EP0716673A1 - Self-adhesive film and laminate using the same - Google Patents

Self-adhesive film and laminate using the same

Info

Publication number
EP0716673A1
EP0716673A1 EP94924476A EP94924476A EP0716673A1 EP 0716673 A1 EP0716673 A1 EP 0716673A1 EP 94924476 A EP94924476 A EP 94924476A EP 94924476 A EP94924476 A EP 94924476A EP 0716673 A1 EP0716673 A1 EP 0716673A1
Authority
EP
European Patent Office
Prior art keywords
oligomer
self
monomer
adhesive film
acrylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP94924476A
Other languages
German (de)
English (en)
French (fr)
Inventor
Sana Fujii
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0716673A1 publication Critical patent/EP0716673A1/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

Definitions

  • the self-adhesive film has substantially no surface tackiness.
  • the "self-adhesive film” herein referred to means a film-like adhesive capable of imparting a high adhesion strength by being self-contacted and pressed.
  • Japanese Unexamined Patent Publication (Kokai) No. 2-102282 discloses a self- adhesive material formed by applying a pressure-sensitive adhesive onto a base material.
  • this pressure-sensitive adhesive is tacky.
  • Japanese Unexamined Patent Publication (Kokai) No. 2-6578 discloses a self-fusion-bonding tape prepared by mixing uncrosslinked rubber and crosslinked rubber.
  • this tape is self-contacted and allowed to stand for a predetermined period of time, so as to be integrated, cohesive failure results when the adhered parts are debonded. It is, therefore, impossible to use the tape again.
  • this tape requires a long period of time in order to obtain a sufficient adhesion strength.
  • Japanese Unexamined Patent Publication (Kokai) No. 1-138280 discloses a self-adhesive tape having an adhesive layer obtained by adding a tackifier to a styrene-ethylene-butylene-styrene copolymer. Although the coated surfaces of this self-adhesive tape are adhered under a slight pressure, this tape does not adhere to the surfaces of many other articles, even to a smooth surface such as that of stainless steel, even if a high pressure is applied. In addition, since this adhesive layer is of an uncrosslinked type, it dissolves when it comes into contact with a solvent. Furthermore, the adhesive layer is applied to a base material, from a solvent solution of the adhesive.
  • At least 3 components should be added. Accordingly, in this high molecular weight material, it has been observed that homogeneous dispersion and mixing are comparatively difficult to achieve. When a homogeneous dispersion is not achieved, irregular adhesion strengths frequently result.
  • the present invention provides a self-adhesive film made of a simple and inexpensive material, which has little or no surface tackiness, which is unlikely to be contaminated with dust and which causes no cohesive failure, even when parts of a same film are adhered to each other and thereafter debonded.
  • the film of the invention is repeatedly usable.
  • the present invention also provides an adhesive laminate prepared by use of such a self- adhesive film.
  • the present invention provides a film having no or little surface tackiness.
  • the film comprises a copolymer of (A) at least one (meth)acrylic acid ester monomer and (B) at least one (meth)acrylic acid ester oligomer.
  • Oligomer (B) contains a reactive functional group. Preferably, this group is a radiation polymerizable group.
  • the glass transition temperature of a homopolymer derived from monomer (A) has a Tg of greater than 20°C.
  • the glass transition temperature of oligomer (B) is less than -20°C.
  • a film of the copolymer resulting from the polymerization of monomer (A) and oligomer (B) preferably has a glass transition of from 0-60°C. When expressed in terms of the Fox equation, the copolymer film has an F value of from about 2.8 x 10 "3 to 3.7 x 10 "3 .
  • Tg, Tg 2 ... Tg n denote the respective glass transition temperatures (in °C) of each of the first to the n-th components of the polymer prepared from monomer (A) and oligomer (B).
  • the present invention provides a self-adhesive film which is not easily contaminated with dust and the like owing to the absence of tackiness.
  • the film can repeatedly be used because no cohesive failure is caused even if the crosslinked films are adhered and then debonded.
  • the film is excellent in weather (light) resistance and water resistance, and can be prepared from a simple and inexpensive material.
  • Fig. 1 is a perspective view of a handle-bearing sample with the applied self-adhesive film of the invention as prepared in Example 1 hereinafter.
  • Fig. 2 is a graph showing the change of the self-adhesive strength (0 degree peel strength) of the self-adhesive film of the present invention as contrasted to the compositions of the oligomer and monomer of the present film.
  • Fig. 3 is a graph showing the change of the self-adhesion strength (0 degree peel strength) of the self-adhesive film of the present invention as contrasted to the thickness of the present film.
  • Examples of useful (meth)acrylic acid ester monomers useful as monomer (A) materials include tert-butyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, 2-t-butylphenyl acrylate, 2-naphthyl acrylate, methoxyphenyl acrylate, n-hexadecyl acrylate, dicyclopentenyl acrylate, 2- methoxycarbonylphenyl acrylate, 2-ethoxycarbonylphenyl acrylate, 2- chlorophenyl acrylate, p-tolyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2- hydroxypropyl methacrylate,
  • Examples of (meth)acrylic acid ester monomers useful in preparing oligomer (B) include ethyl acrylate, n-butyl acrylate, i-butyl acrylate, 2- ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, n-heptyl acrylate, n-hexyl acrylate, phenoxyethyl acrylate, propyl acrylate, i-octyl acrylate, isoamyl acrylate, butoxyethyl acrylate, methoxyethlene glycol acrylate, 2-methoxyethyl acrylate, 3-methoxypropyl acrylate, 3-methoxybutyl acrylate, 2-ethoxymethyl acrylate, 3-ethoxypropyl acrylate, isodecyl acrylate, lauryl methacrylate, n-octyl
  • ethyl acrylate is preferable, because it is easily available and favorable for the F value to be within the aforesaid range.
  • the molecular weight of oligomer (B) is preferably within the range between 1000 and 20000. When this molecular weight is too low, the tack of the film of the present invention become too high. When this molecular weight is too high, the viscosity of the oligomer becomes so high that its handling becomes difficult.
  • the reactive functional group useful in the invention include a (meth)acryloyl group, an allyl group, a vinyl group, an epoxy group, and an hydroxyl group.
  • the number of these is at least 1 based on 10 or more, preferably 50 or more of the acrylic acid ester units in the oligomer, and preferably 1 based on 1000 or less, preferably 200 or less of the acrylic acid ester units of the oligomer.
  • the number of this functional groups is too small, the copolymer of the aforesaid monomer and oligomer becomes paste-like, and does not form a film.
  • the number of the functional group is too many, self-adhesiveness is lost.
  • the Tg value of the homopolymer derived from monomer (A) is preferably 20 °C or higher.
  • the Tg value of this homopolymer is lower than 20°C, the requirement cannot be satisfied that the self-adhesive film of the present invention has no or little tackiness.
  • the Tg value of oligomer (B) is preferably lower than -20 °C.
  • the adhesiveness of the self-adhesive film of the present invention becomes insufficient and it becomes impossible to impart flexibility to this film.
  • the obtained film has no self-adhesiveness.
  • the copolymer film of the invention may be prepared by exposing a mixture of monomer (A) and oligomer (B) to active energy radiation such as ultraviolet light or electron beam radiation so as to polymerize and harden the mixture.
  • active energy radiation such as ultraviolet light or electron beam radiation
  • photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-n-propyl ether, benzoin-n- butyl ether, benzyl, benzophenone, p-methylbenzophenone, diacetyl, eosin, thionine, Michler's ketone, acetophenone, 2-chlorothioxanthone, anthraquinone, chloroanthraquinone, 2-methylanthraquinone, ⁇ -hydroxyisobutylphenone, p-isopropyl- ⁇ -hydroxyisobutylphenone, o-, ⁇ -'-dichloro-4-phenoxyacetonhenone, 1-hydroxy-l-cyclohexylacetophenone, 2,2-
  • the photopolymerization initiator is used preferably in a proportional amount normally ranging from about 0.1 to about 5 parts by weight based on 100 parts by weight of the sum amount of monomer (A) and oligomer (B).
  • a photopolymerization promotor can be combined with the initiator.
  • the photopolymerization promotor include tertiary amines such as triethylamine, triethanolamine, and 2- dimethylaminoethanol; alkylphosphines such as triphenylphosphine; thiols such as 3-thioglycol; and the like.
  • the ultraviolet light may be provided by, for example, a mercury lamp, a high pressure mercury lamp, a ultra high pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, etc.
  • the atmosphere in which the mixture is irradiated is preferably air or inert gas. When the atmosphere is air, it is preferable to use a high pressure mercury lamp as an irradiation source.
  • the irradiation intensity of ultraviolet rays is preferably within the range between 0.1 and 100 mW, and the dose thereof is preferably within the range between 100 and 20,000 mJ/cm 2 .
  • Polymerization by exposure to electron beam irradiation may be accomplished by employing a Cockcroft type accelerator, Cockcroft- Walton type one, resonant transformer type one, transformer type one, insulating core transformer type one, dynamitron type one, linear filament type one, broad beam type one, area beam type one, cathode electron type one, high frequency type one, and the like.
  • the accelerating voltage for the electron beam irradiation is preferably within the range between 100 and 500 kN, and the dose thereof is preferably within the range between 10 and 1000 kGy.
  • the aforesaid F value is within the range between 2.8 x 10 "3 and 3.7 x 10 "3 .
  • the F value is less than 2.8 x 10 "3 , the adhesiveness is insufficient and this case is not preferable.
  • this value is larger than 3.7 x 10 "3 , the present self-adhesive film has tackiness, and therefore, this case is also not preferable.
  • the criterion as to whether or not there is tackiness referred to in the present invention is defined by finger tackiness.
  • the films of the invention exhibit substantially no finger tackiness.
  • the thickness of the film of the present invention is preferably within the range between 20 and 5000 ⁇ .
  • the film When the film is too thin, the self- adhesiveness become lowered. On the contrary, when the film is too thick, the film becomes difficult to cure.
  • This film may have smooth surfaces. Alternatively, it may employ uneven surfaces. When the film has such uneven surfaces it is preferred that they mate with each other.
  • the height of the unevennesses is preferably within the range between 10 and 1000 ⁇ m. When the height is less than 10 ⁇ m, the adhesion strength is only minimally improved, and when the height exceeds 1000 ⁇ m, it becomes difficult for parts of the film to be fitted to each other.
  • the self-adhesive film may be adhered to a substrate so as to be laminated.
  • the utility value of the film is increased.
  • the film adhered to many different substrates include plates, tapes or other molded products having any shape.
  • the substrate may be made from plastic, glass, metal, and the like.
  • 1-octanethiol were subjected to reflux in 1 L of methyl ethyl ketone in a nitrogen gas flow (about 80°C).
  • a solution obtained by dissolving 0.8 g of azobisisobutylonitrile in methyl ethyl ketone was added dropwise to the reaction system, whereafter reflux under stirring was continued for 6 hours, so as to effect polymerization. Stopping the heating and the introduction of nitrogen, the obtained polymer was cooled to room temperature, whereafter 4.8 g of pyridine were added and stirred.
  • a solution obtained by dissolving 5.4 g of acrylic acid chloride in methyl ethyl ketone was then added dropwise to the mixture, and stirred for 3 hours.
  • the sandwiched mixture was cured by UV irradiation (UVL- ⁇ high pressure mercury lamp produced by Ushio Co., Ltd.; integral intensity: 900 mJ/cm 2 , measured by "UV-350” produced by ORC Inc.), so that a polymer film was prepared.
  • UV irradiation UVL- ⁇ high pressure mercury lamp produced by Ushio Co., Ltd.; integral intensity: 900 mJ/cm 2 , measured by "UV-350” produced by ORC Inc.
  • Fig. 1 shows a test specimen which comprises handle 1 secured acrylic plate 2.
  • a layer of cyanoacrylate adhesive 3 secures a section of the self-adhesive film 4 to the plate 2.
  • a PET film 5 covers the self- adhesive film 4.
  • a second test identical specimen (now shown) is used to measure the 0 degree peel strength.
  • the PET film 5 is removed from each of the test specimens.
  • the self-adhesive films 4 were then mutually contacted to each other.
  • a load of 500 g was applied to each of the test specimens for one minute after which these films were pulled in the direction perpendicular to the plane of the contacted surfaces by gripping the handles in the jaws of a "Tensilon 100". The force applied between these surfaces when they were debonded was reported as the 0 degree peel strength.
  • the 0 degree peel strength was found to be 8.7 kgf/cm 2 (average value of 5 measured results).
  • Example 2 The same experiment as in Example 1 was conducted with the exception that various acrylic acid ester monomers were used as reactive diluents.
  • the Tg values of a homopolymer derived from the monomers used as the reactive diluent, F values, whether or not there was tackiness, and 0 degree peeling strength (kgf/cm 2 ) in these cases are set forth in Table 1.
  • whether or not there was tackiness, and the degree of tackiness were judged according to whether or not there was sticky feeling and the degree of stickiness when a naked self-adhesive film was touched with a hand.
  • EHA 2-ethylhexyl acrylate
  • EA ethyl acrylate
  • DCPA dicyclopentanyl acrylate
  • Example 2 The same experiments as in Example 1 were conducted, with the exception that the ethyl acrylate oligomer synthesized in Example 1(1) was used as an oligomer, DCPA as a reactive diluent, so as to vary the composition ratio.
  • the composition was applied between two 50 ⁇ m thick PET films and exposed to UV irradiation.
  • whether or not there was tackiness was judged according to whether a naked self-adhesive film was sticky or not when it was touched with a hand. The results are set forth in Table 2.
  • Table 2 Table 2
  • Example 26 when the thickness of the self-adhesive film was varied is set forth in Fig. 3 (film thickness: 25 ⁇ m (Example 21), 50 ⁇ m (Example 22), 100 ⁇ m (Example 23), 200 ⁇ m (Example 24), and 300 ⁇ m (Example 25)).
  • the composition used the ethyl acrylate oligomer synthesized in Example l(l)as an oligomer, and IBA as a reactive diluent. It can be seen from Fig. 3 that before the film thickness reaches to about 200 ⁇ m, the self-adhesion strength of the film increases as the film thickness is increased, and even if the film thickness is increased above this value, the self-adhesion strength is hardly changed.
  • Example 26 Example 26
  • a mixture of 50 parts of the ethyl acrylate oligomer synthesized in Example 1 (1) and 50 parts of isobornyl acrylate was sandwiched between two parts of a PET film with a thickness of 100 ⁇ m, and the whole film thickness was controlled by use of a knife coater, so as to become 300 ⁇ m, following which the sandwiched mixture was cured by electron beam irradiation (EB accelerator: an area beam type electron beam irradiator produced by Nisshin High Voltage Co., Ltd.; in a nitrogen atmosphere, at an accelerating voltage of 300 kV, at an electron current of 30 mA, and at a dose of 100 kGy), whereby a film was prepared.
  • EB accelerator an area beam type electron beam irradiator produced by Nisshin High Voltage Co., Ltd.; in a nitrogen atmosphere, at an accelerating voltage of 300 kV, at an electron current of 30 mA, and at a dose of 100 kGy
  • EB accelerator
  • Example 27 A test sample with a handle was prepared as described in Example 1.
  • Example 1 shows that the self-adhesive film of the present invention is hard to be influenced by dust and the like.
  • Example 1 Test samples, each with a handle, were prepared as described in Example 1.
  • the self-adhesive film surfaces were then adhered to each other according to the method in Example 1, and were then once debonded. These film surfaces were then again adhered in the same way as above, and 0 degree peel strength of the sample was determined and found to be 8.6 kgf/cm 2 . This value is almost equal to the result obtained in Example 1 , which shows that the self-adhesive film of the present invention can repeatedly used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP94924476A 1993-09-01 1994-07-20 Self-adhesive film and laminate using the same Ceased EP0716673A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP217477/93 1993-09-01
JP5217477A JPH0782388A (ja) 1993-09-01 1993-09-01 自己接着性フィルム及びそれを用いた積層体
PCT/US1994/008166 WO1995006692A1 (en) 1993-09-01 1994-07-20 Self-adhesive film and laminate using the same

Publications (1)

Publication Number Publication Date
EP0716673A1 true EP0716673A1 (en) 1996-06-19

Family

ID=16704852

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94924476A Ceased EP0716673A1 (en) 1993-09-01 1994-07-20 Self-adhesive film and laminate using the same

Country Status (5)

Country Link
EP (1) EP0716673A1 (ko)
JP (1) JPH0782388A (ko)
KR (1) KR960703999A (ko)
CA (1) CA2168972A1 (ko)
WO (1) WO1995006692A1 (ko)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6972141B1 (en) 1997-12-12 2005-12-06 3M Innovative Properties Company Removable adhesive tape laminate and separable fastener
US6491781B1 (en) 1999-03-19 2002-12-10 3M Innovative Properties Company Image graphic system comprising a highly tacky adhesive and method for using same
US6870670B2 (en) 2001-04-06 2005-03-22 3M Innovative Properties Company Screens and methods for displaying information
KR20150095746A (ko) * 2012-12-10 2015-08-21 쓰리엠 이노베이티브 프로퍼티즈 컴파니 액체 광학 접착제 조성물

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04216886A (ja) * 1990-12-17 1992-08-06 Lintec Corp 耐ブリスター性粘着シート

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9506692A1 *

Also Published As

Publication number Publication date
WO1995006692A1 (en) 1995-03-09
JPH0782388A (ja) 1995-03-28
CA2168972A1 (en) 1995-03-09
KR960703999A (ko) 1996-08-31

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