JPH06506253A - Polymerizable fluorochemical surfactants and acrylate adhesives containing them - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Polymerizable fluorochemical surfactants and acrylate adhesives containing them Background of the invention field of invention The present invention relates to polymerizable mixtures containing acrylates. From another perspective, the original The use of surfactants, especially fluorochemicals, in acrylate-containing adhesive compositions Regarding the use of surfactants.

Description of related technology Fluorochemical surfactants are generally used to reduce the surface tension of organic solvents. used for For example, Pa1nt and Varnish Prod's Fluorochemical surfactants such as FC-430 and FC-431 for (3M) is described. Use fluorochemical surfactants Problems that can be raised include shrinkage of the casing membrane into beads, crater formation, dull skin, floating pigments and flooding; as well as low leveling properties.

U.S. Pat. No. 3,787,351 (Olson) describes fluoroaliphatic radicals and and oligomers containing poly(oxyalkylene) solubilizing components. . This oligomer is used in filled resin composites (e.g. glass fiber reinforced polyester). To improve the mechanical properties of molded products (Stell resin or epoxy resin composite materials) , is said to be used for blue as a wetting agent. Additionally, U.S. Patent No. 4.415.6 No. 15 (Esmay et al.) uses a cellular pressure-sensitive adhesive to create a uniform cellular structure. Oligomers of U.S. Pat. No. 3,787,351 as surfactants in the preparation describes some uses of -.

Non-fluorinated polymerizable surfactants are described, for example, in U.S. Pat. No. 4.560.599 (R egen). This patent is based on the solid state produced by polyfunctional polymerizable surfactants. A direct stepwise sheathing method for the support is described. In this polymerizable surfactant , methacrylate-functional phosphatidyl choline and phosphate esters were used. Ru. U.S. Pat. No. 4,569,798 (Nieh) discloses the use of surfactants in aqueous solutions. and in the synthesis of water-soluble copolymers with surface-active properties. Describes acrylamide substituted with said to be amphoteric tertiary amine. are doing.

U.S. Pat. No. 4,246,387 (Deutsch) discloses ring-sulfonated male Partial esters of alkoxylated alkyl/arylols are described. and U.S. Pat. No. 4,617,343 (Walker et al.) The use of such surfactants in the synthesis of emulsion polymers for adhesives The purpose is described.

Res, Discl, 1981.208.309 contains one active hydrogen. surfactants such as esters of secondary alcohols of polyethylene glycol , an addition-polymerizable isocyanate, such as 2-isocyanato ethyl methacrylate. Describes the preparation of vinyl surfactant v4 by reacting with There is.

lh, Fiz, Khim, 1982.56.2898 (Abstra ct) is used to impart hydrophobicity and chemical resistance to the surface of polymers through copolymerization. The formula CH1=CHC0, CH2(CF, CF2), In the RC formula, R is H or F, and n is 1-4. ] Fluorine-containing Contains acrylate.

British patent GB 2.172.8898 (Wakatsuki et al.) provides phosphoric acid of the formula Esters [wherein R1 is hydrogen or methyl, R is especially from 1 to 36] Straight chain or branched fluorocarbons having a carbon atom and at least one fluorine atom It is an alkyl group. ] is described. These compounds have good surface activity. property, self-organizability, and polymerizability. That's what I'm talking about.

Summary of the invention The present invention is a polymeric adhesive composition comprising: (a) an acrylate as a base material; obtained from an acrylate-containing mixture comprising the monomer components of a pressure-sensitive adhesive a large amount of polymerized units; and (b) at least two fluoroaliphatic side chains, at least two organic soluble groups, and at least one polymerizable olefin group side chain. is a polymerizable, organic soluble, Contains a small amount of polymerized units, obtained from oligomeric fluorochemical surfactants Provide something consisting of.

In a preferred embodiment, the fluorinated oligomer in the surfactant composition is: Under; (i) at least two fluorinated polymers each having a fully fluorinated end group; b) Aliphatic group: (ii) each comprising a number of carbon atoms, and optionally l or at least one organic soluble group comprising more catenary oxygen atoms than: as well as, (iii) at least one polymerizable olefin group; It has an aliphatic skeleton, and contains fluoroaliphatic groups, organic soluble groups, and polymerizable olefin groups. Each independently binds to the above lipid via a covalent bond, a heteroatom, or an organic bonding group. Comprising those attached to an aliphatic skeleton.

In a further preferred embodiment, the above polymerizable fluorochemical surfactant composition The object is expressed by the following formula 1: R1, R2, and R3 are independently obtained from polymerizable resin monomers. represents a polymerized unit and together form an aliphatic skeleton.

Each Q is independently a covalent bond, a heteroatom, or an organic bonding group.

R4 is a fluoroaliphatic group containing a fully fluorinated end group.

R4 comprises a large number of carbon atoms and optionally one or more carbon atoms. It is an organic soluble group containing many catenary oxygen atoms.

R2 is a polymerizable olefin group; and a, b, c, d and e are the above-mentioned The total number is such that the compound becomes an oligomer, and each n is independently 0 or is 1. ] one or more oligos comprising a moiety represented by It consists of mer.

In the embodiment where n is 0, the above-mentioned soluble group R8 is a pendant group, and the above-mentioned soluble group Ligomers are not crosslinked. In the embodiment where n is 1, the above-mentioned soluble group R 8 is a catenary, and the oligomer is cross-linked. has been done.

The acrylate-containing mixture preferably has an alkyl group containing from 1 to about 14 carbon atoms. large amounts of alkyl acrylates, and small amounts of polar monomers copolymerizable with these It consists of

The present invention provides a large monomer component of acrylate-based pressure sensitive adhesives and and a small amount of a fluorochemical surfactant as described above. We also provide products.

In a preferred embodiment of this prepolymer composition, the acrylate-containing mixture The material is partially polymerized to provide optimal viscosity for the coating.

The present invention is a method for preparing a pressure sensitive adhesive composition comprising the following steps: (i>acrylic The monomer components of the pressure-sensitive adhesive based on the base material and the photoinitiator are combined: (11) the composition from step (i) so as to increase its viscosity for application purposes; (iii) providing a prepolymer composition; a polymerizable fluorochemical surfactant as described above and step (2). and the composition of et al.

(iv) applying the prepolymer composition from step (ii) onto a support; and , (V) substantially completely photopolymerized in an inert atmosphere;

Also provided is a method comprising:

a fluorochemical surfactant and an acrylate-containing mixture of the above prepolymer; During the copolymerization of the adhesive composition of the present invention, the adhesive composition generally maintains adhesive performance over time related to the retention and migration of surfactants to the surface of the cured adhesive composition. avoid reduced adhesion performance. Furthermore, the copolymerization may be performed using the above surfactants or the above-mentioned surfactants. The surfactant remains dispersed throughout the composition and prevents agglomeration of the surfactant into larger droplets. To avoid. Therefore, the adhesive composition of the present invention has good properties due to the presence of the surfactant. Preparation of pressure-sensitive adhesive coatings that can be applied and do not show a decrease in adhesive performance during aging can be used in

The present invention provides a low adhesion carrier having a coating of polymeric adhesive as described above thereon. Also provided is an adhesive transfer tape comprising a rear.

This adhesive transfer tape of the present invention can be used for a long time after being initially placed on a support. After this time, the adhesive layer becomes "permanent". This way For example, the adhesive composition and transfer tape of the present invention may contain two or more The layers of the membrane should be glued together by precise positioning of each layer. Overlooking the application in the assembly of I-Sochi, the above layers were initially mispositioned. If so, they can be repositioned rather than discarded. .

The present invention provides at least two fluoroaliphatic side chains, at least two organic soluble and one polymerizable olefin group side chain in each of n. Also provided are organic soluble, oligomeric fluorochemical surfactant compositions.

In a preferred embodiment, one or more fluorinated oligomers are included. A polymerizable, organic-soluble, oligomeric fluorochemical surfactant composition consisting of each of the fluorinated oligomers: (i) at least two fluorinated polymers each having a fully fluorinated end group; b) Aliphatic group: (ii) each comprising a large number of carbon atoms, and optionally at least two organic soluble groups comprising more catenary oxygen atoms than: as well as, (iii) at least one polymerizable olefin group; It has an aliphatic skeleton, and contains fluoroaliphatic groups, organic soluble groups, and polymerizable olefin groups. Each independently binds to the above lipid via a coexisting bond, a heteroatom, or an organic bonding group. attached to an aliphatic skeleton, Provided is a surfactant composition comprising:

In a further preferred embodiment, the present invention provides polymerizable fluorochemical surfactants A composition of the following formula I: R', R'', and R3 are independently fluorinated. represents a polymerized unit obtained from a soluble and difunctional monomer, and - Together they form an aliphatic skeleton: Each Q is independently a coexisting bond, a heteroatom, or an organic bonding group.

R1 is a fluoroaliphatic group containing a fully fluorinated end group.

R8 comprises multiple carbon atoms, and optionally one or more carbon atoms. It is an organic soluble group containing many catenary oxygen atoms.

R2 is a polymerizable olefin group; and a, b, c, d and e are the above-mentioned The total number is such that the compound becomes an oligomer, and each n is independently 0 or is l. ] one or more oligos comprising a moiety represented by In the embodiment in which n is O, the above-mentioned soluble group R1 is a side group, and the oligomer is not crosslinked and n is 1. In the example, the above-mentioned soluble group R5 is catenary (CatenarY), And the above oligomer is a crosslinked one, I will provide a.

The present invention provides a method for synthesizing the composition as described above, comprising the following steps. (i) side chains of at least two fluoroaliphatic groups, at least two organic soluble groups; , and one that can be converted and further synthesized into a polymerizable olefin group one or more fluorinated ribomers each comprising a side group of to form an intermediate composition comprising a fluorinated monomer, a soluble monomer , and oligomerize the difunctional monomer: and (11) polymerizable olefin. the above intermediate from step (1) to provide the above composition comprising a fin group; A method is also provided comprising converting or further compositing.

The polymerizable fluorochemical surfactants of the present invention can be used in combinations of acrylate-containing mixtures and To reduce the interfacial turbulence of pressure-sensitive adhesives based on acrylate. that are well coated due to the presence of their surfactants and have good adhesion during aging. used in the preparation of acrylate-based pressure-sensitive adhesives that maintain can be done.

Detailed description of the invention The polymer adhesive composition of the present invention is a polymeric adhesive composition obtained from a polymerizable fluorinated oligomer. It consists of units. used herein to represent the structure of this fluorinated ribomer. The chemical formula shown is the presence of a chain of randomly polymerized units resulting from several types of monomers. These formulas show units of units, e.g. ``blocks'', e.g. intended to indicate the order of other alternating units in the lock copolymer or within the chain It's not a thing. The term “oligomer” or “oligomer〇” is used herein contains a large number of polymerized units, but the number of polymerized units present in the polymer is It refers to a compound containing a chain of polymerized units, for example, from 5 to about 1 oo.

Fluoroaliphatic groups are designated herein as R4.

R7 is a stable, inert, non-polar, preferably saturated, monovalent oleophobic and It is an ingredient that is both aqueous. The fluorinated oligomer preferably contains 2 to about 2 5 R4 groups, and the total weight of the oligomer includes the fluorine position is present essentially within the R group, preferably about 5 percent by weight. from about 30 weight percent, and more preferably from about 8 weight percent It comprises about 20 weight percent fluorine. R, is preferably at least , about 3 carbon atoms, more preferably about 6 to about 12 carbon atoms. R 1 is a linear, branched, or cyclic fluorinated alkyl group or a combination thereof or may include combinations thereof with straight-chain, branched-chain, or cyclic alkyl groups. Wear. R, is preferably free of polymerizable olefinic unsaturation and optionally more catenary heteroatoms, such as oxygen, divalent or hexavalent sulfur, or Can contain nitrogen. R4 is about 40% to about 78% by weight of fluorine, or more Preferably, the fluorine content is from about 50% to about 78% by weight. this The terminal component of the R1 group comprises a fully fluorinated terminal group. This terminal group is , preferably at least 7 fluorine atoms, e.g. CF, CF, CF t-, (CF, ') 2 CF-, -CF.

SFs, etc. Perfluorinated aliphatic groups, ie, chemical formulas C, F,.

0. The latter is the most preferred embodiment of R1.

Organic soluble groups are designated herein as R1. Fluorinated compounds are Preferably, the compound is carried out in an organic medium, such as a conventional solvent such as a ketone, an Polymerizable mixture of esters, hydrocarbons, and acrylic acid and methacrylic acid, acrylic acid. Contains enough R5 groups to be able to dissolve in rylates and methacrylates etc. It consists of A particularly preferred number of R1 groups is a specific R1 group and whether the compound or dissolved It will depend on the nature of the particular medium being contemplated. However, in general, A large number of R8 groups is preferred, for example from 2 to about 60, more preferably from 4 to about 30. Ru. Each R1 has at least 4 carbon atoms, and optionally at least Both contain one catenary oxygen atom. R6 is preferably from 8 to about 50 Contains carbon atoms and is linear, branched, cyclic, or any combination thereof be able to. Said soluble group is preferably a side chain of said fluorinated oligomer. It is. In such examples, n in Formula I is 0. n in the formula is 1 If so, it can also be a catenary group. At least one n is 0 , and one n is l, both the side chain and the catenary soluble group are present. I can exist. Preferred R6 groups are polyoxyalkylenyl groups, such as polyoxy ethylene or polyoxyethylene, and straight-chain, branched-chain, or cyclic alkyl or or alkylene groups, such as butyl, butylene, octyl, octisine, iso octyl, isooctyln, octadecyl, or octadecyln; including combinations of these.

The above polymerizable olefin group is designated herein as R2. The above The fluorinated compound is polymerized via R, into the adhesive composition of the present invention. R. Any olefin group capable of undergoing a free-radical polymerization reaction Can be done. Examples of such groups are, for example, acrylates or vinyl ethers. ethynyl, as found in Contains propenyl. Fluorinated compounds can contain a large number of polymerizable olefin groups. and preferably can contain one polymerizable olefin group.

The above polymerizable fluorochemical surfactant composition has a preferred embodiment shown in Formula 1. It will be further explained with reference to Mr.

In a preferred embodiment shown in Formula 1, the aliphatic skeleton described above is It comprises a sufficient number of polymerized units to provide oligomeric properties. This skeleton is about 5 to about 1 00 polymerized units, more preferably 10 to about 50, and most preferably 2 Preferably, it comprises from 0 to about 40 polymerized units. The homopolymerized unit is! more It can contain many types of side groups. However, this polymerized unit is preferably In particular, fluorinated monomers, i.e. those containing fluoroaliphatic groups, difunctional Monomers, i.e., those that can be converted or further synthesized into polymerizable olefin groups. soluble monomers, i.e. those containing soluble groups; is induced from The relative and absolute numbers of several types of polymerized units in the compound are preferably , such that a preferred number of several types of corresponding side groups are present in the oligomer. be. Therefore, referring to formula l, the sum of a and all occurrences of e is about 2 to about 2 5, more preferably 5 to about 15, and the sum of b and all the products of d is less than C is at least 1 to about 60, more preferably 2 to about 30, and C is about 2 to about 30. Preferably it is about 60, more preferably 4 to about 30.

The molar ratio of several types of polymerized units in the aliphatic skeleton and hence the fluorine The number of converted, soluble, and polymerizable reflex groups present in the compositions of the invention It will not be the same in each oligomer present. Therefore, the set of the present invention Compositions and oligomers are generally referred to herein as each of several types of monomers. of the polymerized units obtained therefrom and their relative amounts used in the preparation of the composition. It is characterized with respect to the overall ratio, which is more explicitly determined.

The above fluorinated, soluble, and polymerizable group is named Q in formula I. The aliphatic skeleton is bonded to the aliphatic skeleton through a bonding group. The bonding group Q is a covalent bond, a hetero bond, It can be an atom, for example 0 or S, or an organic moiety. This bonding group Q preferably contains from 1 to about 20 carbon atoms, optionally oxygen, nitrogen, or or a sulfur-containing group, or a combination thereof; Functional groups, e.g. double bonds of polymerizable olefins, thiols, easily separable hydrogen Atoms, such as cumyl hydrogen, and other free radical oligomerization entities It does not contain any functionalities known to those skilled in the art that would be a nuisance. Suitable for bonding group Q Examples of such structures are linear, branched or cyclic alkylene, arylene, aralkylene, Oxy, oxo, thio, sulfonyl, sulfinyl, imino, sulfonamide, carbon Rufokidiamide, carbonyloxy, uretanisin, ureylene, and their combinations, such as sulfonamide alkylenes. A preferred bonding group Q is a synthetic can be selected according to ease and commercial availability and that R, , R , , or R2 depending on whether it is attached to the aliphatic backbone.

Below is a partially representative list of suitable organic Q groups. The purpose of this list For, each k is independently an integer from ■ to about 20, and g is is an integer from 0 to about 10, h is an integer from ■ to about 20, and R is , hydrogen, phenyl, or alkyl of 1 to about 4 carbon atoms, and R'' is Alkyl of 1 to about 20 carbon atoms.

-5o2NR' (0M2)kO(0)C--CONR'(CH,)kO( 0)C-(CH,)kO(0)c- -CH2CH(OH) CH2O(0) C--CH2CH(OR' I)CH 20(0)C--(CH2)kC(0)O- -(CH2), 5C(0)- -(CH2)7(CH2)kO(0)C-"" (CHz) *S (CHz) kO(0)C--(CHt)k(OCHzCHz)ko(0)C--(CH2 ) *S02 (CH2) *o(0) C--5O,NR(CH2)kO(C 1(,CH,)kO(0)C--(CH,)R50,NR(CH2)kO( 0)C--(CHt)kSot- -SO Kuni' (CH2)k- -OC, H4CH2O(0) C- -(CH2)　,O(CH,CM2O)　ICH2CH,QC(0)　--(C Hz)bO((0)C(CH2)60),C(0)(CH2)60C(0) --(CH,), O((0) C(CM, ), NH), C(0)(CH2 )-5c (o)--C(0) O(CH2) 2QC(0) NH(CH, ), QC(0)-R, Q is preferably alkylene or is a sulfonamide or sulfonamide alkylene. Combine R5 For this purpose, Q is preferably carbonyloxy. To attach the R2 group , Q is preferably -C(0)0(CH2)20C(0)NH(CH2 )! QC(0)-.

The aliphatic skeleton mentioned above is of course not present in the form shown in formula I. Rather, It can be modified by hydrogen or by some organic group (not shown in formula I). are terminated at each end. This terminal group is the same as that used in the synthesis of the above composition. Exist by law. The specific end groups present in certain fluorinated compounds are , is not unduly essential to the functioning of the compositions of the invention. Typically the terminal groups are hydrogen, or containing an alkylthio group that would result from an alkylthiol chain transfer agent. .

The polymeric adhesive compositions described above are obtained from monomer components of acrylate-containing mixtures. It also contains polymerized units. This acrylate-containing mixture contains acrylates. It comprises as a base material the monomer component of a pressure sensitive adhesive. The nature of such ingredients and relative amounts are well known to those skilled in the art. Particularly preferred in acrylate-containing mixtures are alkyl acrylates, preferably containing from 1 to about 14 alkyl groups. functional unsaturated alkylate of a non-tertiary alkyl alcohol containing carbon atoms. Contains ester. Included within this class of monomers are e.g. , isooctyl acrylate, isononyl acrylate, 2-ethylhexy acrylate, decyl acrylate, dodecyl acrylate, n-butyl acrylate acrylate, and hexyl acrylate. Preferred monomers are isooctyl acrylate, isononyl acrylate, and butyl acrylate Including rate.

Optionally and preferably, a polar copolymerizable monomer is added to the acrylate. present in the containing mixture. Polar copolymerizable monomer in the above acrylate-containing mixture The inclusion of - improves the adhesion of the final adhesive composition to metal and this final It also improves cohesion in standard adhesive compositions. Strongly polar and moderately polar Polymerizable monomers can be used. Strongly polar copolymerizable monomers Acrylic acid, itaconic acid, hydroxyalkyl acrylate, cyanoalkyl Includes acrylates, acrylamides, and substituted acrylamides. strong pole The copolymerizable monomer preferably contains a small amount, e.g. It makes up up to about 25%, more preferably up to about 15%, of the mixture. strong pole When a specific copolymerizable monomer is present, the above alkyl acrylate monomer generally contains a large amount of the monomers in the acrylate-containing mixture, e.g. , making up at least about 75% by weight of the monomers.

Medium polar copolymerizable monomers include N-vinyl pyrrolidone, acrylonitrile, vinyl, vinyl chloride, and diallyl phthalate. medium polarity The polymerizable monomers are preferably present in small amounts, e.g. in the acrylate-containing mixtures described above. more preferably from 5% to about 40%. middle When a highly polar copolymerizable monomer is present, the above alkyl acrylate The monomer generally makes up at least about 60% of the acrylate-containing mixture. Configure.

The polymeric adhesive composition of item 2 is preferably crosslinked.

The polymer adhesive composition of the present invention comprises a polymeric adhesive composition obtained from the above-mentioned acrylate-containing mixture. amount of polymerized units and a small amount of polymerized units obtained from the above fluorinated surfactant. It consists of Preferably, this fluorinated unit comprises the above-mentioned acrylate as the base material. as an effective amount to reduce the surface tension of the composition as compared to pressure sensitive adhesives. Yes, it exists.

The amount that constitutes an effective amount depends on the particular surfactant and acrylate-containing mixture used. It will vary depending on the item. However, generally based on the weight of the composition, , about 0.05 to about 2 weight percent surfactant is preferred, and about 0.1 to about 1 % surfactant is preferred, and about 0.2% or most preferably stomach.

The polymeric adhesive composition of the present invention may contain other substances such as fillers, pigments, plasticizers, Tackifiers, fibrous reinforcements, woven and non-woven fabrics, blowing agents, antioxidants, stabilizers, Contains flame retardants and viscosity modifiers. Such substances can be readily determined by those skilled in the art. can be used in any suitable amount.

Particularly useful fillers include U.S. Pat. No. 0 (Klingen et al.), both of which are incorporated herein by reference. It is a hydrophobic silica as disclosed in

Other adjuncts used in the above prepolymer and adhesive compositions include glass containing microspheres of gas or polymer. This microsphere has a size of 10 to 200 micrometers. and should constitute about 5 to about 65% by volume of the layer. I can do that. Suitable polymeric microspheres are described in U.S. Pat. No. 4,287,398 (N akayama) (incorporated herein by reference). including things.

Hydrocarbon elastomers, such as styrene-butadiene block copolymers, Commonly Assigned Concurrent U.S. Patent Applications Filed June 28, 1988 Modification of adhesion to high solids coatings as described in Application No. 07/210.712. It can also be taken in for good.

Such elastomer preferably accounts for 100 parts by weight of the composition. based on about 5 to about 35 parts by weight of the composition.

Fluorinated surfactant compositions with side chain solubilizing groups (e.g., when the mouth of Formula I is 0 and A non-crosslinkable composition) can be synthesized as shown in the reaction scheme below. (where R', R'', R', Q, R,, R,, R,, a, b, and C are (same as defined earlier). G corresponds to, can be converted to, the bonding group Q. or may be further synthesized. Each R is hydrogen, halogen or methyl, and R1 is converted into a polymerizable olefin group. It is a group that can be synthesized or further synthesized. The above oligomer chain The terminating group is not shown in this reaction scheme.

RfQCR″″″0(2 ■ In step (i) of the above reaction mechanism, a fluorinated monomer, a soluble monomer, and and difunctional monomers are oligomerized to make intermediates of formula I+.

R5 in the compound of formula II and in the difunctional monomer is transformed and further It is a group that can be synthesized into a polymerizable double bond. R, is a reaction, e.g. Groups that are sensitive to nuclear or electronic attack by reagents containing synthetic olefinic groups .

Exemplary groups of this nature include epoxy, azlactone (i.e., 2-oxanoyl) 5-one), acyl halide, alkyl halide, carboxylink ・Anhydride, isocyanato, and other electronic groups, as well as hydroxy, amino , and other nuclear groups. Difunctional monomers containing such groups are known to those skilled in the art. are well known and generally commercially available or easily synthesized. Ru.

An exemplary difunctional monomer is 2-alkenyl-2-year-old xabrine-5-ounce, e.g. 2-ethynyl-2- Oxazolin-5-one and 2-propenyl-2-oxazolin-5-one Niacrylamide: Methacrylamide: Maleamide, maleimide diN-isopro Pill acrylamide; N-methylol methacrylamide; diacetone acrylamide Lylamide and methacrylamide: methylolation, diacetone, acrylamide and methacrylamide: 2-hydroxy-3-chloropropyl acrylate and and methacrylate: aziridinyl acrylate and methacrylate: anhydrous male Inric acid: Allyl Alcohol: Allyl Glycolate: Isobutene diyl: A Ryloxyethanol 20-Allyl Phenol: Divinyl Carbinol: Gly Cerol α-allyl ether; acrylic acid, methacrylic acid and their metal salts , vinyl sulfonic acid and styrene/p-sulfonic acid and their metal salts: 3-a Minocrotonitrile; monoallylamide = 2-acrylamide-2-methylpropylene Pansulfonic acid (AMPS) and its salts nigericidyl acrylate and meth Acrylate: Allyl glycidyl ether: Acrolein: N,N-dimethyl Aminoethyl acrylate and methacrylate: N-tert-butylamino Ethyl methacrylate: Olefinic unsaturations, e.g. isocyanatoethyl Methacrylate, bis(2-isocyanatoethyl)-fumarate, methacrylate isocyanate, 1(1'-isocyanato-1'-methylethyl)-3-( 1'-methylethynyl)-benzene (American Cyanamide) (available as M-TλII), and isocyanates containing allyl isocyanate. Anate: halogenated lower olefinic hydrocarbon, e.g. 3-chloro-2-iso Butane, allyl bromide, allyl chloride, and methallyl chloride, vinyl esters, e.g. , vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl sulphate uccinate, vinyl stearate, divinyl carbonate, allyl ester, For example, allyl acetate and allyl heptanoate, vinyl alkyl keto For example, vinyl methyl ketone: unsaturated acids such as acrylic acid, α-chloro Fluoro-acrylic acid, α-fluoro-acrylic acid, crotonic acid, maleic acid, fumer acid, itaconic acid, and citraconic acid, and their anhydrides and esters; For example, dimethyl maleate, ethyl crotonate, acid methyl maleate , acid butyl itaconate, and C1-C4 alkyl acrylate and meth acrylate, including.

Dissolving monomers are well known and generally commercially available by those skilled in the art. or can be easily synthesized. Exemplary soluble monomers include C2 and above. Long, preferably C4 and longer alkyl acrylates and methacrylates esters, such as octadecyl methacrylate, polyalkylene glycols, etc. acrylates and methacrylates such as triethylene glycol acrylates rylate, methquinopolyethylene glycol and polyethylene glycol ( Acrylates and methacrylates (available as CARBOW, AX”) propylene end-capped with ethylene oxide and hydroxy groups. block copolymerization of carbon oxide (available as PLLIRONIC'') body, as well as tetramethylene oxide/glycol (TERATHANE”’) ): as well as amino-terminated polyethers (JEFFAMINE Acrylamide and methacrylamide (available as '').

Fluorinated monomers and methods of their synthesis are known and, for example, in the US Patents No. 2.803.615 (Ahlbrecht et al.) and No. 2.841.57 No. 3 (Ahlbrecht et al.), incorporated herein by reference. Disclosed. Examples of these compounds include common fluorochemicals. Olefins, such as acrylates, methacrylates, vinyl ethers, and fluorinated sulfonamide groups from fluoromical telomer alcohols. , acrylates or methacrylates obtained from fluorochemical thiols, etc. Contains allyl compounds containing Certain fluorinated monomers include N-methyl per Fluorooctanesulfonamide ethyl acrylate, N-methyl perfluor Orooctanesulfonamidoethyl methacrylate, N-ethyl perfluoro Rooctanesulfonamidoethyl acrylate, N-methyl-perfluorohene Xylsulfonamide ethyl acrylate, isocyanatoethyl methacrylate and N-methyl-perfluorooctanesulfonamidoethyl alcohol. reaction product, perfluorooctyl acrylate, N-methyl perfluoro Octane sulfonamide ethyl vinyl ether, and C, F,, 502N HCH2CH=CH2, and others such as perfluorocyclohexyl ・Acrylate and tetramer hexafluoropropylene oxide dihydrogen Contains doroacrylate.

In step (i) of the above reaction mechanism, several types of monomers are used, each with their own type. present in the amount necessary to produce a product containing the desired relative numbers of monomers. Also , in step Iv(i), in order to terminate the oligomer chain at an appropriate length. There are also chain transfer agents that can serve to Control the absolute number of type monomers. A suitable chain transfer agent is a free radical Contains groups capable of propagating and terminating reactions and are known to those skilled in the art.

Typical chain transfer agents are thiols, e.g. ethanethiol, propanethiol , butanethiol, n-octylthiol, t-dodecylthiol, 2-merca Includes ptoethyl ether, 2-mercapto-imidazole, and the like. This chain transfer The motive agent in step (i) controls the number of polymerized units within the aliphatic backbone. present in sufficient quantities. This chain transfer agent is based on the number of moles of monomers in the reaction above. and generally about 1 to about 20 mole percent, preferably about 3 to about 10 mole percent. Used in amounts of cents.

A free radical initiator is also present in step (i).

Such compounds are known to those skilled in the art and include persulfates, azo compounds, For example, azo-osobutyronitrile and azo-2-cyanohalerianic acid, etc. Peroxides such as cumene, t-butyl, and [-amyl hydroperoxide sid, dialkyl peroxides such as di-t-butyl and dicumyl peroxide. Oxides, peroxyesters, such as t-butyl perbenzoate and di -t-butyl peroxy phthalate, diacyl peroxide, e.g. Contains yl peroxide and lauroyl peroxide.

The suitable amount of initiator depends on the particular initiator and other reaction substrates used. . from about 0.1% to about 5% by weight, based on the total weight of all other reactants in the reaction. % of the initiator, preferably from about 0.1% to about 1% by weight, may be used. can.

Step (1) is preferably carried out in an inert atmosphere, for example a dry nitrogen atmosphere. Ru. Step (1) can be carried out in a solvent suitable for organic free radical reactions. Wear. The reaction substrate can be present in this solvent and is present in the entire reaction mixture. Any suitable concentration by weight, such as from about 5 weight percent to about 90 weight percent Can be a percentage. Examples of suitable solvents are aliphatic and cycloaliphatic hydrocarbons. aromatic solvents, such as hexane, heptane, and cyclohexane; benzene, toluene, and xylene, ethers such as diethyl ether, glycerol Lime, diglyme, and diisopropyl ethers, esters, such as acetic acid Ethyl and butyl acetate: Ketones such as acetone, methyl ethyl ketone, and and methyl isobutyl ketone: sulfoxides, e.g. dimethyl sulfoxy Amides, such as N,N-dimethylformamide and N,N-dimethylacetic acid toamide halogenated solvents, e.g. methyl chloroform, FRi:aN1113 , trichloroethylene, and α, α, α-trifluorotoluene secondary, and including mixtures of these.

Similarly, step (i) may include any suitable method for inducing an organic free radical reaction. It can be carried out at any temperature. The particular temperature and solvent used may vary, e.g. A person skilled in the art can easily can be selected.

It is impractical to list specific temperatures suitable for all initiators and all solvents. However, generally suitable temperatures range between about 30''C and about 200'C.

The product of step (i), i.e. the oligomer of formula 1, may be further or different functionalized. can be synthesized or transformed in one or more steps via conventional methods to include groups Wear. However, this product would still be within the scope of Formula II. example For example, hydroxy-functional oligomers or oligomers with both hydroxy and chloro groups. , is reacted with shrimp chlorohydrin to provide further oligomers. be able to. As a further example, acid-functional oligomers (which can then be Abrolactam to provide amine-functional oligomers that also contain stellate linkages. can be reacted with) to provide a hydroxy-functional oligomer. can be reduced by methods known to those skilled in the art.

In step (11), the oligomer of formula I+ contains a polymerizable olefin group R2. converted or further synthesized to consist of Any one of the many reactions This can be done during step (11). Step (ii) generally comprises the R group and a reagent comprising a polymerizable olefin group and a functional group reactive with R1. including response. Conventional reactions such as charged nucleation, electrophilic addition, and free radical addition reactions can be used. Generally, the customary condition is that in step (11) It is suitable for carrying out various reactions that can be used. Specific conditions can be determined by a person skilled in the art. is well known and depends on R, the nature of the group, and the nature of the group chosen to react with R1. will depend on the nature of the reagent used.

Fluorine with catenary soluble groups, e.g. crosslinking compositions where n in formula I is 1 The method for synthesizing the chemical surfactant composition involves the synthesis of dissolved monomers of the l-functionality described. Instead, bifunctional dissolved monomers, i.e. two polymerizable olefin components and including the use in step (i) of a compound containing an attached solubilizing group. suitable 2 An example of a functional dissolved monomer is the polyoxyalkylene diol diacrylate. and dimethacrylates, such as CARBOWAXT″″1000.1450 ．． and U3350. Such difunctional soluble monomers When a polymer is used, step (1) comprises a catenary soluble group. Create cross-linked fluorinated oligomers. R, depending on the nature of the group, the above-mentioned separate steps The product of (i) is a step (ii) of making a polymerizable fluorochemical surfactant composition. can be converted or further synthesized as described above.

Known to those skilled in the art and, for example, US Pat. ens et al.) (incorporated herein by reference). According to the media method, the polymer adhesive composition of the present invention is mixed, applied, and Can be hardened.

Generally, the acrylate-containing mixture contains any elastomer (if any). by dissolving or dispersing in the acrylate monomer and then optionally by adding a polar copolymerizable monomer (if any) and a photoinitiator. and can be synthesized. Suitable photoinitiators include benzoin ether, Benzoin ethers such as benzoin methyl ether or benzoin ethers Zoin isopropyl ether, substituted acetophenones, e.g. Toxy-acetophenone and 2,2-dimethoxy-2-phenyl-acetophene Non-substituted alphaketols, such as 2-methyl-2-hydroxy-propylene Ophenone, aromatic sulfonyl chloride, e.g. 2-naphthalene sulfonyl chloride , and photoactive oximes, such as ■-phenyl-1,1-propanedione-2- Contains (0-ethoxycarbonyl)oxime. Generally, this photoinitiator is In an amount sufficient to initiate photopolymerization of the acrylate-containing mixture, e.g. Based on 100 parts of mer, about 0. From 1 part by weight to about 1.0 part by weight of O is present.

Optional crosslinkers or other additives may also be incorporated. Acrylate pressure sensitive welding Preferred crosslinkers for the adhesive are polyfunctional acrylates, such as 1,6-hexyl Sandiol diacrylate and U.S. Pat. No. 4.379.201 (H ei1mann et al.) (incorporated herein by reference). , e.g. trimethylolpropane triacrylate, pentaerythritol ・Tetraacrylate, 1,2-ethylene glycol diacrylate, and 1 ．． Contains 2-dodecanediol diacrylate. Crosslinking is a polyacrylate It is very easy to control when photopolymerizing the above monomers in the addition of crosslinking agents . Other blue crosslinking agents include substituted triazines, such as U.S. Pat. No. 4,329,38 4 and 4.330.590 (both incorporated herein by reference by Vesley For example, 2,4-bis(trichloromethyl)-6 -p-methoxystyrene-3-triazine. This crosslinking agent is typically Based on the total weight of monomers in the mixture, approximately 0. O exists in the range of 1% to about 5% by weight. Exists.

This acrylate-containing mixture is then allowed to increase its viscosity for coating purposes. can be partially polymerized in order to Approximately 500CpS ~ Approximately 50,000 cps, preferably polymerization to an optimum viscosity of about 3.000 cps is preferred. .

The above fluorochemical surfactant composition is then combined with the prepolymer composition of the present invention. is added to the above acrylate-containing mixture to make. This fluorochemical The acrylate-containing surfactant is preferably used to improve coating properties. In order to reduce the interfacial energy of the prepolymer composition as compared to the mixture, Added in sufficient quantity. A suitable amount of fluorochemical surfactant is Along with the polymeric adhesive composition, the same formulation as previously described is used.

During curing of the above composition, a chain transfer agent or prepolymer is added to control the polymer chain length. can be included in remer compositions. Suitable chain transfer agents are well known to those skilled in the art. and can be used in any suitable amount, e.g. The chain transfer agent is preferably used in an amount of about 0.05 to about 1 weight percent. Ru.

The above prepolymer composition can then be coated onto a support and in an inert, i.e. substantially oxygen-free, atmosphere, such as a nitrogen atmosphere. , substantially completely photopolymerized. Preferably the support is a siliconized sheet material, e.g. For example, siliconized polyethylene coated papers and siliconized polymers (e.g. containing low adhesion carriers, including tyrene, polypropylene, or polyester) films. nothing.

For photopolymerization, a sufficient inert atmosphere must be substantially by covering said coating with a plastic film that is transparent; and It can also be accomplished by radiating through the film into the air. Up Instead of covering the coating, the photopolymerization may be carried out in an inert atmosphere. If the permissible oxygen content of the inert atmosphere is U.S. Pat. No. 4,303,485 (Levens) (herein incorporated by reference) by incorporating an oxidizable tin compound as taught in can be increased. The patent states that such a procedure is photopolymerized in air. It is also taught that this would allow for thicker coatings.

The compositions of the present invention can be used in adhesive transfer tapes, pressure sensitive adhesive tapes, such as those described in U.S. Pat. No. 415.615 (Esmay et al.), incorporated herein by reference. as described, as well as multilayer pressure sensitive adhesive tapes, e.g. US Pat. No. 4.8 No. 94.259 (Kuller) (incorporated herein by reference). It can be used in the form as described.

The composition of the present invention was tested according to the test method described below.

90° peel adhesion The adhesive layer to be tested was made of chemically primed, 50 μm aluminum. Transfer to a foil backing and then swath this to a width of 1/2 inch (1.27 cm). Lit. Place the resulting tape on one end or on a smooth support plate, e.g. steel, acrylonitrile/butadiene/styrene copolymer, or test results Place it so that it sticks out on the edge of the surface, as shown in the table below. child of the tape under the weight of a 2.04 kg hard rubber covered steel roller. The substrate is attached to the support plate. Two buses in each direction are attached to the above rollers. It is done more. one end of the tape extends from an end of the support plate, and thereby allowing this tape to be pulled by a tensile tester , left as a free end. After exposure to the indicated conditions, 90° peel adhesion Using a testing machine, test the support at 90° and at a speed of about 0.5 cm per second. Measured by pulling the free end of the tape away from the plate. The conditions are as follows. In the example below, it is shown as follows: Initial 15 minute residence time of adhesive on test support before 1N peel test 3RT = 3 days residence time at room temperature before peel test 31 (A = 3 days at 70°C Residence time in days (conditions representing accelerated ripening)Surface tension The interfacial energy is fischer 5 surface Tensiomat N Measured using DuNouy's ring method on Iodel 21.

In the following examples, all reactions were performed under a dry nitrogen atmosphere, and all portions were and percentages are by weight unless otherwise specified.

The specific substances and their amounts, as well as other conditions and details expressed in the examples, are Nothing herein shall be construed as unduly limiting the invention.

Example 1 In a 950 mL bottle, 75.0 g (0,120 mol) of N-ethyl paroxylate was added. -Fluoro(octane)-sulfonamidoethyl methacrylate, II7.5 g (0,146 mo1) of CARBOWAXTM750 acrylate, 25.0 g (0,216 mol) of hydroxy ethyl acrylate, 250 g of acetic acid ethyl solvent, 5.0 g (0°034 mol) n-octyl thiol and 0.0 g (0°034 mol) n-octyl thiol; 625 g of azoisobutyronitrile was charged. This bottle and its contents are removed under reduced pressure. Degassed, flushed with nitrogen, sealed, then in a launder-0-Meter. Heating and stirring at 65° C. for 16 hours produced a hydroxy-functional intermediate of formula [[ Gave. The bottle was cooled, degassed under reduced pressure, and injected with air.

Part B 32.5 g (0.21 mol) of isocyanatoethyl. methacrylate, 0.25 g of hydroxyl monomethyl as polymerization inhibitor ether, and 0.25 g of tin(nine) octoate & TChe as catalyst micals, [catalyst T-9, available from NC] did.

The above sealed bottle was placed in a launder-0-meter at 70°C for 5 hours. Heated. Infrared analysis of the clear, dark amber polymer solution reveals unreacted isocyanate. Shows no nato groups and contains urethanes, methacrylates, fluoroaliphatics, and It showed the presence of polyoxyethylene groups.

Examples 2-17 Additional compositions of the invention were synthesized following the general procedure of Example 1.

Specific monomers, other reaction substrates, and catalysts are shown in Table 1 below. In the table: EtFOSEMA is C, F　,,S02　N(C2HS　)C,H,QC(0 )C(CH3)=CH2: EtFO3EA is C, F, 7S02 N (C2HS) C2H, QC (0) CH=C) represents I2.

Enter 1eFO3E,A is C,F　,,SO,N(CH,)C,H,QC(0)C I (= represents CH2: 2:0NYL 8A AIA is C, F t,, +c t represents H4QC(0)C(CH3)=CH2, n=6-12.

CARBOX 750A is CH30(C2H40)-C(0)CH=CH2, m = approximately 18.

OD^IA represents CIxHz70c(0)C(C)I　3　　”CH2; H OEA stands for HOC2H, QC(0)CH=CH1; HOPμ stands for HO(C H2) ff QC(0)C(CH!)=CH, represents: TBAE81A is to (CH,') 2 CNHC, H4QC(0)C(CI(,)=C1(, represents 716M represents 0CNC,H, QC(0)C(CH, door CHI: T9 is represents stannous ctanoate (Al&T Chemicals, [nc,), and TI2 is dibutyltin dilaurate (λl&T Chemicals, Inc. ) represents.

Molecular weight data was obtained for three compositions of the invention. in the synthesis of these compositions. The only significant variable was the amount of chain transfer agent used. This data is shown in Table 2. write down

Molecular weight and dispersity Example Chain transfer agent (g) Molecular weight (weight average) Former supervisory history 6 0.0625 20.0 12 4.497 1.25 12.313 1.758 0.5 16.97 4 2.38 The data in Table 2 shows that the amount of chain transfer agent depends on the length of the oligomer chain of the above fluorinated compound. It has been shown that it affects

In a bottle of about 110 mL, 7.0 g (0,011 mol) of N-ethyl per Fluoro(octane)-sulfonamidoethyl methacrylate, 12.0 g ( 0,015 mol) CARBOWAX 750 acrylate (750A), 1. Og (0,007 mol) of 2-bi)Iv-4,4-dimethyl-2-o Xazolin-5-one (VDAI), 32.6g ethyl acetate, 0.30g Add n-octyl thiol and 0.20 g of azobisisobutyronitrile. Ta. The second bottle was degassed on vacuum, flushed with nitrogen, sealed, and then 1 au Heating and stirring at 75°C for 16 hours in an Ieter to give the formula + The azlactone-functional intermediate of 1 was provided. Take out this bottle and let it cool to room temperature. Cooled.

Bart B 0.66 g (0,006 mol) of 2-hydroxyethylene was added to the solution from Bart A. acrylate and 0.04 g (2W4) of methane sulfonic acid catalyst. Ta. Next, the bottle was sealed and shaken at room temperature (approximately 22°C) for 8 hours. did. [R and NIIR analysis of a sample of the resulting amber solution revealed unreacted az. Shows no lactone groups and contains acrylates, fluoroaliphatics, and polyoxy It showed the presence of cyethylene group.

Examples 19-22 The general procedure of Example 18 was followed. However, in Example 22, the reaction temperature of Baat B The temperature was 70°C and the reaction time was 40 hours. The composition is shown in Table 3 below. It was synthesized as shown. In the table, EtFOSEUA is 08F, ? SO□S(C , HS)cz H4QC(0)C(CH,)=CHt; DMVA is 2 -vinyl-4,4-dimethyl-2-year-old xabrin-5-one: GMA is HOEA stands for HOC2H, QC(0)CH=CH2: AMC-2 stands for Ae Obtained from rojet Strategic Propulsion Co. represents chromium octoate in mineral spirits, and 4-D^IAP is , represents 4-(dimethylamino)pyridine.

Example 1 in acrylate monomers and mixtures thereof as shown in Table 4 Surface tension lowering properties were obtained for ~22 compositions at four concentrations. In the formula, I OA is isooctyl acrylate (surface tension = 27.5 dynes/cm) and IOA/AA is isooctyl acrylate in a 90/10 weight ratio /acrylic acid (surface tension = 27.8 dynes/cm). lack of information indicates that the value was not measured.

The data in Table 4 shows that the polymerizable surfactants of the present invention Acrylate monomers and their It has been shown that the interfacial energy of the mixture of

Table 5 below lists the indicated concentrations of polymerizable fluorochemical surfactants of the present invention. for a cured isooctyl acrylate/acrylic acid adhesive composition comprising: Adhesion data is shown. Adhesion data is for stainless steel and acrylonitrile/ - Shown for a butadiene/stycine copolymer (ABS) support. child data were obtained according to the test method described above and whose composition was formulated as follows: Done: Partially polymerized acrylate-containing mixtures are described in U.S. Pat. No. 4,330,590. Following the general procedure described in Example 1 of Ves 1ey, isooctyl 90 parts by weight of acrylate, 10 parts by weight of acrylic acid, and 2゜2-dimethoxy -Using a monomer mixture containing 0.04 parts by weight of 2-phenyl acetophenone I synthesized it. The resulting acrylate-containing mixture was heated to approximately 3,300 cps of blue water. It was partially polymerized by UV irradiation to Kuffield viscosity. Next, this substance 2,2-dimethoxy-2-phenyl acetophenone (0.15 parts by weight) and and 4-(p-methoxyphenyl)-2,6-pisdolichloromethyl-S-tria Modified by adding gin (0.15 parts by weight).

The resulting partially polymerized acrylate-containing mixture was transferred to a pressure-sensitive adhesive transfer technique as follows. I imported it into the group: Add the surfactant in the desired amount to the above partially polymerized acrylate-containing mixture. Ru. This composition is then applied to a low adhesion carrier using a knife applicator at 0% ．． Apply at a thickness of 0.05 mm. This coated carrier was then coated with 300 nm and 400 nm. have 90 percent of their irradiation energy between Approximately 125 mJ/cm” of UV irradiation (DY Irradiation is performed using a NACHEM 500 radiometer.

l　Under the title FLUORAD TMFC-431 housing additive, commercially available from Sansuke 1 et al. Oligomeric fluorokes, free of polymerizable olefinic unsaturations, available in The data for surface active removal of chemical acrylate copolymer 5 are based on the polymerizable surface of the present invention. These cured adhesive compositions comprising a surfactant or generally as indicated above. It shows that it maintains good adhesion to the substrate. On the other hand, non-polymerizable fluoride Adhesive compositions comprising primed surfactants are generally suitable for accelerated aging. Afterwards, it has a lower adhesion to the supports indicated above.

Examples 23-24 and Comparative Example CI, the nature of surface tension reduction at C24 concentration is shown in Table In non-polymerizable acrylate monomers and mixtures thereof as shown in 6. Thus, the surfactants of Examples 1 to 22 were obtained. In the table, 10A is isooctyl acetate. Relate (surface tension = 27.5 dynes/cm), and IOA/ AA is an isooctyl acrylate/acrylic acid 90/10 weight/weight ratio (Table Surface tension = 27.8 dynes/Cm). The reason for the omission is that This indicates that the value was not measured.

The data in Table 6 are with alkyl acrylates or acrylate-containing mixtures. These prepolymer mixtures of the invention comprising a polymerizable surfactant in lower interface than the corresponding alkyl acrylate or acrylate-containing mixture It shows that it has energy. This data further supports this invention. Their prepolymer mixture comprises a non-polymerizable fluorinated surfactant. It has also been shown to have interfacial energies comparable to compositions with

On the other hand, in Comparative Example C3, the non-fluorinated polyoxyethylene surfactant substantially This shows no reduction in the interfacial energy of acrylate-containing mixtures.

Examples 45-53 Partially polymerized acrylate-containing mixtures are described in U.S. Pat. No. 4,330,590. Following the general procedure described in Example 1 of Vesley, isooctyl acetate 90 parts by weight of acrylate, 10 parts of acrylic acid and 2,2-dimethoxy- Using a monomer mixture containing 2 to 0.04 parts by weight of phenyl acetophenone , synthesized. The resulting acrylate-containing mixture was heated to approximately 3,300 cps of Brook The field viscosity was then partially polymerized by UV irradiation. Next, this substance , 2,2-dimethoxy-2-phenyl acetophenone (0,15ffi amount fa ) and 4-(ρ-methoxyphenyl)-2,6-pisdolichloromethyl-s-h Modified by adding riazine (0.15 parts by weight).

The resulting partially polymerized acrylate-containing mixture was transferred to a pressure-sensitive adhesive transfer technique as follows. imported into the group, Add the surfactant (if used) in the desired amount to the partially polymerized acrylate described above. to the rate-containing mixture to form the prepolymer composition of the present invention. Next, this The composition of 0.05 mm of Apply in thickness. This coated carrier is then applied between 300 nm and 400 nm. has 90 percent of the irradiation energy and has a maximum value of 351 nm. Approximately 125 mJ/cm” of ultraviolet irradiation from a bank of lamps (DYNACHEM Irradiation by 500 radiometers).

Incorporating compositions of the invention and the like using the procedures described above. An adhesive transfer tape was synthesized from the components shown in Table 7 below. Adhesion data, Measurements were made using a stainless steel support.

The results are shown in Table 7 below. In the table, the surfactant is the weight of the acrylate-containing mixture. was used in an amount of 1 weight percent based on (The table below is divided into two parts. Each part represents an experiment performed together for comparison purposes. ) Available from 3+ under the trade name FLUORAD” FC-431 Coating Additive An oligomeric fluorochemical containing no polymerizable olefinic unsaturation. Acrylate Copolymer Surfactants The data in Table 7 shows that these polymers of the invention The adhesive composition has a lower boundary than its corresponding adhesive composition that does not contain any surfactant. This shows that it has surface energy. Table 7 shows that during accelerated aging, the polymerizable world Comparison of the adhesive composition of the present invention when no surfactant was used It has also been shown that it is possible to maintain adhesion to stainless steel compared to that of the example. are doing. On the other hand, Table 7 shows adhesive compositions comprising non-polymerizable fluorinated surfactants. indicates that the material does not maintain good adhesion to stainless steel during accelerated aging. are doing.

Examples 54-71 Adhesive transfer tapes were prepared according to the general method described in Examples 45-53 above.

Regarding surfactants and their amounts and transfer tapes prepared as described above Stainless steel adhesion data for 100% is reported in Table 8 below.

54 12 (0+21 64 96 164, 55 12 (1, Ol) 68 83 16056 15 (0+24) 64 85 16457 15 (1, ON) 66 83 1625822 (0,21) 70 103 15B59 22 (1,0%) 61 72 19560 7 (0,2k) 66 74 16661 7 (1,ot) 59 79 15362 17 (0,2%) 6 1 83 14063 17 (1,0%) 68 70 13464 2 (0, 2t) 68 72 15165 2 (1, Cn) 59 64 15366 5 (0+24) 64 72 15567 5 (1,ot) 61 81 14 568 B (0, 21) 64 88 16469 8 (1, (n) 70 9 4': L7370 6 (0,2%) 61 85 17771 6 (1,01 ) 64 85 173 The data in Table 8 is for these polymer adhesive sets of the present invention. Comparative Example C8 also showed good adhesion to stainless steel even during accelerated aging. This shows that the adhesiveness is maintained.

Examples 72-77 Adhesive transfer tapes were prepared according to the general method described in Examples 45-53 above using the following table. Partially polymerized prepolymer mixture, surfactant, initiator, and crosslinking agent described in 9. Prepared using a crosslinking agent. Support surfaces named in Table 9 and test methods described above. Adhesion tests were conducted using the method. The results are shown in Table 9. In the table, “PC” is , indicates that a polycarbonate support was used for the adhesion test; ABS" Acrylonitrile/butadiene/styrene copolymer surfaces were used for adhesion tests. and “PP” indicates that the polypropylene support was used for adhesion testing. It shows that it was done.

Table 9 (continued) Ao, 15 parts of 4-(-p-methquinphenyl)-2,6-pisdrichloromethy using S-triazine and 0.39 parts of 1-benzoylcyclohexanol. 93.5 parts of isooctyl acrylate, 6.5 parts of acrylic Ruic acid, '0.10 parts of 4-(-p-methoxyphenyl)-2,6-pisdolichloromethane Thiru S-triazine and 0.14 parts of 2,2-dimethoxy-2-phenyl a 80 parts of isooctyl acrylate, synthesized using cetophenone, 2 0 parts of N-vinyl pyrrolidinone' 0.10 parts of 4-(-p-methoxyphenylene )-2,6-pisdochloromethyl-S-triazine and 0.14 parts of 2.2 -dimethoxy-2-phenyl acetophenone, 90 parts of Isononyl acrylate, 10 parts acrylic acid 0 "part" is based on 100 parts by weight of monomer in the acrylate-containing mixture .

'FORALTM-85 resin is commercially available from Hercules, A tackifier set said to contain glyceryl aster, a highly hydrogenated resin. product '　Trade name FLUORAD　TMFC-740 Under good stimulation additive, 3λI? Commercially available oligomers free of polymerizable olefinic unsaturation. Fluorochemical acrylate copolymer surfactant removal data 9 These copolymerizable monomers of the invention (Examples 72, 73, 76 and 77) polymer adhesive compositions or for various support materials even during accelerated aging. This shows that good adhesion is maintained. Medium polar copolymerizable monomer - (Examples 74 and 75), these compositions of the invention contain polycarbonate, A BS, or when used with a polypropylene support, the comparative composition Comparable.

Various modifications and variations of this invention may be made without departing from the scope and core of this invention. This will be made clear to the dealer. If the invention is not suitable for the embodiments described herein, It is not a limitation that is limited, but a limitation that is understood.

Continuation of front page (72) Inventor: Magri, Imelda Ni.

United States, Minnesota 55133-3427゜St. Paul, Post Office Fis box 33427 (72) Inventor Alm, Roger Earle.

United States, Minnesota 55133-3427゜St. Paul, Post Office Fis box 33427

Claims (11)

[Claims] 1. at least two fluoroaliphatic side chains, at least two organic soluble groups, and one or more fluorophores each comprising at least one polymerizable olefin group side chain; Polymerizable, organic soluble, oligomeric fluorocarbons comprising hydrogenated oligomers Chemical surfactant composition. 2. The above fluorinated oligomer is (i) at least two fluorinated polymers each having a fully fluorinated end group; b) Aliphatic group; (ii) each comprising a large number of carbon atoms and one or more catenary acids; at least one organic soluble group, each of which may contain an elementary atom; and (iii) an aliphatic backbone bonded to at least one polymerizable olefin group; each containing a fluoroaliphatic group, an organic soluble group, and a polymerizable olefin group. This fatty acid group can be independently bonded via a covalent bond, a heteroatom, or an organic bridging group. What is attached to the skeleton of the family. 3. The polymerizable fluorochemical surfactant composition according to claim 1, comprising: The fluorinated oligomer has the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [During the ceremony, R1, R2, and R3 are independently derived from polymerizable olefin monomers; represents the polymerized units which together form an aliphatic skeleton: each Q is independently a covalent bond, a heteroatom, or an organic bonding group; Rf is a fluoroaliphatic group containing a fully fluorinated end group; Rs comprises a large number of carbon atoms and optionally one or more catenary is an organic soluble group that may contain an oxygen atom; Rp is a polymerizable olefin group; and a, b, c, d and e are all such that the above compound becomes an oligomer. and each n is independently 0 or 1. ] 2. The polymerizable fluorochemical surfactant composition of claim 1, comprising: 4. Following stages: (i) bringing together a fluorinated monomer, a soluble monomer, and a difunctional monomer; (ii) at least two fluoroaliphatic group side chains, at least two organic soluble groups; , and further contain side groups that can be synthesized into the polymerizable olefin group. to form an intermediate composition comprising one or more fluorinated oligomers comprising: Then, a fluorinated monomer, a soluble monomer, and a difunctional monomer are combined into an oligomer. become; and (iii) providing a composition according to claim 1, comprising a polymerizable olefin group; converting or further synthesizing said intermediate from step (ii) in order to A method for synthesizing the composition according to claim 1, comprising: 5. (a) Contains the monomer component of a pressure-sensitive adhesive based on acrylate. a large amount of polymerized units obtained from an acrylate-containing mixture; and (b) at least two fluoroaliphatic side chains, at least two organic soluble groups, and and at least one polymerizable olefin group side chain. Polymerizable, organic soluble, oligomeric polymers comprising fluorinated oligomers A polymer comprising a small amount of polymerized units obtained from an orochemical surfactant. Adhesive composition. 6. The above fluorinated oligomer is (i) at least two fluorinated polymers each having a fully fluorinated end group; rofatty acid group; (ii) each comprising a number of carbon atoms, and optionally one or more carbon atoms; at least one organic soluble group comprising more catenary oxygen atoms; as well as, (iii) an aliphatic backbone bonded to at least one polymerizable olefin group; each of a fluoroaliphatic group, an organic soluble group, and a polymerizable olefin group. is independently linked to this fatty acid via a covalent bond, a heteroatom, or an organic bonding group. 6. The adhesive composition of claim 5, wherein the adhesive composition is bonded to a backbone. 7. The above polymerizable fluorochemical surfactant has the following formula: ▲ mathematical formula, chemical formula, table There are etc.▼ [During the ceremony, R1, R2, and R3 are independently polymers obtained from polymerizable olefin monomers. represents a combination unit and together form an aliphatic skeleton; each Q is independently a covalent bond, a heteroatom, or an organic bonding group; Rf is a fluoroaliphatic group containing a fully fluorinated end group; Rs comprises a large number of carbon atoms and one or more catenary oxygen atoms; Rp or a polymerizable olefin group; and a, b, c, d and e are total numbers such that the above compound becomes an oligomer; and each n is independently 0 or 1. ] 6. The adhesive composition of claim 5, comprising an oligomer comprising: 8. The acrylate-containing mixture described above is characterized in that the alkyl group has from 1 to about 14 carbon atoms. large amounts of alkyl acrylates, including 6. The adhesive composition of claim 5, comprising a nomer. 9. The polymerized unit obtained from the polymerizable surfactant converts the acrylate into a base material. It is effective in reducing the surface tension of the composition compared to the pressure sensitive adhesive used as a material. 6. The adhesive composition of claim 5, wherein the adhesive composition is present in an amount of . 10. (a) Contains a monomer component of a pressure-sensitive adhesive based on acrylate. an acrylate-containing mixture consisting of; and (b) at least two fluoroaliphatic sides. chain, at least two organic soluble groups, and at least one polymerizable olefin group side polymerizable comprising one or more fluorinated oligomers each comprising a chain an organic soluble, oligomeric fluorochemical surfactant composition. a prepolymer composition comprising the above-mentioned surfactant composition; to lower the surface tension of this prepolymer composition compared to a mixture containing Something that is present in an effective amount. 11. Following stages: (i) Monomer components and photopolymerization initiator of pressure-sensitive adhesive based on acrylate put together; (ii) the composition from step (i) so as to increase its viscosity for application purposes; (iii) providing a prepolymer composition; the polymerizable fluorochemical surfactant and the composition from step (ii) to obtain (iv) combining the prepolymer composition from step (iii) with a low adhesion coating it on the carrier; and (v) Substantially completely photopolymerizing in an inert atmosphere. A method for preparing a pressure sensitive adhesive composition according to claim 5, comprising: