Some polymerisable compounds are with in the range of 0 to 5 weight %, at 0.5 to 5 weight In the range of amount %, in the range of 1 to 5 weight %, in the range of 0 to 3 weight % or 0.5 Amount to 3 weight % contains vinyl monomer.
The crosslinkers monomers with at least two ethylenic unsaturated group can be used as second comonomer. Although in addition to the cross-linking agent being suitable as second comonomer, there is also other type of cross-linking agent, but Be use any kind of cross-linking agent all tend to increase based on (methyl) acrylic acid elastomeric material cohesion Intensity and hot strength.
Suitable crosslinking agents as second comonomer has multiple (methyl) acryl group.Have multiple The cross-linking agent of (methyl) acryloyl group can be two (methyl) acrylate, three (methyl) acrylate, four (methyl) acrylate, five (methyl) acrylate etc..These cross-linking agent can be such as by making (methyl) Acrylic acid reacts with polyhydric alcohol (that is, having the alcohol of at least two hydroxyl) and is formed.Described polyhydric alcohol It is generally of 2,3,4 or 5 hydroxyls.The mixture of cross-linking agent can be used.
In many examples, cross-linking agent comprises two (methyl) acryloyl groups.There are two (first Base) Exemplary cross linking agents of acryloyl group includes diacrylate 1,2-glycol ester, diacrylate 1,3-third Diol ester, diacrylate 1,9-nonanediol ester, diacrylate 1,12-dodecanediol ester, diacrylate 1,4-butanediol ester, diacrylate 1,6-HD ester, butanediol diacrylate, bisphenol-A two propylene Acid esters, diethyleneglycol diacrylate, diacrylate triglycol ester, diacrylate TEG ester, Diacrylate tripropylene glycol ester, polyethyleneglycol diacrylate, polypropyleneglycol diacrylate, polyethylene / polypropylene copolymer diacrylate, polybutadiene two (methyl) acrylate, propenoxylated three (first Base) glycerol acrylate and the ester modified caprolactone of neopentyl glycol hydroxy new pentane acid ester diacrylate.
The exemplary cross-linking agent with three or four (methyl) acryl group includes but not limited to three Hydroxymethyl-propane triacrylate is (for example, it is possible to trade name TMPTA-N is from State of Georgia, US scholar The Qing Te industrial group (Cytec Industries, Inc.) of wheat that (Smyrna, GA, USA) and with business Name of an article SR-351 is public from the Sartomer of Pennsylvania, America Exton (Exton, PA, USA) Department (Sartomer) is commercially available), pentaerythritol triacrylate is (for example, it is possible to trade name SR- 444 is commercially available from Sartomer (Sartomer)), three (2-hydroxyethylisocyanurate) 3 third Olefin(e) acid ester (obtains for example, it is possible to trade name SR-368 is purchased from Sartomer (Sartomer) ), the mixture of pentaerythritol triacrylate and tetramethylol methane tetraacrylate (for example, it is possible to Trade name PETIA (wherein tetraacrylate is of about 1:1 with the ratio of triacrylate) and commodity Name PETA-K (wherein tetraacrylate is of about 3:1 with the ratio of triacrylate) is from cyanogen secret service industry Company (Cytec Industries, Inc.) is commercially available), tetramethylol methane tetraacrylate (such as, may be used Commercially available from Sartomer (Sartomer) with trade name SR-295), two-trimethylolpropane Tetraacrylate (obtains for example, it is possible to trade name SR-355 is purchased from Sartomer (Sartomer) ), and the tetramethylol methane tetraacrylate of ethoxylation is (for example, it is possible to trade name SR-494 is certainly Sartomer (Sartomer) is commercially available).There is the example sexual intercourse of five (methyl) acryloyl groups Connection agent includes but not limited to, five acrylic acid two pentaerythrityl esters (such as can be with trade name SR-399 from sand Duo Ma company (Sartomer) is commercially available).
In certain embodiments, cross-linking agent is the polymeric material comprising at least two (methyl) acryloyl group Material.Such as, cross-linking agent can be that poly-(alkylene oxide) with at least two acryl group (such as, gathers Glycol diacrylate can be commercially available from Sartomer (Sartomer), as SR210, SR252 and SR603) or there is the polyurethane of at least two (methyl) acryl group (such as, From the urethane diacrylate of Sartomer (Sartomer), such as CN9018).Along with crosslinking The molecular weight of agent increases, gained tend to having based on (methyl) acrylic acid elastomeric material higher disconnected Split elongation.Polymeric crosslinker tends to than their non-polymeric homologue with bigger percentage by weight Content uses.
For wherein needing to degrade at the end of its service life and/or remove the application of contact adhesive, Preferably there is the cross-linking agent of ester bond rather than with those of ethylenic unsaturated group.That is, these are handed over The use of connection agent can improve ester hydrolysis rate based on (methyl) acrylic acid elastomeric material.Such friendship Connection agent can have formula (X)
H2C=C (R4)-(CO)-Z-R5-(CO)-O-R6-O-(CO)-R5-Z-(CO)-C(R4)=CH2
(X)
In formula (X), each group R4For hydrogen or methyl.Each group R5For having 1 to 20 carbon Atom (such as, 1 to 20 carbon atom, 1 to 12 carbon atom, 1 to 6 carbon atom or 1 to 4 Individual carbon atom) alkylidene.Group R6For alkylidene, poly-(alkylene oxide), arlydene or their group Close.Suitably alkylidene group have 1 to 20 carbon atom (such as, 1 to 20 carbon atom, 1 To 12 carbon atoms, 1 to 6 carbon atom or 1 to 4 carbon atom).The most poly-(alkylene oxide) base Group has formula (CnH2n-O)x(CnH2n)-, wherein x be 1 to 1000 (such as, 1 to 500,1 to 100,10 to 500 or 10 to 1000) integer in the range of.Suitably arylene group has 6 To 20 carbon atoms, 6 to 12 carbon atoms or 6 to 10 carbon atoms.The usually from sub-benzene of arlydene Base or diphenylene.Each Z is epoxide or NH-.These cross-linking agent are in such as U.S. Patent No. No. 7,754,241 (Webb et al.) and No. 6,521,431 (Kiser et al.) have and further retouches State.One object lesson of the cross-linking agent of formula (X) is double (acryloxy) lactic acid 1,4-butyl esters.
In addition to there are those cross-linking agent of at least two ethylenic unsaturated group, can be used other The cross-linking agent of type.A type of cross-linking agent can have multiple group, and described group can be with second Functional group on the monomer functional group of ethylenic unsaturated group (that is, be not) such as acidic-group is anti- Should.Such as, can use there is the cross-linking agent of the multiple '-aziridinos with carboxyl reaction.Exemplary crosslinking Agent includes Bisamide crosslinker, as being described in United States Patent (USP) 6, in 777,079 (Zhou et al.).These Cross-linking agent is not qualified as second comonomer.
In other cross-linking method, add photocrosslinking agent (such as, UV photocrosslinking agent).Although some Photocrosslinking agent has ethylenic unsaturated group (such as, acryloyl group benzophenone) and can be used as Two monomers, but most of light trigger does not have ethylenic unsaturated group and is not qualified as second Monomer.Not having the photocrosslinking agent of ethylenic unsaturated group usually can after polymerisation, or at least Some polymerizations are added after occurring.Such as, photocrosslinking agent can be at polymerizable material (such as, monovalence list Body) the most partially polymerized interpolation after the slurry-like composition of formation thickness.In polymerization or partially polymerized The suitable photocrosslinking agent added afterwards includes such as polyfunctional benzophenone, triazine, and (such as, 2,4-is double (trichloromethyl)-6-(4-methoxyphenyl)-triazine), 1-Phenylethanone. etc..
If there is and do not consider the specific mechanism of cross-linking agent, can use any with any suitable amount Cross-linking agent.In many examples, in terms of the gross weight of polymerizable material, the amount of cross-linking agent is At most 5 weight portions.In certain embodiments, the amount of cross-linking agent be at most 4 weight %, at most 3 Weight %, at most 2 weight % or at most 1 weight %.The amount of cross-linking agent can be to be greater than 0.01 weight %, more than 0.05 weight % or more than 1 weight %.In certain embodiments, cross-linking agent Amount at 0 to 5 weight %, 0.01 to 5 weight %, 0.05 to 5 weight %, 0 to 3 weight Amount %, 0.01 to 3 weight %, 0.05 to 3 weight %, 0 to 1 weight %, 0.01 to 1 weight %, Or 0.05 to 1 in the range of weight %.
As the alternative plan of interpolation cross-linking agent (including photocrosslinking agent), high energy electricity can be used Magnetic radiation such as gamma-radiation or electron beam irradiation make to cross-link based on (methyl) acrylic acid elastomeric material.
In certain embodiments, at least some of monomer in polymerizable material is material based on plant Rather than material of based on oil.Such as, the first monomer of formula (I) can be according to reaction scheme A and B Hydroxy carboxylic acid based on plant such as glycolic and lactic acid is used to prepare as the compound of formula (V).Breast Acid can be obtained by sweat and glycolic can be from some natural sources (including Caulis Sacchari sinensis and Radix Betae) point From.Alcohol based on plant such as ethanol, the 1-of formula (IV) can be used according to reaction scheme B, C and D Butanol and isobutanol.These alcohol can obtain from sweat.Can by the hydroxy ester of such formula (II) or The halogenated intermediates of formula (VII) and the formula (III) or the list of (VII) that are alternatively material based on plant Body such as (methyl) acrylic acid combinations.Such as, can be by the hydrolysis derived from soybean oil or other triglyceride oil Glycerol be converted into (methyl) acrylic acid.Alternatively, can be by the enzyme of corn starch Solve and produce glucose, to form lactic acid.Then acid by dehydrating lactic can be become (methyl) acrylic acid.Separately In a kind of method, glucose can become the 3-hydracrylic acid as intermediate by biofermentation.This intermediate can Dehydration is to form (methyl) acrylic acid.These methods are also described in U.S. Patent application In 2009/0270003 A1 (Anderson et al.).
Generally speaking, it is used for forming polymerizable material based on (methyl) acrylic acid elastomeric material to lead to Often comprise the monomer of first formula (I) of 20 to 99.5 weight % and the second list of 0.5 to 80 weight % Body, the monomer of the first formula (I) of 20 to 99 weight % and the second comonomer of 1 to 80 weight %, 30 The monomer of the first formula (I) and the second comonomer of 5 to 70 weight %, 40 to 95 weights to 95 weight % The monomer of first formula (I) of amount % and the second comonomer of 5 to 30 weight %.Described second comonomer can be In those of being described above any one and the mixture of different second comonomer can be used.Weight hundred Proportion by subtraction is for the gross weight meter forming polymerizable material based on (methyl) acrylic acid elastomeric material.
In many examples, based on (methyl) acrylic acid elastomeric material by based on polymerizable material The monomer of the first formula (I) of gross weight meter at least 50 weight % and at most 50 weight % second single Body prepares.Some are single by the first of 50 to 99.5 weight % based on (methyl) acrylic acid elastomeric material Body and the second comonomer of 0.5 to 50 weight %, the first monomer of 50 to 99 weight % and 1 to 50 weight The second comonomer of amount %, the first monomer of 60 to 99 weight % and the second comonomer of 1 to 40 weight %, First monomer of 70 to 99 weight % and the second comonomer of 1 to 30 weight %, 80 to 99 weight % First monomer and the second comonomer of 1 to 20 weight %, the first monomer of 85 to 99 weight % and 1 to The second comonomer of 15 weight %, or the first monomer of 90 to 99 weight % and the of 1 to 10 weight % Two monomers are formed.
In some more specifically embodiment, based on (methyl) acrylic acid elastomeric material by polymerizable Prepared by material, described polymerizable material includes the monomer and at most 15 of the formula (I) of at least 50 weight % The second comonomer of weight %, described second comonomer is polar monomer.Such as, polymerizable material can include The monomer of the formula (I) of 50 to 99.5 weight % and the polar monomer of 0.5 to 15 weight %, 50 to 99 The monomer of the formula (I) of weight % and the polar monomer of 1 to 15 weight %, the formula of 60 to 99 weight % (I) monomer and the polar monomer of 1 to 15 weight %, the monomer of the formula (I) of 70 to 99 weight % With the polar monomer of 1 to 15 weight %, the monomer of the formula (I) of 80 to 99 weight % and 1 to 15 weight Amount % polar monomer, or the monomer of the formula (I) of 85 to 99 weight % and the polarity of 1 to 15 weight % Monomer.Other second comonomer such as non-polar monomer, crosslinking can be added in these polymerizable materials any Agent or the two is so that total amount reaches 100 weight %.Such as, polymerizable material can include at least 1 weight Amount %, such as 1 to 40 weight %, 1 to 35 weight %, 1 to 30 weight %, 1 to 20 weight The non-polar monomer of amount % or 1 to 10 weight %.And for example, any one in polymerizable material can be wrapped Include at most 5 weight %, such as 0.01 to 5 weight %, 0.05 to 5 weight % or 1 to 5 weight % The cross-linking agent with at least two ethylenic unsaturated group.Percentage by weight for formed based on The gross weight meter of the polymerizable material of (methyl) acrylic acid elastomeric material.
The initiator that would commonly be used for radical polymerization adds for being formed based on (methyl) acrylic acid bullet In the various monomers of elastomer material.Polymerization initiator can be thermal initiator, light trigger or above-mentioned two Person.Any suitable thermal initiator or the light trigger becoming known for Raolical polymerizable can be used. In terms of the gross weight of polymerizable material, initiator amount in the first polymerizable mixture generally exists In the range of 0.01 to 5 weight %, in the range of 0.01 to 2 weight %, in 0.01 to 1 weight % In the range of or in the range of 0.01 to 0.5 weight %.
As used herein, polymerizable mixture (getting final product polymerization reaction mixture) refers to polymerizable material Plus adding in polymerizable material to prepare other component any of polymerizate.
In certain embodiments, thermal initiator is used.According to concrete polymerization used, thermal initiation Agent can be water solublity or water-insoluble (that is, oil-soluble).Suitably water soluble starter bag Include but be not limited to, persulfate such as potassium peroxydisulfate, Ammonium persulfate., sodium peroxydisulfate and theirs is mixed Compound；Oxidation-reduction initiator such as persulfate and the product of reducing agent, described reducing agent is all Such as metabisulfite (such as, sodium metabisulfite) or disulfate (such as, hydrogen sulfate Sodium)；Or 4,4'-azo double (4-cyanopentanoic acid) and soluble-salt thereof (such as, sodium salt or potassium salt).Close Suitable oil-soluble initiator includes but not limited to, various azo-compounds such as can be with trade name VAZO From commercially available for E I company limited of E.I.Du Pont Company (E.I.DuPont de Nemours Co.) those, It include VAZO 67 (it is 2,2 '-azo double (2-methylbutyronitrile), VAZO 64, (it is 2,2 '- (it is double (the 2,4-dimethyl-penten of 2,2 '-azo for azo double (isopropyl cyanide) and VAZO 52 Nitrile)；And various peroxide such as benzoyl peroxide, cyclohexane peroxide, peroxidating Laurel Acyl and their mixture.
In many examples, light trigger is used.Some exemplary light triggers are benzoin ether (such as benzoin methyl ether or benzoin isopropyl ether) or substituted benzoin ether (such as anisoin first Ether).Other exemplary light trigger is substituted 1-Phenylethanone., such as 2,2-diethoxy acetophenone or 2,2-dimethoxy-2-phenyl acetophenone (can be with trade name IRGACURE 651 from New Jersey The BASF AG (BASF) in Fu Lunhan park (Florham Park, NJ, USA) is commercially available, Or with trade name ESACURE KB-1 from Pennsylvania, America Exton (Exton, PA, USA) Sartomer (Sartomer) is commercially available).Other exemplary light trigger is for taking The α-one alcohol in generation, such as 2-methyl-2-hydroxypropiophenonepreparation, aromatics sulfonic acid chloride (such as 2-naphthalene sulfonyl chloride), And photolytic activity oxime, such as 1-phenyl-1,2-propanedione-2-(O-ethoxy carbonyl) oxime.Other is suitable Light trigger includes, such as 1-hydroxycyclohexylphenylketone (IRGACURE 184), double (2,4,6-tri- Methyl benzoyl) phenyl phosphine oxide (IRGACURE 819), 1-[4-(2-hydroxy ethoxy) phenyl]- 2-hydroxy-2-methyl-1-propane-1-ketone (IRGACURE 2959), 2-benzyl-2-dimethylamino-1- (4-morphlinophenyl) butanone (IRGACURE 369), 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2- Morpholino acrylate-1-ketone (IRGACURE 907) and 2-hydroxy-2-methyl-1-phenyl acrylate-1-ketone (DAROCUR 1173)。
Polymerisable mixture the most optionally comprises chain-transferring agent to control the elastomeric material of gained Molecular weight.The example of available chain-transferring agent includes but not limited to, carbon tetrabromide, alcohol, mercaptan such as mercapto The different monooctyl ester of guanidine-acetic acid and their mixture.If used, the most polymerisable mixture can include In terms of the gross weight of polymerizable material, the chain-transferring agent of at most 0.5 weight.Such as, polymerizable mixture The chain that can comprise 0.01 to 0.5 weight %, 0.05 to 0.5 weight % or 0.05 to 0.2 weight % turns Move agent.
Can include organic molten for forming polymerizable mixture based on (methyl) acrylic acid elastomeric material Agent or can be free of or be substantially free of an organic solvent.As used herein, about the term " base of organic solvent Do not contain in basis " mean the amount of organic solvent in terms of the weight of polymerizable mixture or polymerizable material, Less than 5 weight %, less than 4 weight %, less than 3 weight %, less than 2 weight % or less than 1 weight Amount %.If comprising organic solvent in polymerizable mixture, the most described amount is ordinarily selected to provide desired Viscosity.The suitably example of organic solvent includes but not limited to, methanol, oxolane, ethanol, isopropyl Alcohol, heptane, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, dimethylbenzene and second Glycol alkyl ether.These solvents can be used alone or mixture as them uses.
Can be by multiple conventional radical polymerization method system based on (methyl) acrylic acid elastomeric material Standby, described method include polymerisation in solution, polymerisation in bulk (that is, have on a small quantity or not there is solvent), Dispersin polymerization, emulsion polymerization and suspension polymerization.Ad hoc approach used can be by the most pressure-sensitive The impact of the purposes of adhesive composition.Gained based on (methyl) acrylic acid elastomeric material can be Random or block copolymer.In many embodiments, it is nothing based on (methyl) acrylic acid elastomeric material Rule copolymer.
At second aspect, it is provided that a kind of contact adhesive, its contain copolymerization based on (methyl) third The elastomeric material of olefin(e) acid.Described comprise multiple first formula based on (methyl) acrylic acid elastomeric material (XX) unit
Unit with multiple second formulas (XXI).
In formula (XX), group R1For alkyl, aryl or combinations thereof.Group Y is side chain or straight Formula C of chainn(R2)2nAlkylidene, wherein group R2For hydrogen or alkyl and wherein variable n be 1 Integer in the range of 12.The unit of the second formula (XXI) derived from second comonomer, described second Monomer is to have the crosslinkers monomers of at least two ethylenic unsaturated group, have single ethylenic not The non-polar monomer of saturated group or there is the polar monomer of single ethylenic unsaturated group.Group Q Vinyl groups (CH is deducted equal to second comonomer2=CHR3-).At formula (XX) and (XXI) In, group R3For hydrogen or methyl and asterisk (*) represent in copolymerization based on (methyl) acrylic acid bullet Each unit in elastomer material is connected to the position of another unit.
The unit of the plurality of first formula (XX) is typically derived from the monomer of the first formula (I).Or Person, the unit of the first formula (XX) can be derived from the precursor of the monomer of the first formula (I).That is, the first formula (I) precursor of monomer can be described with second comonomer generation radical polymerization to form copolymerization intermediate Copolymerization intermediate reacts to provide formula R further1-O-(CO)-Y-O-(CO)-pendant group.At some In embodiment, the precursor of the monomer of the first formula (I) is (methyl) acrylic acid.(methyl) acrylic acid can be prepared Copolymer with second comonomer such as (methyl) alkyl acrylate.Then described copolymer and as above institute can be made State as R1The compound of the formula (VII) of-O-(CO)-Y-X is reacted to form the list of the first formula (XX) Unit.The hydroxy-acid group of whole or any required parts in copolymer can be made anti-with the compound of formula (VII) Should.In other embodiments, (methyl) acrylate homopolymer can be formed and only one can be made in this homopolymer The hydroxy-acid group divided reacts with the compound of formula (VII).
The unit of the plurality of second formula (XXI) is derived from second comonomer, and described second comonomer is tool There is the polar monomer of single ethylenic unsaturated group, there is the non-pole of single ethylenic unsaturated group Property monomer or crosslinkers monomers.Any of above monomer can be used as second comonomer.Group Q is Two monomers deduct vinyl groups.When second comonomer is the non-pole with single ethylenic unsaturated group During property (methyl) alkyl acrylate, group Q can have formula (CO)-O-R7, wherein R7For alkyl. When second comonomer is (methyl) acrylic acid, group Q can have formula (CO)-O-OH.
In certain embodiments, itself can be used as pressure-sensitive gluing based on (methyl) acrylic acid elastomeric material Mixture.In other embodiments, can by one or more viscosifier, one or more plasticizers or Their mixture combines with elastomeric material.Usually add viscosifier (that is, viscosifier or thickening tree Fat) and plasticizer (that is, plasticizer) to regulate Tg, regulate storage modulus, and change pressure-sensitive adhesion The cohesiveness of agent.Viscosifier are ordinarily selected to mix based on (methyl) acrylic acid elastomeric material with described Molten.Solid or liquid tackifiers all can add.Solid tackifier be generally of 10,000 grams every mole or Less number-average molecular weight (Mn) and the softening point of greater than about 70 DEG C.Liquid tackifiers is that softening point is The viscous material of about 0 DEG C to about 70 DEG C.
Suitably tackifying resin includes rosin resin, and such as rosin acid and their derivant are (such as, Rosin ester)；Terpene resin such as polyterpene (such as, resin based on australene, based on nopinene Resin, and resin based on limonene) and aromatic modified polyterpene resin (such as, phenol-modified many Terpene resin)；Coumarone-indene resin；And hydrocarbon resin of based on oil, such as hydrocarbon tree based on C5 Fat, hydrocarbon resin based on C9, hydrocarbon resin based on C5/C9 and resin based on bicyclopentadiene.As Fruit adds, then can hydrogenate these tackifying resins to reduce they colors to contact adhesive composition Contribution.If it is required, the combination of various viscosifier can be used.In many examples, viscosifier are Rosin ester or comprise rosin ester.
It is the product of multiple rosin acid and alcohol for the viscosifier of rosin ester.These include but do not limit In, the methyl ester of rosin acid, the triethyleneglycol ester of rosin acid, the glyceride of rosin acid, the season of rosin acid Doutrate.These rosin esters can partly or completely perhydrogenating to improve stability and to reduce them to pressure The color contribution of sensitive adhesive compositions.Rosin resin viscosifier can be such as with trade name PERMALYN, STAYBELITE and FORAL are from tennessee,USA spun gold baud The Eastman Chemical Company (Eastman Chemical Company) of (Kingsport, TN, USA) And with trade name NUROZ and NUTAC from the New Port industrial group (Newport of London Industries) commercially available.Complete all hydrogenated rosin resin can be such as with trade name FORAL AX-E From Eastman Chemical Company, (Eastman Chemical Company) is commercially available.Partially hydrogenated pine Balsam can such as with trade name STAYBELITE-E from Eastman Chemical Company (Eastman Chemical Company) commercially available.
Viscosifier for hydrocarbon resin can be prepared by various raw materials based on oil.These raw materials can be fat Race's hydro carbons (some other monomer, such as anti-form-1s of mainly C5 monomer and existence, 3-pentadiene, suitable Formula-1,3-pentadiene, 2-methyl-2-butene, bicyclopentadiene, cyclopentadiene, and cyclopentenes is mixed Compound), aromatic hydrocarbons (some other monomer, such as vinyl first of mainly C9 monomer and existence Benzene, bicyclopentadiene, indenes, methyl styrene, styrene and the mixture of methyl indenes) or it Mixture.Viscosifier derived from C5 monomer are referred to as hydrocarbon resin based on C5, and derived from C9 The viscosifier of monomer are referred to as hydrocarbon resin based on C9.Some viscosifier are derived from C5 and C9 monomer Mixture, or be hydrocarbon viscosifier based on C5 and the blend of hydrocarbon viscosifier based on C9.These increase Stick is referred to alternatively as hydrocarbon viscosifier based on C5/C9.In these resins, any one can partly or completely perhydro Change color and the heat stability to improve them.
Hydrocarbon resin based on C5 can be with trade name PICCOTAC and EASTOTA from Eastman Chemical Company, with trade name WINGTACK from Pennsylvania, United States Exton (Exton, PA, USA) Cray Valleylad Inc. (Cray Valley), with trade name NEVTAC LX from U.S. guest Neville chemical company (the Neville of Western method Ni Ya state Pittsburgh (Pittsburg, PA, USA) Chemical Company) and with trade name HIKOREZ from Korea S can grand industrial group (Kolon Industries, Inc.) is commercially available.Hydrocarbon resin based on C5 can be with trade name EASTOTACK is commercially available from Eastman Chemical Company (Eastman Chemical), and it has not Same hydrogenation degree.
Hydrocarbon resin based on C9 can with trade name PICCO, KRISTLEX, PLASTOLYN, PICCOTAC and ENDEX from Eastman Chemical Company (Eastman Chemical Company), With trade name NORSOLENE from Pennsylvania, United States Exton (Exton, PA, USA) Cray Valleylad Inc. (Cray Valley), with trade name NOVAREZ, from Belgian Johanna Lüttge, this is public Department (Ruetgers N.V.) and with trade name HIKOTAC from Korea S can grand industrial group (Kolon Industries, Inc.) commercially available.These resins can partly or completely perhydrogenating.Before hydrogenation, based on The hydrocarbon resin of C9 usually has the aromatics of about 40%, as by measured by proton magnetic resonance (PMR).The base of hydrogenation Hydrocarbon resin in C9 can be such as public from Eastman Chemical with trade name REGALITE and REGALREX 50 to 100% (such as, department (Eastman Chemical Company) is commercially available, and it is 50%, 70%, 90% and 100%) hydrogenate.Partially hydrogenated resin is generally of some aromatic rings.
Various hydrocarbon viscosifier based on C5/C9 can be with trade name ARKON from the Huang Chuan company of Germany (Arakawa), with trade name QUINTONE from the Rui Weng company (Zeon of Japan Corporation), with trade name ESCOREZ from the ExxonMobil Chemical of Houston, Texas Company and with trade name NURES and H-REZ from the New Port industrial group (Newport of London Industries) commercially available.
Any described viscosifier can be used with any suitable amount.In certain embodiments, particularly exist Wherein it is desirable to contact adhesive is degraded so that in those embodiments being easily removed, it is often necessary to without thickening Agent or only there is the polymerizable mixture of a small amount of viscosifier.Described viscosifier are degraded and/or are moved can be used to Except non-degradable usual under the conditions of described alkalescence based on (methyl) acrylic acid elastomeric material.At other In embodiment, based on described gross weight meter based on (methyl) acrylic acid elastomeric material, it may be desirable to Comprise at most 60 weight %, at most 50 weight %, at most 40 weight % or the increasing of at most 30 weight % Stick.Such as, based on described gross weight meter based on (methyl) acrylic acid elastomeric material, viscosifier Can 0 to 60 weight %, 1 to 60 weight %, 0 to 50 weight %, 1 to 50 weight %, 0 To 40 weight %, 1 to 40 weight %, 0 to 30 weight %, 1 to 30 weight %, 0 to 20 weight Amount in the range of amount % or 1 to 20 weight % exists.
Some contact adhesive compositions can comprise one or more plasticizers.Plasticizer is ordinarily selected to Can the most described with other component in compositions based on (methyl) acrylic acid elastomeric material and any optionally Viscosifier compatible (that is, miscible).Suitably plasticizer includes but not limited to, various poly-alkylenes Base oxide (such as poly(ethylene oxide) or expoxy propane), adipate ester, formic acid esters, phosphate ester, Benzoate, phthalic acid ester, sulfonamide and naphthenic oil.Can drop in the basic conditions for expectation Solving and/or for the contact adhesive that removes, plasticizer is usually chosen as comprising can be in such a situa-tion The ester of reaction or other group.Plasticizer can arbitrarily required amount use, described amount such as with based on The weight meter of (methyl) acrylic acid elastomeric material, in the range of 0 to 100 weight %, or 1 To 100 weight %.Such as, based on described based on (methyl) acrylic acid elastomeric material Gross weight meter, plasticizer can 0 to 50 weight %, 5 to 50 weight %, 1 to 25 weight %, 5 To 25 weight % or 1 to 10 weight %.
Polymerizable mixture also can comprise other optional components, such as, pigment, bead, polymer Pearl (such as, inflatable pearl or expanded pearl), hydrophobicity or hydrophilic silicon oxides, calcium carbonate, Fiber (such as, glass, polymeric material, ceramic material or their mixture), foaming Agent, fire retardant, oxidant and stabilizer.These optional components can be enough to obtain pressure-sensitive adhesion Any amount of the character needed for the special-purpose of agent is added.
In the certain methods preparing contact adhesive, will comprise for being formed based on (methyl) acrylic acid The polymerizable mixture of monomer of elastomeric material partially polymerized so that viscosity increases to be equivalent to pulpous state The viscosity of material.Usually by the monomer of formula (I) and any monovalence second comonomer and a part of radical polymerization Conjunction initiator mixes.According to the initiator type added, expose the mixture to actinic radiation or heating Under, so that monovalence monomer (that is, having the monomer of single ethylenic unsaturated group) is partially polymerized. Then, the part any nubbin of cross-linking agent or photocrosslinking agent and initiator adding pulpous state is gathered In the material closed.Also can be by optional viscosifier and plasticizer and partially polymerized material mixing.Gained Mixture more easily can be applied to substrate such as carrier (such as, release liner) or another as coating On one layer (such as, backing layer).Then, if there is light trigger, then this coating can be exposed In actinic radiation, or, if there is thermal initiator, then can expose the coat to heat.It is exposed to light Change the further of polymerizable material in radiation or heat will cause coating to react and the shape of pressure sensitive adhesive layer Become.
In yet another aspect, it is provided that a kind of goods, it comprises pressure sensitive adhesive layer and is positioned adjacent to pressure The substrate of sensitive adhesive layer.Described pressure sensitive adhesive layer contains as defined above based on (methyl) acrylic acid Elastomeric material.As used herein, term " neighbouring " refers to that ground floor contacts with the second layer or by one Individual or multiple extra plays separate with the second layer.Such as, contact adhesive can contact substrate or by the middle end Enamelled coating or adhesion promoting layer separate with substrate.Described goods can have single pressure sensitive adhesive layer and maybe can have There is multiple pressure sensitive adhesive layer.These goods any can comprise single substrate maybe can have multiple substrate. Any specific substrate can be that monolayer material maybe can have multi-ply construction.
Contact adhesive is typically adhered to substrate, but adhesion strength can be change.In release liner In the case of substrate, adhere to the lowest.Substrate can be flexible or not deflection, and can be by gathering Laminate material, glass or ceramic material, metal or combinations thereof are formed.Suitably polymer base The end, includes but not limited to that polymeric film is as from polypropylene, polyethylene, polrvinyl chloride, polyester (such as, Polyethylene terephthalate, PEN and various aliphatic polyester), poly-carbonic acid Ester, poly-(methyl) acrylic acid methyl ester. (PMMA), polyurethane, cellulose acetate, cellulose triacetate Those prepared with ethyl cellulose.Foam-back can be used.The example of other substrate includes but does not limits In, metal such as rustless steel, metal or the polymeric material of metal oxide-coated, metal or metal The glass etc. of oxide-coated.When contact adhesive is laminated to substrate, it would be desirable to process The surface of substrate is to improve adhesiveness.This process is typically based on material in contact adhesive composition The character of character and substrate selects, and include priming paint and surface modification (such as, sided corona treatment and Surface abrasion).
Should be used for selecting can applying the substrate of contact adhesive to it according to concrete.Pressure sensitive adhesive layer Can be used in any goods of the most known use such composition, described goods such as label, glue Band, direction board, front cover, marked index, display unit, touch panel, decoration sheet etc..Also may be used Expect the flexible backing material with microreplicated surface.
Contact adhesive can provide with the form of contact adhesive transfering belt, and at least one of which is pressure-sensitive Adhesive phase is arranged in release liner to be applied to permanent substrate later.Contact adhesive group Compound can provide with the form of one side coating adhesive tape or dual coating adhesive tape, and wherein binding agent is arranged on On permanent backing.Backing can (such as, polypropylene, including Biaially oriented polypropylene, poly-by plastics Vinyl chloride, polyvinyl acetate, polyethylene), polyester (such as, polyethylene terephthalate Ester, PEN and various aliphatic polyester), non-woven fabric (such as, paper, cloth, Non-woven scrim), metal forming, foam (such as, polyacrylic, polyethylene, polyurethane, Neoprene) etc. make.Foam is purchased from various supplier, such as 3M Co., Voltek, Sekisui and Other.Foam is formed as on the one or both sides of foam and the sheet material of contact adhesive coextrusion, Or can be by contact adhesive lamination on it.
In certain embodiments, the backing for pressure sensitive adhesive tape is aliphatic polyester.Particularly useful Aliphatic polyester be by material based on plant as polylactic acid is formed.Lactic acid dimerization can be passed through Polylactic acid is prepared in body, the ring-opening polymerisation of lactide.Lactic acid has optical activity, and dimer is deposited Four kinds of different forms: L, L-lactide, D, L-lactide, D, D-lactide and L, L-lactide with The racemic mixture of D, D-lactide.It is used as the copolymer of lactic acid and other comonomer.Show Example comonomer include Acetic acid, hydroxy-, bimol. cyclic ester, beta-propiolactone, tetramethyl glycolide, beta-butyrolactone, gamma-butyrolacton, Pivalolactone, 2-hydroxybutyric acid, alpha-hydroxybutyric dehydrogenase, Alpha-hydroxy valeric acid, Alpha-hydroxy isovaleric acid, α-hydroxyl Base caproic acid, α-ethoxy butanoic acid, Alpha-hydroxy isocaproic acid, HMV, Alpha-hydroxy octanoic acid, Alpha-hydroxy capric acid, Alpha-hydroxy myristic acid and Alpha-hydroxy stearic acid.
For one-faced tapes, contact adhesive it is administered on a surface of back lining materials and will close Suitable release liner is administered on the apparent surface of back lining materials.Release liner is known, and includes The such as material of organosilicon, polyethylene, polyurethanes, polyacrylic etc..With regard to dual coating Adhesive tape for, contact adhesive is administered on a surface of back lining materials, and by second bond Agent is arranged on the apparent surface of back lining materials.Second binding agent can identical with contact adhesive (i.e., Described contact adhesive include use formula (I) the additional second comonomer of monomer formed based on (methyl) third The elastomeric material of olefin(e) acid), can (such as, in different formulations identical base similar to contact adhesive In (methyl) acrylic acid elastomeric material) or can (different types of binding agents different from contact adhesive Or different based on (methyl) acrylic acid elastomeric material).The adhesive tape of dual coating is usually supported on anti- On viscous liner.
Any conventional coating techniques being modified as being suitable to particular substrate can be used to be coated with in substrate pressure-sensitive viscous Mixture layer.Such as, method such as roller coat, flow coat, dip-coating, spin coating, spraying, scraper for coating can be passed through The polymerizable applying to be used for forming pressure sensitive adhesive layer to many kinds of solids substrate with die head coating mixes Thing.These various coating processes allow pressure sensitive adhesive layer to be placed in substrate with variable thickness, thus Allow the goods widely purposes formed.
Any suitable thickness can be used for one or more pressure sensitive adhesive layers.In a lot of embodiments In, each pressure sensitive adhesive layer has no more than 20 mils (500 microns), is not more than 10 mils (250 microns), no more than 5 mils (125 microns), no more than 4 mils (100 microns), It is not more than the thickness of 3 mils (75 microns), no more than 2 mils (50 microns).Contact adhesive The thickness of layer is generally at least 0.5 mil (12.5 microns) or at least 1 mil (25 microns).Example As, the thickness of described pressure sensitive adhesive layer can be in 0.5 mil (2.5 microns) to 20 mils (500 Micron) in the range of, in the range of 0.5 mil (5 microns) to 10 mils (250 microns), 0.5 Mil (12.5 microns) is in the range of 5 mils (125 microns), and 1 mil (25 microns) is to 3 In the range of mil (75 microns), or 1 mil (25 microns) is to the model of 2 mils (50 microns) In enclosing.
When being maintained at a temperature of 80 DEG C, pressure sensitive adhesive layer comprises based on (methyl) acrylic acid Elastomeric material can pH more than 7 aqueous solution in 24 hours occur ester hydrolysis.This ester water Solve the degraded that will cause polymeric material (that is, copolymerization based on (methyl) acrylic acid elastomeric material) And/or polymeric material suprabasil is removed from what it adhered to.Contact adhesive can be adhered to from it Separate in substrate, degraded can occur and/or dissolve or combinations thereof.In certain embodiments, pressure-sensitive Binding agent can separate from substrate as film.In other embodiments, contact adhesive tend to degraded and/or Fully dissolve, so that it is no longer film.
Described composition based on (methyl) acrylic acid elastomeric material may be selected to be the ester water needed for offer Solve easiness.Ester hydrolysis can be by changing the chemical constitution of the monomer of the first formula (I) and by selecting the The type of two monomers and amount change.Branched normally tending in first monomer reduces esterolytic speed Rate.That is, straight chain first monomer with the first branched monomer with same carbon atoms number is often easier to There is ester hydrolysis in ground.Additionally, hydrophobic property based on (methyl) acrylic acid elastomeric material tends to reducing Esterolytic speed.Hydrophobic property can be come by increasing the amount of nonpolar second comonomer in polymerizable material Improve.Tend to increasing water on the contrary, improve water-wet behavior based on (methyl) acrylic acid elastomeric material The speed solved.Hydrophobic property can improve by adding the second comonomer of polarity.Increase pole in copolymer Property the amount of second comonomer or reduce the amount of nonpolar second comonomer in copolymer and tend to increasing ester hydrolysis Speed.Also additionally, use crosslinkers monomers to be often conducive to based on (methyl) as formula (X) The ester hydrolysis of acrylic acid elastomeric material.
Multiple item, described item is provided to be contact adhesive composition or comprise the combination of described contact adhesive The goods of thing.
Embodiment 1 is a kind of contact adhesive, its contain copolymerization based on (methyl) acrylic acid elastomer Material.The described product comprising polymerizable material based on (methyl) acrylic acid elastomeric material, institute State polymerizable material and contain the monomer of (a) first formula (I)
R1-O-(CO)-Y-O-(CO)-C(R3)=CH2
(I)
(b) there is the second comonomer of ethylenic unsaturated group.In formula (I), group R1For alkane Base, aryl or combinations thereof.Group Y is formula C of side chain or straight chainn(R2)2nAlkylidene, its Middle group R2For hydrogen or alkyl and wherein variable n be the integer in the range of 1 to 12.Group R3For hydrogen or methyl.
Embodiment 2 is for according to the contact adhesive described in embodiment 1, wherein said based on (methyl) propylene The elastomeric material of acid has the glass transition temperature (T of not higher than 10 DEG Cg)。
Embodiment 3 is for according to the contact adhesive described in embodiment 1 or 2, wherein said first formula (I) monomer has formula (Ia) or (Ic)
R1-O-(CO)-CnH2n-O-(CO)-C(R3)=CH2
(Ia)
R1-O-(CO)-CnHp(R2a)q-O-(CO)-C(R3)=CH2
(Ic)
In these formulas, R2aFor alkyl, variable p is the integer equal at least about zero, and variable q is for being equal at least about The integer of 1, and (p+q) sum is equal to 2n.
Embodiment 4 is for according to the contact adhesive described in embodiment 1 or 2, wherein said first formula (I) monomer has formula (Ib) (Id) or (Ie)
R1-O-(CO)-CH2-O-(CO)-C(R3)=CH2
(Ib)
R1-O-(CO)-CHR2a-O-(CO)-C(R3)=CH2
(Id)
R1-O-(CO)-C(R2a)2-O-(CO)-C(R3)=CH2
(Ie)
Wherein R2aFor alkyl.
Embodiment 5 for according to the contact adhesive according to any one of embodiment 1 to 4, wherein R3For Hydrogen.
Embodiment 6 is for according to the contact adhesive according to any one of embodiment 1 or 2, wherein said First monomer is CH3CH2CH2CH2-O-(CO)-CH2-O-(CO)-CH2=CH2Or CH3CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2。
Embodiment 7 is for according to the contact adhesive according to any one of embodiment 1 to 6, based on gathering The gross weight meter of condensation material, wherein said polymerizable material comprises the first formula of 20 to 99.5 weight % (I) monomer and the second comonomer of 0.5 to 80 weight %.
Embodiment 8 is for according to the contact adhesive according to any one of embodiment 1 to 7, wherein said Second comonomer is to have the crosslinkers monomers of at least two ethylenic unsaturated group, have single ethylene linkage The non-polar monomer of formula unsaturated group, have the polar monomer of single ethylenic unsaturated group or it Mixture.
Embodiment 9 is for according to the contact adhesive described in embodiment 8, gross weight based on polymerizable material Gauge, wherein said polymerizable material comprises the monomer and at most of first formula (I) of at least 50 weight % The polar monomer of 15 weight %.
Embodiment 10 is for according to the contact adhesive described in embodiment 9, and described contact adhesive also comprises The crosslinkers monomers of at most 5 weight %.
Embodiment 11 for according to the contact adhesive according to any one of embodiment 1 to 10, wherein R1 For having the alkyl of at least 4 carbon atoms.
Embodiment 12 is for according to the contact adhesive according to any one of embodiment 1 to 11, Qi Zhongsuo State contact adhesive and ester hydrolysis occurred in the pH aqueous solution more than 7 at 80 DEG C in 24 hours.
Embodiment 13 is for according to the contact adhesive described in embodiment 1, wherein said first formula (I) Monomer be
CH3CH2CH2CH2-O-(CO)-CH2-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH2CH2CH2CH2-O-(CO)-CH2-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH(CH2CH3)CH2-O-(CO)-CH2-O-(CO)-CH2=CH2、 CH3CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2-O-(CO)-C(CH3)2-O-(CO)-CH2=CH2、 CH3CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH2CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH(CH2CH3)CH2-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2CH2CH2CH2CH2CH(CH3)-O-(CO)-CH(CH3)-O-(CO)-CH2=CH2、 CH3CH2-O-(CO)-CH2CH2CH2CH2CH2-O-(CO)-CH2=CH2、 CH3CH2CH2CH2-O-(CO)-CH2CH(CH3)-O-(CO)-CH2=CH2Or CH3CH2CH2CH2-O-(CO)-CH(CH2CH2CH2CH3)-O-(CO)-CH2=CH2。
Embodiment 14 is a kind of contact adhesive, its contain copolymerization based on (methyl) acrylic acid elastomer Material.The described unit comprising multiple first formula (XX) based on (methyl) acrylic acid elastomeric material
Unit with multiple second formulas (XXI).
In formula (XX), group R1For alkyl, aryl or combinations thereof.Group Y is side chain or straight Formula C of chainn(R2)2nAlkylidene, wherein group R2For hydrogen or alkyl and wherein variable n be 1 Integer in the range of 12.The unit of the second formula (XXI) derived from second comonomer, described second Monomer is to have the crosslinkers monomers of at least two ethylenic unsaturated group, have single ethylenic not The non-polar monomer of saturated group or there is the polar monomer of single ethylenic unsaturated group.Group Q Vinyl groups (CH is deducted equal to second comonomer2=CHR3-).At formula (XX) and (XXI) In, group R3For hydrogen or methyl and asterisk (*) represent in copolymerization based on (methyl) acrylic acid bullet Each unit in elastomer material is connected to the position of another unit.
Embodiment 15 is for according to the contact adhesive described in embodiment 14, wherein said based on (methyl) third The elastomeric material of olefin(e) acid has the glass transition temperature (T of not higher than 10 DEG Cg)。
Embodiment 16 is for according to the contact adhesive described in embodiment 14 or 15, wherein
The group R of the unit of the first formula (XX)1-O-(CO)-Y-O-(CO)-for R1-O-(CO)-CnH2n- O-(CO)-or R1-O-(CO)-CnHp(R2a)q-O-(CO)-, wherein R2aFor alkyl, variable p is for being equal to The integer of at least zero, variable q is the integer equal at least about 1, and (p+q) sum is equal to 2n.
Embodiment 17 is for according to the contact adhesive described in embodiment 14 or 15, wherein
The group R of the unit of the first formula (XX)1-O-(CO)-Y-O-(CO)-for R1-O-(CO)-CH2- O-(CO)-、R1-O-(CO)-CHR2a-O-(CO)-or R1-O-(CO)-C(R2a)2-O-(CO)-, wherein R2aFor alkyl.
Embodiment 18 for according to the contact adhesive according to any one of embodiment 14 to 17, wherein R3 For hydrogen.
Embodiment 19 is for according to the contact adhesive according to any one of embodiment 14 or 15, Qi Zhong The group R of the unit of one formula (XX)1-O-(CO)-Y-O-(CO)-for CH3CH2CH2CH2-O- (CO)-CH2-O-(CO)-or CH3CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-。
Embodiment 20 is for according to the contact adhesive according to any one of embodiment 14 to 19, Qi Zhongsuo State unit and 0.5 to 80 weight of the first formula (XX) that polymerizable material comprises 20 to 99.5 weight % The unit of second formula (XXI) of amount %.
Embodiment 21 is for according to the contact adhesive according to any one of embodiment 14 to 20, Qi Zhongji Group Q deducts vinyl groups equal to polar monomer or deducts vinyl groups equal to non-polar monomer.
Embodiment 22 is for according to the contact adhesive according to any one of embodiment 14 to 21, Qi Zhongsuo State contact adhesive and ester hydrolysis occurred in the pH aqueous solution more than 7 at 80 DEG C in 24 hours.
Embodiment 23 is for according to the contact adhesive according to any one of embodiment 14 to 22, Qi Zhong The group R of the unit of one formula (XX)1-O-(CO)-Y-O-(CO)-be
CH3CH2CH2CH2-O-(CO)-CH2-O-(CO)-、 CH3CH2CH2CH2CH2CH2CH2CH2-O-(CO)-CH2-O-(CO)-、 CH3CH2CH2CH2CH(CH2CH3)CH2-O-(CO)-CH2-O-(CO)-、 CH3CH2-O-(CO)-CH(CH3)-O-(CO)-、 CH3CH2-O-(CO)-C(CH3)2-O-(CO)-、 CH3CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-、 CH3CH2CH2CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-、 CH3CH2CH2CH2CH2CH2CH2CH2-O-(CO)-CH(CH3)-O-(CO)-、 CH3CH2CH2CH2CH(CH2CH3)CH2-O-(CO)-CH(CH3)-O-(CO)-、 CH3CH2CH2CH2CH2CH2CH(CH3)-O-(CO)-CH(CH3)-O-(CO)-、 CH3CH2-O-(CO)-CH2CH2CH2CH2CH2-O-(CO)-、 CH3CH2CH2CH2-O-(CO)-CH2CH(CH3)-O-(CO)-or CH3CH2CH2CH2-O-(CO)-CH(CH2CH2CH2CH3)-O-(CO)-。
Embodiment 24 is a kind of goods, and it comprises pressure sensitive adhesive layer and is positioned adjacent to described pressure-sensitive adhesion The substrate of oxidant layer.Described pressure sensitive adhesive layer is according to any one in those in embodiment 1 to 23.
Embodiment 25 is for according to the goods described in embodiment 24, and wherein said goods are adhesive tape Or transfering belt.
Embodiment 26 is for according to the goods described in embodiment 24 or 25, and wherein said contact adhesive exists PH is more than ester hydrolysis occurred in the aqueous solution of 7 at 80 DEG C in 24 hours.
Example
Material
Following material derive from Milwaukee, WI, USA aldrich company (Aldrich, Milwaukee, WI, USA): butyl glycolate, acryloyl chloride, bromoacetic acid, ethyl lactate, lactic acid 1-butyl ester, 2-chloropropionic acid, 2-bromocaproic acid, ethyl-2-hydroxy-isobutyric acid esters, sodium borohydride, ethyl-6- Hydroxycaproic ester, 1,4-butanediol and 2 bromopropionic acid.
Following material derives from the EDM chemical company (EDM in Pennsylvania, United States Philadelphia Chemicals, Philadelphia, PA, USA): toluene, triethylamine, dichloromethane and dimethyl methyl Amide.
Following material derive from Pennsylvania, United States rad promise VWR company (VWR, Radnor, PA, USA): ethyl acetate and potassium carbonate.
Following material derive from Massachusetts, United States Ward Xi Er AlfaAesar company (Alfa Aesar, Ward Hill, MA, USA): glycolic (70 weight % solution in water), 1-capryl alcohol, first sulphur Acid, 2-Ethylhexyl Alcohol, acrylic acid, 1-hexanol, n-butyl alcohol and TBAH.
Following material derive from Holland Purao AS (Purac, Netherlands): lactic acid 2-ethyl Own ester (can obtain with trade name PURASOLV EHL).
CELITE is that the English lattice porcelain deriving from California, USA san jose filters company (Imerys Filtration, San Jose, CA, USA) the trade name of kieselguhr filtering agent.
IRGACURE 651 is the BASF AG deriving from New Jersey not Lip river Farnham Parker The commodity of the 2,2-dimethoxy-1,2-diphenyl second-1-ketone of (BASF, Florham Park, NJ, USA) Name.This is used as light trigger.
DAROCUR 1173 is the BASF AG deriving from New Jersey not Lip river Farnham Parker The commodity of the 2-hydroxy-2-methyl-1-phenyl-propyl-1-ketone of (BASF, Florham Park, NJ, USA) Name.This is used as light trigger.
HDDA refer to derive from Pennsylvania, United States Exton Sartomer (Sartomer, Exton, PA, USA) 1,6 hexanediol diacrylate.
Isooctyl acrylate monomer (IOA) derives from the 3M company (3M of St.Paul, Minnesota Company, St.Paul, MN, USA).
HOSTAPHAN 3SAB is the Rhizoma Sparganii polyester film public affairs deriving from South Carolina, United States Greer Poly-(the terephthalate of department (Mitsubishi Polyester Film Inc., Greer, SC, USA) Ester) (PET).
T10 and T50 be derive from Virginia, USA Fei Erdaier CP film company (CP Films, Fieldale, VA, USA) the trade name of mould release membrance.
Monomeric acrylic 2-Octyl Nitrite (EHA) is available from the Tao Shiization of Michigan, USA Midland Company (Dow Chemical, Midland, MI, USA) or New Jersey not Lip river Farnham Parker BASF AG (BASF, Florham Park, NJ, USA).
Preparation example 1: 1-butyl propyleneglycol acyloxy ethyl glycolate (BGA)
Stirring glycolic 1-butyl ester (90.00 grams, 0.681 mole), toluene (200mL) and three second The mixture of amine (57.42 grams, 0.567 mole) is also cooled to 0 DEG C under nitrogen atmosphere.Via charging leakage Bucket is added dropwise over acryloyl chloride (51.4 grams, 0.567 mole), within 4 hours, adds.The most under reduced pressure Remove solvent.Add ethyl acetate (300mL) and by CELITE filtering mixt, with saturated Sodium bicarbonate aqueous solution washs.Under reduced pressure remove solvent.Yellow by vacuum distilling purification of crude Oil.Water white oil (1-butyl propyleneglycol acyloxy ethyl glycolate) is collected under 59-65 DEG C and 0.66mmHg (90.16 grams).
Preparation example 2: 1-octyl group acryloxy ethyl glycolate (OGA)
By glycolic (100.00 grams, 0.92 mole, 70 weight % solution in water), 1-capryl alcohol (185.16 grams, 1.42 moles), toluene (250mL) and methanesulfonic acid (0.12 gram, 1.2 mmoles You) mixture be heated to refluxing 3 hours.The water of releasing is collected in water knockout drum.Cooling mixing Thing, then with saturated sodium bicarbonate aqueous solution washing.Vacuum removes solvent, obtains crude oil, and leads to Cross this crude oil of vacuum distilling purification.Water white oil (glycolic 1-is collected under 95-96 DEG C and 0.2mmHg Monooctyl ester) (22.76 grams).
Glycolic 1-monooctyl ester (20.00 grams, 0.11 mole), dichloromethane is cooled down in ice bath (100mL) and the mixture of triethylamine (12.14 grams, 0.12 mole).It is added dropwise over acryloyl chloride (10.86 grams, 0.12 mole), add for 30 minutes.Stir the mixture for 2 hours, then filter. Vacuum concentrated solution, dilutes by ethyl acetate (100mL), and with saturated sodium bicarbonate aqueous solution Washing.Vacuum removes solvent, obtains crude oil, and by this crude oil of vacuum distilling purification.At 102- Water white oil (1-octyl group acryloxy ethyl glycolate) (20.88 is collected under 108 DEG C and 0.20mmHg Gram).
Preparation example 3: 2-ethylhexyl acryloxy ethyl glycolate (EHGA)
By 2-Ethylhexyl Alcohol (156.28 grams, 1.2 moles), (142.90 grams, 1.04 rub bromoacetic acid You), the mixture of toluene (400mL) and methanesulfonic acid (0.40 gram, 4.2 mMs) is heated to back Flow 3 hours.The water of releasing is collected in water knockout drum.Cooling mixture, then with saturated carbonic acid Hydrogen sodium water solution washs.Vacuum removes solvent, obtains crude oil, and this is thick to pass through vacuum distilling purification Oil.Water white oil (bromoacetic acid 2-Octyl Nitrite) (263.55 is collected under 75-80 DEG C and 0.25mmHg Gram).
Under agitation by bromoacetic acid 2-Octyl Nitrite (150.00 grams, 0.60 mole), acrylic acid (54.71 grams, 0.76 mole), potassium carbonate (62.66 grams, 0.45 mole) and dimethylformamide (450mL) mixture is heated to 90 DEG C, keeps two hours.Filtering mixt, uses water (700mL) dilution, and extract by ethyl acetate (500mL).With saturated sodium bicarbonate aqueous solution Washing organic facies is also dried with magnesium sulfate.Vacuum removes solvent, obtains crude oil, and passes through vacuum distilling This crude oil of purification.Water white oil (2-ethylhexyl acryloyl is collected under 95-100 DEG C and 0.30mmHg Ethoxy-ethanol acid esters) (112.84 grams).
Preparation example 4-8: various alkyl acyloxy lactate (ethyl propylene acyloxy lactates (ELA), 1-butyl propyleneglycol acyloxy lactate (BLA), 1-octyl group acryloxy lactate (OLA), 2-octyl group acryloxy lactate (2OLA) and 2-ethylhexyl acryloxy breast Acid esters (EHLA).
Following two alkyl lactate ester is synthesis, and remaining alkyl lactate ester is commercially available: lactic acid 1-monooctyl ester and lactic acid 2-monooctyl ester.
By lactic acid (90% solution in water, aldrich (Aldrich)), alcohol (1-capryl alcohol or Sec-n-octyl alcohol), the mixture of toluene and methanesulfonic acid (MSA) is heated to refluxing 3 hours.By release Water is collected in water knockout drum.Cooling mixture, then with saturated sodium bicarbonate aqueous solution washing.Very Sky removes solvent, obtains crude oil, and by this crude oil of vacuum distilling purification.In two reactant mixtures The amount of each component is shown in Table 1.
Table 1: lactic acid n-octyl and the preparation of lactic acid 2-monooctyl ester
Lactic acid alkyl ester is cooled down (for preparation example 4, ethyl lactate in ice bath；For preparation example 5, Lactic acid 1-butyl ester；For preparation example 6, lactic acid 1-monooctyl ester；For preparation example 7, lactic acid 2-monooctyl ester；Right In preparation example 8, lactic acid 2-Octyl Nitrite), dichloromethane and the mixture of triethylamine (TEA).By It is added dropwise to acryloyl chloride, within 30 minutes, adds.Each mixture is stirred 2 hours, then filters. Vacuum concentrated solution, with diluted ethyl acetate, and with saturated sodium bicarbonate aqueous solution washing.Vacuum Remove solvent, obtain crude oil, and by this crude oil of vacuum distilling purification.Separate all products, in nothing Color oil.Composition collects in table 2.
Table 2: the synthesis condition of preparation example 4-8
Preparation example 9: 1-hexyl acryloxy lactate (HLA)
By 1-hexanol (200.00 grams, 2.0 moles), (206.19 grams, 1.9 rub 2-chloropropionic acid You), the mixture of toluene (500mL) and methanesulfonic acid (0.50 gram, 5.2 mMs) is heated to back Flow 4 hours.The water of releasing is collected in water knockout drum.Cooling mixture, with saturated sodium bicarbonate Solution washing, and be dried with magnesium sulfate.Vacuum removes solvent, obtains crude oil, and is steamed by vacuum Evaporate this crude oil of purification.Water white oil (1-hexyl-2-chloropropionic acid is collected under 63-66 DEG C and 0.30mmHg Ester) (358.29 grams).
Under agitation by 1-hexyl-2-chloropropionate (80.00 grams, 0.60 mole), acrylic acid (37.38 grams, 0.52 mole), potassium carbonate (35.93 grams, 0.26 mole) and dimethylformamide (300mL) mixture is heated to 90 DEG C, keeps 5 hours.Filtering mixt, uses water (300mL) dilution, and extract by ethyl acetate (400mL).With saturated sodium bicarbonate aqueous solution Washing organic facies is also dried with magnesium sulfate.Vacuum removes solvent, obtains crude oil, and passes through vacuum distilling This crude oil of purification.Water white oil (1-hexyl acryloxy breast is collected under 88-89 DEG C and 0.80mmHg Acid esters) (77.71 grams).
Preparation example 10: 1-butyl-2-acryloxy alkyl caproate (BAH)
By n-butyl alcohol (60.17 grams, 0.81 mole), (126.53 grams, 0.65 rubs 2-bromocaproic acid You), the mixture of toluene (200mL) and methanesulfonic acid (0.17 gram, 1.8 mMs) is heated to back Flow 3 hours.The water of releasing is collected in water knockout drum.Cooling mixture, uses ethyl acetate (100mL) dilute and wash with saturated sodium bicarbonate aqueous solution.Vacuum removes solvent, obtains thick Oil, and by this crude oil of vacuum distilling purification.Water white oil is collected under 80-82 DEG C and 2.0mmHg (1-butyl-2-bromocaproic acid ester) (142.02 grams).
Under agitation by 1-butyl-2-bromocaproic acid ester (60.00 grams, 0.24 mole), acrylic acid (21.53 grams, 0.30 mole), potassium carbonate (21.00 grams, 0.15 mole) and dimethylformamide (200mL) mixture is heated to 90 DEG C, keeps 2 hours.Filtering mixt, uses water (500mL) dilution, and extract by ethyl acetate (200mL).With saturated sodium bicarbonate aqueous solution Washing organic facies is also dried with magnesium sulfate.Vacuum removes solvent, obtains crude oil, and passes through vacuum distilling This crude oil of purification.Water white oil (1-butyl-2-acryloxy is collected under 96-98 DEG C and 0.90mmHg Alkyl caproate) (49.44 grams).
Preparation example 11: ethyl-2-acryloxy-2 Methylpropionic acid ester (EAMP)
Ethyl-2-hydroxy-isobutyric acid esters (60.00 grams, 0.45 mole), dichloromethane is cooled down in ice bath (300mL) and the mixture of triethylamine (52.62 grams, 0.52 mole).It is added dropwise over acryloyl chloride (47.07 grams, 0.52 mole), add for 60 minutes.Stir the mixture for 17 hours, then mistake Filter.Vacuum concentrated solution, dilutes by ethyl acetate (200mL), and with saturated sodium bicarbonate water Solution washs.Vacuum removes solvent, obtains crude oil, and by this crude oil of vacuum distilling purification.At 42- Water white oil (32.59 grams) is collected under 45 DEG C and 0.80mmHg.Then at 42-45 DEG C and 0.80mmHg Under product of distillation again, obtain the ethyl-2-acryloxy-2 Methylpropionic acid ester (25.29 in water white oil Gram).
Preparation example 12: 1-butyl-3-acryloxy-butyrate (BAB)
Acetoacetic acid 1-butyl ester (40.00 grams, 0.25 mole) and n-butyl alcohol is cooled down in psychrolusia (200mL) mixture.It is added portionwise into sodium borohydride (4.78 grams, 0.13 mole), within 1 hour, adds Complete.Then described mixture it is stirred at room temperature 17 hours.Filtering mixt is also concentrated in vacuo.Crude oil Dilute by ethyl acetate (200mL), wash with water and saturated sodium bicarbonate aqueous solution, then use Magnesium sulfate is dried.Vacuum removes solvent, obtains crude oil, and by this crude oil of vacuum distilling purification.? Water white oil (1-butyl-3-hydroxybutyrate ester) (20.11 grams) is collected under 65-66 DEG C and 1.0mmHg.
1-butyl-2-hydroxy butyrate (20.11 grams, 0.13 mole), dichloromethane is cooled down in ice bath (100mL) and the mixture of triethylamine (14.17 grams, 0.14 mole).It is added dropwise over acryloyl chloride (12.67 grams, 0.14 mole), add for 60 minutes.Stir the mixture for 1 hour and filter.Vacuum Concentrate solution, dilute by ethyl acetate (250mL), and wash with saturated sodium bicarbonate aqueous solution Wash.Vacuum removes solvent, obtains crude oil, and by this crude oil of vacuum distilling purification.At 80-84 DEG C and Water white oil (1-butyl-3-acryloxy butyrate) (16.18 grams) is collected under 0.50mmHg.
Preparation example 13: ethyl-6-acryloxy-alkyl caproate (EAH)
Ethyl-6 hydroxycaproic acid ester (49.44 grams, 0.31 mole), dichloromethane is cooled down in ice bath (200mL) and the mixture of triethylamine (36.26 grams, 0.36 mole).It is added dropwise over acryloyl chloride (29.87 grams, 0.33 mole), add for 60 minutes.Stir the mixture for 3 hours and filter.Vacuum Concentrate solution and dilute by ethyl acetate (300mL).With saturated sodium bicarbonate aqueous solution and washing Wash mixture, be then dried with magnesium sulfate.Vacuum removes solvent, obtains crude oil, and is steamed by vacuum Evaporate this crude oil of purification.Light yellow oil (ethyl-6-acryloyl-oxy is collected under 90-92 DEG C and 0.70mmHg Base-alkyl caproate) (51.27 grams).Use the ethyl acetate/hexane of 10 volume % by this oil Divide (40 grams) to be further purified on silica gel by column chromatography, obtain the product in water white oil.
Preparation example 14: double (acryloxy) lactic acid 1,4-butyl ester
By BDO (39.65 grams, 0.44 mole), (150.00 grams, 0.98 rubs 2 bromopropionic acid You), the mixture of toluene (400mL) and methanesulfonic acid (0.20 gram, 2.1 mMs) is heated to back Flow 3 hours.The water of releasing is collected in water knockout drum.Cooling mixture, then with saturated carbonic acid Hydrogen sodium water solution washs, and is dried with magnesium sulfate.Vacuum removes solvent, obtains crude oil (160.37 Gram), this crude oil the most i.e. uses.
Under agitation by Isosorbide-5-Nitrae-bis--butyl-2 bromopropionic acid ester (130.31 grams, 0.36 mole), acrylic acid (69.13 grams, 0.96 mole), potassium carbonate (76.54 grams, 0.55 mole) and dimethylformamide (450mL) mixture is heated to 90 DEG C, keeps 2 hours.Filtering mixt, is concentrated in vacuo, Dilute with water (300mL), and extract by ethyl acetate (400mL).With saturated sodium bicarbonate water Solution washing organic facies is also dried with magnesium sulfate.Vacuum removes solvent, obtains crude oil, uses 20-40 weight The gradient of the ethyl acetate/hexane of amount % is by column chromatography this crude oil of purification on silica gel.Separate product, In water white oil (double (acryloxy) lactic acid Isosorbide-5-Nitrae-butyl ester, 27.60 grams).
Preparation example 15: benzyl-2-acryloxy lactate (BzLA)
By benzylalcohol (102.73 grams, 0.95 mole), 2 bromopropionic acid (151.03 grams, 0.99 mole), The mixture of toluene (400mL) and methanesulfonic acid (0.30 gram, 3.1 mMs) is heated to refluxing 3 little Time.The water of releasing is collected in water knockout drum.Cooling mixture with saturated sodium bicarbonate aqueous solution Washing.Vacuum removes solvent, obtains crude oil, and by this crude oil of vacuum distilling purification.At 100- Water white oil (benzyl-2 bromopropionic acid ester) (215.91 grams) is collected under 103 DEG C and 0.3mmHg.
Under agitation by benzyl-2 bromopropionic acid ester (140.25 grams, 0.58 mole), acrylic acid (52.24 Gram, 0.30 mole), potassium carbonate (59.64 grams, 0.43 mole) and dimethylformamide (450mL) mixture is heated to 90 DEG C, keeps 2 hours.Cooling mixture, uses water (300mL) dilution, and extract by ethyl acetate (300mL).With saturated sodium bicarbonate aqueous solution Organic facies is washed with water.It is dried organic facies with magnesium sulfate and is filtered by CELITE.Vacuum removes molten Agent, obtains crude oil, and by this crude oil of vacuum distilling purification.Under 110-112 DEG C and 0.20mmHg Collect water white oil (benzyl-2-acryloxy lactate) (50.13 grams).
Method of testing 1: the means of differential scanning calorimetry (DSC) of polymeric film is analyzed
Will each of about 10 milligrams polymer (homopolymer and based on (methyl) acrylic acid elastomer Material) be placed on one by one individually in standard DSC aluminum dish (thermal model T080715) also It is placed in the automatic sampler of differential scanning calorimeter (TA DSC Q200, thermal-analysis instrumentation). For each sample analysis, dish is individually placed in the differential in the closed cell of DSC On one of post (differential post), empty reference dish is placed on another post.Make temperature- Circulation twice between 85 DEG C and 150 DEG C, 10 DEG C per minute.Glass transition temperature (Tg) be defined as The scanning hot-fluid peak value to the temperature of the second heating cycle.Glass transition is generally by heat flow curve Skew represents.After glass transition, before heat flow curve is parallel to glass transition but be offset to relatively Low heat flow value.Glass transition is recorded at the knee of curve of this skew in heat flow curve Temperature.
Method of testing 2: shear strength is tested
Binder film described in example is cut into the bar of wide 1.27 centimetres and adhered to by its binding agent To smooth rigidity stainless steel sheet so that each binder film bar just length of 2.54 centimetres and its The plate contact adhered to.Roll across from adhesion section with the counterweight of 2 kilograms (4.5 pounds).Allow and have Each sheets thus obtained balance 15 minute under room temperature (23 DEG C) of the film bar adhered to.Then, from adhesion Film bar free end hang 1000 grams of counterweights, and make panel from vertical direction tilt 2 degree with take precautions against times What peeling force.Counterweight falls because binder film bar is discharged from plate by the failure mode being illustrated below Time (minute) is " RT shears (minute) " under 23 DEG C (1000 grams).Without Any inefficacy, 10, interrupt test when 000 minute.In table 4, this is designated as 10,000+ minute. Test three samples of each adhesive tape (binder film bar) and by shear strength test value averagely to obtain To given shear force.
Method of testing 3: peel adhesion is tested
Peel adhesion be specific angle and remove under speed measure remove coating from test panel Power needed for the test sample of binding agent.In instances, this power is with per inch tilted object sample Ounce number is expressed.Employing following procedure:
(1) in the cleaned glass bread board of horizontal positioned, the wide survey of 1.27cm (0.5 inch) is applied Have a try sample.Use the rubber rollers of 2.2 kilograms by test long for 10.16cm (4 inches) Sample is compressed to be in close contact with glass surface.
(2) by the free end inflection of test sample, by adosculation himself, so removing angle be 180°.The free end of test sample is attached to adhesion test machine engraving scale (scale)。
(3) being clipped in by glass test board can be with 30.48 centimetres (12 inches) constant speed per minute In rate makes the tension tester fixture that this plate moves away from graduated disc.
(4) when test sample is peeled off from glass surface, record dial reading (ounce).By institute Obtain peel adhesion and be scaled an ounce per inch (N/dm) from every 0.5 inch of ounce, The final peel adhesion listed in table 4.
Reference example 1-15: homopolymer preparation and sign
Two step light polymerization process are used to prepare homopolymer.In the first step, by 20 grams of monomers and 0.04 gram IRGACURE 651 is placed in bottle.With this solution nitrogen inerting 2 minutes, it is then exposed to From UVP Blak-Ray XX-15BLB UV Bench Lamp (365nm, California A Pu Blue UVP company (UVP, Upland, CA)) UV light until viscosity increases.From through solution Slowing down of nitrogen bubble observe the increase of viscosity qualitatively.By within one minute, terminating light with air bubbling Polymerization is to produce pre-polymer mixture.In second step, it is coated with between T10 and T50 release liner Thickness is the pre-polymer mixture of 0.127 millimeter.Then make all three layer sudden and violent in two-sided solidification process It is exposed to 2.2J/cm2UVA light.
Homopolymer is characterized according to method of testing 1 by differential scanning calorimetry (DSC).
Table 3: the glass transition temperature of the homopolymer of reference example 1-14
Reference example Preparative example Monomer Homopolymer Tg(℃)
1 1 BGA -22.9
2 2 OGA -25.5
3 3 EHGA -33.3
4 4 ELA NM
5 5 BLA -27.8
6 6 OLA -46.1
7 8 EHLA -39.8
8 9 HLA -39.4
9 10 BAH -41.3
10 11 EAMP 17.2
11 12 BAB -32.4
12 13 EAH -62
13 15 BzLA 18.5
14 -- IOA -54.8
15 -- EHA -45.6
NM: unmeasured
Example 1-10 and comparative example 1-2: preparation based on (methyl) acrylic acid elastomeric material
Example 1-7 and comparative example 1 and 2 are prepared by two step light polymerization process.In the first step, will 18 grams of monomers (as marked in table 4), 2 grams of acrylic acid and 0.04 gram of IRGACURE 651 are placed in In bottle.With this solution nitrogen inerting 2 minutes, it is then exposed to from UVP Black-Ray XX- The UV light of 15BLB UV Bench Lamp (365nm) is until viscosity increases.From through mixture The increase of viscosity is observed in slowing down of nitrogen bubble qualitatively.Gather by within one minute, terminating light with air bubbling Close to produce pre-polymer mixture.In second step, in pre-polymer mixture, add 23.8 milliliters (0.12 weight %) cross-linking agent.In example 1-5 and comparative example 1-2, cross-linking agent is 1,6-hexanediol Diacrylate (HDDA).In example 6 and 7, cross-linking agent is BDO diacetyl group two Acrylate (carrys out ester from preparation 14).It is vigorously mixed each gained mixture then by shaking In from Virginia, USA Fei Erdaier CP film company (CP Films, Fieldale, VA, USA) thickness of 0.127 millimeter it is coated with between T10 and T50 release liner to prepare transfer adhesive Band.Then in two-sided solidification process, 2.2J/cm is exposed the membrane to2UVA light.
For example 8, by 6 grams of Isooctyl acrylate monomers, 12 grams of BGA, 2 grams of acrylic acid and 0.04 gram IRGACURE 651 merges in the vial and is polymerized as mentioned above.
For example 9, by 10 grams of IOA, 8 grams of BGA, 2 grams of acrylic acid and 0.04 gram IRGACURE 651 merges in the vial and is polymerized as mentioned above.
For example 10, by 14 grams of IOA, 4 grams of BGA, 2 grams of acrylic acid and 0.04 gram IRGACURE 651 merges in the vial and is polymerized as mentioned above.
Each adhesive phase is shifted and is laminated to 0.0508mm thickness HOSTAPHAN 3SAB and gather The priming paint side of (ethylene glycol terephthalate) film, then characterizes according to method of testing 1-3.As from supply Being received at business, this film is through primary coat.
Table 4: example 1-10 and the sign of comparative example 1-2
Example 11-22 and comparative example 3-4: the degraded of adhesive phase and/or remove
Degraded test is used to simulate the bar that during polyester recycles, contact adhesive will be exposed to Part.At this in test, HOSTAPHAN 3SAB PET is cut into 38.1mm and takes advantage of 127 millimeters Bar, be washed with deionized, and in preweighted aluminum dish at 80 DEG C be dried 2 hours.It is dried After, PET bar and aluminum dish are weighed.Then by the bar of pressure sensitive adhesive layer, (25.4mm takes advantage of 76.2mm's, example 1-10 and comparative example 1-2) it is laminated to treated PEI bar to prepare binding agent Adhesive tape.Table 4 denotes the corresponding adhesive tape of each degraded test sample.By binding agent glue Carry sample is dried 1 hour at 80 DEG C and the most again weighs.After 24 hours, by each 800mL soda lye that adhesive tape sample is placed at 80 DEG C (NaOH/ of 2 weight % go from Sub-water) in.This solution is stirred under 500 rpms.It is immersed in this solution after 8 minutes, takes Go out adhesive tape, be washed with deionized, and be dried 2 hours at 80 DEG C.The most again to sample Product are weighed.If sample still looks like wet, then it is further dried 2 hours at 120 DEG C And again weigh.The weight loss of sample is shown in Table 5.
It addition, example 1-10 and comparative example 1-2 is measured the time that binding agent separates from PET backing. In the case, it is that binding agent is completely separable from PET film by binding agent from the timing definition of backing unsticking Necessary time quantum (minute).Test with such as same way as above, except for the difference that by sample Product are immersed in soda lye until binding agent unsticking.
For example 21, the time of binding agent unsticking determined as outlined above, except for the difference that use 2 weights The KOH/ deionized water solution of amount % replaces the NaOH of 2 weight %.
In example 22, the time of binding agent unsticking determined as outlined above, except for the difference that use 2 weights The TBAH solution of amount % replaces the NaOH of 2 weight %.
Table 5: example 11-20 and the degraded of comparative example 3-4
* after 480 minutes, sample does not separates from backing.
NM: unmeasured
Example 23-35 and comparative example C5-C9: (methyl) acrylic copolymer is in 1.0M sodium hydroxide Degraded
Transparent vial is mixed with the monomer of example 1-13 and acrylic acid (AA) and DAROCUR 1173 prepares example 23-35.Equally, be mixed with the monomer of example 5-7 with DAROCUR 1173 prepares comparative example C5-C7.Mixing IOA with DAROCUR 1173 makes Standby comparative example 8, and mix both IOA Yu AA and DAROCUR 1173 and prepare comparative example 9. Each mixture nitrogen bubble 1 hour, and bottle is closed the lid.Bottle is placed on UVP Under Black-Ray XX-15BLB UV Bench Lamp (365nm) and use 850mJ/cm2Dosage Irradiation is prepared based on (methyl) acrylic acid homopolymer or copolymer.
About each of 100mg sample is placed in the vial and loads 6mL 1.0M in water Sodium hydroxide.Bottle is closed the lid and stays under room temperature (about 32 DEG C) or be placed on the baking oven at 90 DEG C In.Degradation time in table 6 is defined as being completely dissolved (supernatant liquid) or being formed without solid visible Time of biphase liquid liquid mixture.
Table 6:(methyl) degradation results of acrylate copolymer
* degraded test stopped after 240 hours.
Above example illustrates, degradation time can be by using comonomer acrylic acid and by high temperature Aging in alkaline solution shorten.Degradation time also can be controlled by the chemical constitution preparing monomer.
Example 27-29 and comparative example C5-C9: (methyl) acrylic copolymer is at deionized water and 1.0M Degraded in hydrochloric acid.
The same polymer of preparation as described in example above 27-29 and comparative example C5-C9 is used to carry out Following Study on degradation.
About each of 100mg sample is placed in the vial and loads 6mL deionized water or at water In 1.0M hydrochloric acid.Bottle is closed the lid and is placed in the baking oven at 90 DEG C.During degraded in table 7 Between be defined as being completely dissolved (supernatant liquid) or form the biphase liquid liquid mixture without solid visible Time.
Table 7:(methyl) degradation results of acrylate copolymer
* degraded test stopped after 336 hours.
Above example illustrates, compared with 1.0M sodium hydroxide, the degradation time of polymer is at deionization In water or 1.0M hydrochloric acid much longer.

Claims (12)

1. a contact adhesive, described contact adhesive comprise copolymerization based on (methyl) acrylic acid bullet Elastomer material, described elastomeric material comprises the product of polymerizable material, described gathers Condensation material comprises:
A () gross weight based on described polymerizable material meter, the first of 20 to 99.5 weight % is single Body, described first monomer has formula (I)
R1-O-(CO)-Y-O-(CO)-C(R3)=CH2
(I)
Wherein
R1For alkyl, aryl or combinations thereof；
Y is formula C of side chain or straight chainn(R2)2n-alkylidene；
R2For hydrogen or alkyl；
N is the integer in the range of 1 to 12；
R3For hydrogen or methyl；With
B () gross weight based on described polymerizable material meter, the second of 0.5 to 80 weight % is single Body, described second comonomer has ethylenic unsaturated group, wherein said second comonomer It is different from described first monomer.
Contact adhesive the most according to claim 1, wherein said based on (methyl) acrylic acid bullet Elastomer material has the glass transition of not higher than 10 DEG C measured by differential scanning calorimeter Temperature (Tg)。
Contact adhesive the most according to claim 1, the monomer tool of wherein said first formula (I) There are formula (Ia) or (Ic)
R1-O-(CO)-CnH2n-O-(CO)-C(R3)=CH2
(Ia)
R1-O-(CO)-CnHp(R2a)q-O-(CO)-C(R3)=CH2
(Ic)
Wherein
R2aFor alkyl；And
P is the integer equal at least about zero；
Q is the integer equal at least about 1；And
(p+q) sum is equal to 2n.
Contact adhesive the most according to claim 1, the monomer tool of wherein said first formula (I) There is formula (Ib), (Id) or (Ie)
R1-O-(CO)-CH2-O-(CO)-C(R3)=CH2
(Ib)
R1-O-(CO)-CHR2a-O-(CO)-C(R3)=CH2
(Id)
R1-O-(CO)-C(R2a)2-O-(CO)-C(R3)=CH2
(Ie)
Wherein R2aFor alkyl.
Contact adhesive the most according to claim 1, wherein R3For hydrogen.
Contact adhesive the most according to claim 1, wherein said first monomer is CH3CH2CH2CH2-O-(CO)-CH2-O-(CO)-CH2=CH2Or CH3CH2CH2CH2-O- (CO)-CH(CH3)-O-(CO)-CH2=CH2。
Contact adhesive the most according to any one of claim 1 to 6, wherein said second is single Body is to have the crosslinkers monomers of at least two ethylenic unsaturated group, have single ethylene linkage The non-polar monomer of formula unsaturated group, there is the polarity list of single ethylenic unsaturated group Body or their mixture.
Contact adhesive the most according to claim 7, wherein gross weight based on polymerizable material Meter, described polymerizable material comprise described first formula (I) of at least 50 weight % monomer and The described polar monomer of at most 15 weight %.
Contact adhesive the most according to claim 8, described contact adhesive also comprises at most 5 The described crosslinkers monomers of weight %.
Contact adhesive the most according to any one of claim 1 to 5, wherein R1For have to The alkyl of few 4 carbon atoms.
11. contact adhesive according to any one of claim 1 to 6, wherein contact adhesives At 80 DEG C, in 24 hours, ester hydrolysis is there is in the pH aqueous solution more than 7.
12. 1 kinds of goods, described goods comprise:
1) pressure sensitive adhesive layer, described pressure sensitive adhesive layer comprises based on (methyl) acrylic acid elasticity Body material, described elastomeric material comprises the product of polymerizable material, described gathers Condensation material comprises:
(a) gross weight based on described polymerizable material meter, the first of 20 to 99.5 weight % Monomer, described first monomer has formula (I)
R1-O-(CO)-Y-O-(CO)-C(R3)=CH2
(I)
Wherein
R1For alkyl, aryl or combinations thereof；
Y is formula C of side chain or straight chainn(R2)2n-alkylidene；
R2For hydrogen or alkyl；
N is the integer in the range of 1 to 12；
R3For hydrogen or methyl；With
B () gross weight based on described polymerizable material meter, the second of 0.5 to 80 weight % is single Body, described second comonomer has an ethylenic unsaturated group, and wherein said second Monomer is different from described first monomer；With
2) substrate of described pressure sensitive adhesive layer it is positioned adjacent to.
CN201380066683.4A 2012-12-19 2013-11-26 The contact adhesive prepared by degradable monomer and polymer Active CN104870588B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0576128A1 (en) * 1992-06-23 1993-12-29 Rohm And Haas Company Polymer blend containing an acid-rich polymer
EP0637618A1 (en) * 1993-07-28 1995-02-08 LINTEC Corporation Biodegradable adhesive tape and biodegradable adhesive label
CN1938377A (en) * 2004-03-26 2007-03-28 株式会社钟化 Composition curable by both free-radical photocuring and cationic photocuring

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0576128A1 (en) * 1992-06-23 1993-12-29 Rohm And Haas Company Polymer blend containing an acid-rich polymer
EP0637618A1 (en) * 1993-07-28 1995-02-08 LINTEC Corporation Biodegradable adhesive tape and biodegradable adhesive label
CN1938377A (en) * 2004-03-26 2007-03-28 株式会社钟化 Composition curable by both free-radical photocuring and cationic photocuring

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