WO2013135941A1 - An adhesive product, a method for making adhesive product, an use of adhesive product and a final product - Google Patents

An adhesive product, a method for making adhesive product, an use of adhesive product and a final product Download PDF

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Publication number
WO2013135941A1
WO2013135941A1 PCT/FI2012/050237 FI2012050237W WO2013135941A1 WO 2013135941 A1 WO2013135941 A1 WO 2013135941A1 FI 2012050237 W FI2012050237 W FI 2012050237W WO 2013135941 A1 WO2013135941 A1 WO 2013135941A1
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WO
WIPO (PCT)
Prior art keywords
adhesive product
product
thermoplastic polymer
adhesive
core material
Prior art date
Application number
PCT/FI2012/050237
Other languages
French (fr)
Inventor
Samantha Kiljunen
Mikko Tilli
Heikki Ahonen
Original Assignee
Upm-Kymmene Corporation
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 Upm-Kymmene Corporation filed Critical Upm-Kymmene Corporation
Priority to CN201290001221.5U priority Critical patent/CN204824708U/en
Priority to PCT/FI2012/050237 priority patent/WO2013135941A1/en
Priority to DE212012000254.5U priority patent/DE212012000254U1/en
Publication of WO2013135941A1 publication Critical patent/WO2013135941A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/10Adhesives in the form of films or foils without carriers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/20Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/204Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive coating being discontinuous
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/20Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/40Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2451/00Presence of graft polymer

Definitions

  • the invention relates to an adhesive product defined in the preamble of claim 1. Further, the in ⁇ vention relates to a method defined in the preamble of claim 17 for making an adhesive product. Further, the invention relates to use of an adhesive product de ⁇ fined in the preamble of claim 23. Further, the inven ⁇ tion relates to a final product defined in the pream ⁇ ble of claim 26. BACKGROUND OF THE INVENTION
  • the objective of the invention is to disclose a new adhesive product and method for making an adhe ⁇ sive product. Further, another objective of the inven ⁇ tion is to produce a new type of a final product with good quality.
  • the adhesive product according to the present invention is characterized by what is presented in claim 1.
  • the method for making adhesive product ac ⁇ cording to the present invention is characterized by what is presented in claim 17.
  • the use of the adhesive product according to the present invention is characterized by what is pre ⁇ sented in claim 23.
  • the final product according to the present invention is characterized by what is presented in claim 26.
  • Fig 1 is a flow chart illustration of a method according to one embodiment of the present inven ⁇ tion
  • Fig 2 is a flow chart illustration of a blow film process
  • Fig 3a and 3b show examples of the adhesive product
  • Fig 4 shows a structural picture of a film product .
  • the adhe- sive product comprises a core material (21) and an in ⁇ ert surface layer (22) on the core material
  • the core material includes at least active material (20) which contains thermoplastic polymer and thermoplastic polymer with anhydride moieties
  • the inert surface layer (22) contains thermoplastic polymer
  • the in ⁇ ert surface layer has been formed by reconstructing the surface of the core material, preferably toward lower surface free energy, so that the thin inert sur ⁇ face layer consisting of mainly pure non-polar thermoplastic polymer is formed on the surface of the active material, and a thickness of the thin inert surface layer is below 100 nm on the surface of the core mate ⁇ rial, and the inert surface layer covers at least 30 % of the core material surface.
  • the inert sur ⁇ face is arranged on the active material of the core ma- terial.
  • thermoplastic polymer (2) and thermoplastic polymer with anhydride moieties (3) are mixed (1), e.g. in an extruder or other device, to form an active material composition (4)
  • the adhesive prod ⁇ uct (8) which comprises a core material (21) including at least active material composition (4) and an inert surface layer (22) containing thermoplastic polymer on the core material is formed (7) by reconstructing the surface of the core material by means of heat and with pressure or without pressure and by means of the cooling (9) of the adhesive product (8), so that the thin inert surface layer consisting of mainly pure non-polar thermoplastic polymer is formed on the surface of the active material, and a thickness of the thin inert surface layer is below 100 nm on the surface of the core material, and the inert surface layer is arranged to cover at least 30 % of the core material surface.
  • the adhesive product (8) is cooled (9) to provide sufficient time for a surface reconstruction of the core material (21) in order to form inert surface layer (22) on surface of the core material by recon ⁇ structing the surface of the core material, preferably toward lower surface free energy.
  • the adhe ⁇ sive product (8) is cooled (9) slowly to provide suffi- cient time for a surface reconstruction.
  • the anhydrides of the active material composition (4) hydrolyzed to acids are activated (5) back to anhy ⁇ drides during the forming of the adhesive product.
  • free moieties and impurities are preferably evaporated .
  • FIG. 1 An embodiment of the method of the present invention is shown in figure 1.
  • FIG. 2 An embodiment of the film making method is shown in figure 2.
  • Some embodi ⁇ ments of the adhesive products are shown in figures 3a and 3b and 4.
  • the surface of the adhesive product is reconstructed so that long non-modified thermoplastic polymer is arranged on the surface.
  • Dur ⁇ ing the reconstruction polar anhydride moieties, e.g. anhydride groups, and also acid moieties turn inside in air while non-polar and pure thermoplastic polymer segments point out. Pure non-polar thermoplastic poly- mer molecules forms protective layer on the surface.
  • the reconstruction rate can be raised by increasing temperature or reduc ⁇ ing molecular weight and crystallinity of adhesive product components.
  • the reconstruction is energy and entropy driven phenomena and hence spontaneous .
  • Reac ⁇ tive anhydride moieties groups may be protected with thin surface layer of thermoplastic polymer molecules.
  • the thin inert surface layer contains mainly only thermoplastic polymer substantially without the anhy ⁇ dride moieties, preferably without free anhydride and corresponding acid and their residue.
  • the adhesive product when the adhesive product is cooled by air then sufficient time for a surface reconstruction can be achieved.
  • free and residue substances have been removed from the inert surface. It is important for the adhesive product that it contains the active material with anhy ⁇ dride moieties which can be activated. Further, it is important for the adhesive product that it contains non- contaminated coupling moieties compatible with desired surface adhered. By means of the active material the ad ⁇ hesive product can be attached onto desired material surface.
  • the adhesive product of the invention has good wetting and adhesion properties.
  • the core material (21) includes the active material (20) and at least one material without anhydride chem ⁇ ical groups (23) .
  • the active material (20) and the material (23) without anhydride chemical groups are mixed to form the core material mixture.
  • the uniform core material (21) is formed from the formed core material mixture.
  • the core material (21) comprises at least one first layer (25) formed from the active material (20) and at least one second layer (26) formed from the material (23) without anhydride chemical groups, and the first layer (25) is arranged on the second layer (26) .
  • the inert surface layer (22) is arranged on the active material (20) containing layer.
  • material (23) without anhydride chemical groups is se ⁇ lected from natural fibres, wood fibres, cellulose, e.g. nanocellulose, polymer, plastic, e.g. thermo- plastic, metal, glass, carbon fiber, ceramics, semi ⁇ conducting material, photoactive material and similar materials and their combinations.
  • the core material (21) is formed the active material (20) .
  • the core material (21) con ⁇ tains the active material (20) over 80 % by weight.
  • the core material (21) contains the ac ⁇ tive material (20) over 90 % by weight.
  • the adhesive product (8) is in the form of beam, board, plate, coil, tube, sheet, film, foam, granu ⁇ late, particle, pellet, fiber, powder or their combi ⁇ nations .
  • the inert surface layer (22) is arranged on the outer surface of the adhesive product.
  • the inert surface covers at least 50 % of the core material surface, more preferable at least 60 % of the surface and most preferable at least 80 % of the surface.
  • the adhesive product (8) is surrounded by the inert surface layer (22) containing thermoplastic polymer.
  • the active material is under the inert surface layer.
  • thermo- plastic polymer should be understood as any thermo ⁇ plastic polymer suitable to be used in the present in ⁇ vention including also its derivatives and modifica ⁇ tions.
  • Different thermoplastic polymers may have dif ⁇ ferent properties, e.g. molecular composition, molecu- lar weight and molar mass.
  • thermo ⁇ plastic polymer can include at least one polymer com ⁇ ponent or combination of different polymer components.
  • the thermoplastic polymer is grafted.
  • thermoplastic polymer is polyolefin.
  • polyolefin is selected from a group consisting of polyethylene, polypropylene, other polyolefin and their co-polymers and combinations.
  • polyolefin should be understood as any polyolefin suitable to be used in the present invention including also its derivatives and modifica ⁇ tions. Different polyolefin may have different proper ⁇ ties, e.g. molecular weight and molar mass.
  • polyolefin can include at least one polyole- fin component or combination of different polyolefin components .
  • thermoplastic polymer can be other suitable thermoplastic polymer, e.g. EVA (eth ⁇ ylene vinyl acetate copolymer) or PUR (polyurethane) or the like, or their combination or mixture.
  • EVA eth ⁇ ylene vinyl acetate copolymer
  • PUR polyurethane
  • thermoplastic polymer and thermoplastic polymer with anhydride moieties can com ⁇ prise same polymer, e.g. polyolefin, or polymer composition, e.g. polyolefin composition.
  • thermoplastic polymer and thermoplastic polymer with anhydride moieties contain different polymer, e.g. polyolefin, or comprise different polymer composi ⁇ tions .
  • inert surface should be understood as any inert or stable surface of the product.
  • the active material con ⁇ tains less than 1.1 % anhydride moieties, free anhy ⁇ dride and corresponding acid and their residue in re- lation to quantity of thermoplastic polymer in the ac ⁇ tive material.
  • the product contains less than 1.07 mol-%, preferably less than 0.6 mol-% and more preferably less than 0.3 mol-%, free anhy ⁇ dride moieties, such as unbounded anhydride and corre- sponding acid, in relation to total amount of anhydride moieties, such as anhydride and corresponding acid .
  • anhydride moieties act as adhesion promoters.
  • anhydride moieties point out. Then the anhydride moieties set on the surface of the product (8) in order to make the product reactive.
  • a migration of the anhydride moieties into the inside of the product hap ⁇ pens during the reconstruction of the product In the migration the anhydride moieties go inside in the prod ⁇ uct .
  • a re-migration of the anhydride moieties onto the surface of the product happens during the re-reconstruction of the product.
  • the anhydride moieties go from the inside the product toward onto the surface of the product.
  • the anhydride moieties set on the surface of the product and new anhydride moieties groups go from the inside of the product toward onto the surface.
  • the surface free energy of the material can be determined by means of contact angle measurements .
  • the inert surface layer has contact angle with distilled water which contact angle is substantially same than the contact angle of said pure non-polar thermoplastic polymer in the surface layer.
  • the contact angle is measured to ensure the forming of the inert surface layer.
  • the contact angle of the inert surface is 0.9 - 1.1 times the contact angle of the pure same thermoplastic polymer, in one embodiment 0.95 - 1.05 times the contact angle of the pure same thermoplastic polymer.
  • physical form of the mate ⁇ rial surface is preferably similar.
  • the contact angle of the polymer is between 90 - 110 %, when meas- ured with distilled water.
  • wettability of the modified ther ⁇ moplastic polymer product is directly related to the chemical composition of its surface.
  • the wettability is measured by contact angle.
  • the contact angle of the adhesive product must be sub ⁇ stantially in the level of pure thermoplastic polymer when the product is in the stable form.
  • the contact angle of the adhesive product must be low at melted state against polar second mate- rial, e.g. wood based veneer.
  • the adhesive prod ⁇ uct is activated, preferably re-activated, by means of re-reconstruction of the surface before the use of the product. Then the inert surface changes from inert to reactive, preferably to adhesive.
  • the adhesive product can be made chemically reactive by re-reconstructing the surface layer so that anhydride moieties are pointing toward surface to be adhered by exposing it to polar matter.
  • the adhesive product is stable before the re-activation of the product.
  • the adhesive product is re-activated by heat and polar substrate.
  • a technical effect of the invention is that a stable adhesive product with non-contaminated active moieties is achieved but the product can be easily re ⁇ activated by re-heating.
  • An additional technical ef ⁇ fect is forming adhesive product which is moisture re ⁇ sistant and heat resistant under normal surrounding conditions.
  • One additional technical effect is that long term stability against moist air is achieved.
  • the thickness of the inert surface layer is arranged below 70 nm, preferably 50 nm and more preferably below 30 nm. In one embodiment of the present invention the thickness of the inert surface layer is arranged between 0.1 - 100 nm, in one embodiment between 5 - 100 nm.
  • the thickness of the inert surface layer is between 5 - 70 nm, in one embodiment between 5 - 50 nm, in one embodiment between 5 - 30 nm and in one embodiment be- tween 10 - 50 nm. It is important for the thickness of the inert surface that the inert surface protects the product and its reactive anhydride moieties groups, and water is not absorbed on the surface of the product. For example water does not go through the inert surface un- der conditions in which relative humidity is less than 65 % and temperature is about 25 °C. Preferably, free surface energy is determined as a function of tempera ⁇ ture. On the other hand, it is important for the thick ⁇ ness of the inert surface that the product can be easily re-activated, e.g. by heating quickly. Preferably, the inert surface is hydrophobic.
  • the product (8) is formed (7) by means of an extrusion process. In one embodiment the product (8) is formed (7) by means of a blown film pro- cess.
  • firstly an intermediate product is formed and secondly an adhesive product (8) is formed from the intermediate product.
  • an intermediate product in the form of a film (24) is first formed (7) by means of a blown film extrusion process, and the adhesive product (8) is formed from the film (24) .
  • the film is formed by a blown film extrusion and especially by a blown film co- extrusion.
  • the film is formed by means of a cast film extrusion or similar film making extrusion process.
  • the film can be formed any suitable film making process but always the cooling (9) is carried out slowly, for example against non-polar substrate such as air, to ensure inert outer layers on the surface of the film (24) .
  • the blown film production is carried out after an extruder.
  • Blown film extrusion can be used to make thermoplastic films, tubes or bags.
  • the cross-section of the film can be uniform or multilayered .
  • the film extrusion can be carried out by blowing the film up- ward, downward or horizontal depending on the machine construction used.
  • the thermoplastic polymer material starts in a pellet form, which are successively com ⁇ pacted and melted in extruder and molten thermoplastic material is then forced, or extruded, through an annu- lar die.
  • the extruder temperature is typically around 190 - 200°C and temperature can be different in dif ⁇ ferent zones of the extruder heating unit.
  • thermoplastic used to make the film can be homogeneous or mixture of different thermoplastic pol- ymers with or without additives. Measured at the annu ⁇ lar die opening, the temperature of blown film can be as less as about 125 - 135°C or higher. Additionally, higher die temperatures or heated extrusion die lips can be used if needed. Typically production rates are usually in the level of 100 m/min, but can be up to 300 m/min with special machines.
  • Air or other gaseous substance is blown through a hole in the center of the die.
  • the pressure inside the film bubble causes the extruded melt to stretch and expand into a bubble.
  • the gas entering the bubble replaces gas leaving it, so that even and constant pressure is maintained to en- sure uniform thickness of the film.
  • the bubble is pulled continually forwards from the die and a cooling ring blows air or other gaseous substance onto the film.
  • the film can also be cooled from the inside using internal bubble cooling. This reduces the temperature inside the bubble, while main ⁇ taining the blown film diameter at the same time. After solidification at the frost line, the film moves into a set of nip rollers which collapse the bubble and flatten it into two flat film layers.
  • Blown film has a less effective cooling process than flat film keeping the film surface at melted state for longer time.
  • Flat film cooling is done by means of chill rolls or water, which have significantly higher spe- cific heat capacities than the air or other gaseous substance used in the blown film cooling process.
  • the film is then pulled by puller rolls onto windup roll ⁇ ers. Typically the film passes through idler rolls during this process to ensure that there is uniform tension in the film.
  • the film may pass through a treatment zone also. During this zone or stage, the film may be slit to form one or two films, or surface treated with flame, corona or plasma for example.
  • the adhesive product is a blown-formed product which has been arranged in the form of the film.
  • an intermediate product in the form of a fiber is first formed by means of a fiber extrusion process, and the adhesive product (8) is formed from the intermediate product.
  • the product (8) is cooled (9) by air.
  • a technical effect is that then sufficient slow time for a surface reconstruction is achieved.
  • An addi ⁇ tional technical effect is that the surface stays warm sufficient long time against non-polar substrate. Then a sufficient surface reconstruction is achieved on the surface before the thermoplastic surface reaches glass transition temperature.
  • air is cold or warm.
  • air is dried.
  • air is typical room air.
  • air dur ⁇ ing the adhesive product making to ensure the coming of the pure thermoplastic polymer onto the surface of the adhesive product (8) and the going of the anhy ⁇ dride moieties into the inside of the adhesive product (8) .
  • the air used can be dry air or moisture content in the air can be even 80 %.
  • the re-migration of the anhydride moieties towards the surface can happen when the air is completely removed and the adhesive product is pressed against a solid surface, preferably polar surface.
  • process agents and small mo ⁇ lecular thermoplastic polymers can be removed during the adhesive product making. Then the chemical bonding in the adhesive product can be improved.
  • the adhesive product or intermediate product is in the form of a film (24) which contains two active material layers including thermoplastic polymer (2) and thermo ⁇ plastic polymer with anhydride moieties (3) and at least one intermediary thermoplastic polymer layer, e.g. polyolefin layer, and the intermediary thermoplastic polymer layer is arranged between two active material layers and the inert surface layer is ar ⁇ ranged on the outer surface of the film (24) .
  • the thickness of the inter ⁇ mediary thermoplastic polymer layer is between 100 - 300 ym. In one embodiment the thickness of the active material layer is between 30 - 100 ym.
  • the thinner active material layer can be achieved more effective process in the film manufac ⁇ turing, in the adhesive product manufacturing or in the final product manufacturing. Then the manufacturing can be performed at lower temperatures and/or at higher running speed.
  • the inert surface layers containing thermoplastic pol ⁇ ymer, e.g. polyolefin, are formed on the both surfaces of the film (24) .
  • the inert surface layer is formed only on one surface of the film.
  • the adhesive product has been activated (5) before the form ⁇ ing of the inert surface.
  • any free anhydride moieties or pre-compound of the anhydride moieties, e.g. carboxylic acid of the same, is removed or decreased.
  • the ac ⁇ tivation (5) is carried out at temperatures over about 150 °C.
  • the activation process (5) is started at temperature over 150 °C.
  • the activation pro ⁇ cess (5) can be accelerated by increasing temperature and/or by catalyst. In a preferred embodiment all water generated during the activation (5) must be evaporated out .
  • thermoplastic polymer (2) and thermoplastic polymer with anhydride moieties (3) are mixed (1) and heated to temperature over 180 °C during the activation (5) .
  • the thickness of the anhydride moieties con ⁇ taining layer in the product (8) must be small enough to make stable end products. Thin layer releases internal moisture produced in the activation (5) more easily. The internal moisture ruins the stability. Moisture, as well as hazardous impurities, needs to be removed before and/or during the product manufacturing.
  • the anhydride moieties containing layer includes less than 500 ppm, preferably less than 200 ppm and more preferably 150 ppm, free anhydride and corresponding ac- id.
  • the product includes less than 70 %, preferably less than 50 % and more preferably less than 30 %, water in relation to total amount of the an ⁇ hydride moieties.
  • maleic anhydride is used as the anhydride moieties.
  • the anhy ⁇ dride moieties are activated (5) so that free and/or grafted maleic acid in the active material composition is converted to reactive maleic anhydride during less than 2 minutes, preferably during about 1 minute, at temperature over 180 °C.
  • the anhy ⁇ dride moieties are activated (5) so that free and/or grafted maleic acid in the active material composition is converted to reactive maleic anhydride during 2 - 4 minutes at temperature over 180 °C.
  • free and/or grafted maleic acid is converted at tempera ⁇ ture 180 - 190 ° C.
  • the active material composition includes maleic anhydride and maleic acid before the converting maleic acid to maleic anhydride.
  • the anhydride moieties are activated so that free maleic acid is removed.
  • the anhydrides of the active material composition (4) hydrolyzed to ac ⁇ ids are activated (5) back to anhydrides. Free and re ⁇ sidual maleic acid and free anhydrides can be removed or decreased during this activation process before and/or after an extrusion, e.g. in a cooling stage, and/or during an extrusion.
  • moisture and contaminants are removed.
  • conversion with over about 80 % anhydride and below about 20 % acid is pro ⁇ vided by the activation.
  • the inert surface layer is formed so that there is no free maleic anhy ⁇ dride on the surface of the product.
  • the free maleic an ⁇ hydride or corresponding carboxylic acid can be any monomer, oligomer or polymer containing these moieties and able to evaporate or surface segregate below the melting point of the base thermoplastic polymer of the active material .
  • any suitable agent, com- pound or composition containing anhydride or derivate of anhydride can be used as anhydride moieties.
  • the anhydride moieties can include one or more than one anhydride moieties component.
  • the anhydride moieties contain functional groups which may be activated into reactive form and which are capable of forming bonding with the second material.
  • thermoplastic polymer with anhydride moieties is anhydride grafted thermo ⁇ plastic polymer or anhydride grafted thermoplastic polyolefin.
  • thermoplastic polymer has similar or lower molecular weight than molecular weight of the thermoplastic polymer with anhydride moieties .
  • the active material contains less than 10 % by weight, preferably 1 - 4 %, in one embodiment 2 - 7 %, maleic anhydride grafted thermoplastic polymer.
  • the adhesive product in- eludes suitable additives which can be selected from the group: reinforcement fiber, filler, stabilizer agent, fire retardant agent, coloring agent and other suitable additive and their combinations.
  • suitable additives which can be selected from the group: reinforcement fiber, filler, stabilizer agent, fire retardant agent, coloring agent and other suitable additive and their combinations.
  • the intermediary layer includes at least one said additive.
  • the adhesive product is capable of forming covalent bonding with the second material, e.g. wood, metal, paper, plastic or other suitable material.
  • the invention relates to use of the present adhesive product (8) as glue or coating so that the adhesive product (8) is heated (10) at least over the melting point of the thermoplastic polymer in the inert surface for activating the adhesive product and the adhesive product (8) is used in the gluing or the coating.
  • the adhesive product is heated over the melting point of the thermoplastic poly ⁇ mer in the inert surface.
  • the adhesive product is heated over the melting points of the thermo ⁇ plastic polymers in the inert surface and in the active material.
  • the adhesive product (8) is used in the manufacturing (12) of a final product (11) in which the final product is coated by the adhesive product.
  • the adhesive product (8) is used in the manufacturing (12) of a final product (11) in which pieces of the final product are glued together by means of the adhesive product ( 8 ) .
  • the adhesive product (8) is used in the manufacturing (12) of a layered product (11) in which layers of the layered product are glued together by means of the adhesive product ( 8 ) .
  • the adhesive product (8) is used directly as the glue.
  • the glue includes the adhesive product of the present invention which can be treated in a desired way.
  • the protective inert surface layer disappears while polar anhydride moie ⁇ ties groups turn pointing toward interface.
  • Temporari ⁇ ly anhydride moieties free zone under interface anhy- dride moieties will be fulfilled with bulk anhydride moieties by molecular diffusion. Diffusion/migration is energy and entropy driven and hence spontaneous. After this reactive anhydride moieties are able to make covalent bonds with the second material. Re- reconstruction and diffusion rate are higher at ele- vated temperatures.
  • the invention relates to a final product (11) formed of two or more layers, such as ve ⁇ neers, being arranged the one above the other and com ⁇ bined by means of gluing with glue including said ad- hesive product (8) of the present invention.
  • a layered product (11) can be selected from a group consisting of a veneer product, wood board, panel product, plywood, fiber board, film product, composite board, block board, strand board, moulding product or their combinations.
  • a layered product (11) is formed of two or more veneers being arranged the one above the other and combined by means of glue.
  • a layer of the layered product can be formed any suitable material.
  • the layer of the layered product is formed wood, metal, paper, glass, plastic, other suitable material or their com ⁇ binations .
  • a layered product (11) is formed of two or more wood based veneers being ar ⁇ ranged the one above the other and combined by means of glue of the present invention.
  • the method of the present invention offers a possibility to prepare stable adhesive products which are moisture and temperature resistant and are capable of forming covalent bonding with the second material, e.g. with wood, metal, paper, plastic or other suita ⁇ ble material.
  • the adhesive product is easy to process, and it gives good protection to the final product. Further, the layered product with good dimension sta ⁇ bility can be achieved.
  • the layered product is post- and re-formable after re-heating, and it has good im ⁇ pact strength, moisture resistance and fatigue re ⁇ sistance.
  • the adhesive product and final product e.g. the layered product, can be formed cost-effectively.
  • an adhesive product 8 is formed in the form of granulates.
  • the adhesive product comprises an active material layer 25 and a polyolefin layer 26 which form together a core material 21.
  • the polyolefin core layer 26 is surrounded by the active material layer 25.
  • a film 24 is manufactured, and secondly granulates are formed from the film.
  • the active material layer 25 is formed from the active material composition 4 containing maleic anhydride grafted polyethylene 3 in polyethylene 2. Pure polyethylene 2 is mixed 1 with maleic anhydride grafted polyethylene 3 at temperature over 180 °C. The residual and hydrolysed maleic acid in the active ma- terial composition 4 is converted to reactive maleic anhydride during 2 - 4 minutes at temperature 180 - 190 ° C in the activation step 5. Then maleic acid con ⁇ tent decreases significantly and reactive maleic anhy ⁇ dride content increases.
  • the active material composi- tion 4 containing 2 to 10 % by weight maleic anhydride grafted polyethylene 3 in polyethylene 2.
  • Maleic anhy ⁇ dride grafted polyethylene 3 includes 0.2 to 5 mol-% maleic anhydride. Then total molecular anhydride con ⁇ centration is 0.004 to 0.25 mol-%.
  • the film 24 is formed 7 by a blow film co- extrusion which is shown in figure 2.
  • production rate is about 6 m/min and temperature of the extruder is between 180 - 200 °C in the blown film co-extrusion.
  • the residual and hydrolysed maleic acid in the active material com- position 4 can be converted to reactive maleic anhy ⁇ dride.
  • the extrusion step in which the anhydride moie ⁇ ties are activated takes about 1 minute.
  • the length of the film bubble is about 17 m, and the temperature of the film is about 40 °C before nip rollers.
  • the activation step 5 is a part of the extrusion step 7.
  • the thickness of the polyolefin layer 26 is about 200 - 300 ym, and the thickness of the active material layer 25 is about 50 ym.
  • the film 24 is cooled 9 slowly to provide suffi- cient time for re-crystallization of the polyethylene and surface reconstruction and/or to provide suffi ⁇ cient time for solidification of the polyethylene and surface reconstruction.
  • the cool ⁇ ing is made at a rate of about 1 degree per second.
  • the cooling happens so that the film cools about 50 degrees per meter from about 200 °C to 100 °C during the first two meters, i.e. about 5 de ⁇ grees per second.
  • Thin inert surface layers 22 are formed on the both outer surfaces of the film 24, on the surfaces of the active material layers.
  • the inert surface layer is formed by means of reconstruction of the surface. In the reconstruction the polar anhydride groups turn inside the film and non-polar polyethylene segments points out, toward the surface of the film.
  • the inert surface layer contains polyethylene but not reactive maleic anhydride grafted polyethylene. In the film making free anhydride and corresponding acid and their residue are removed. During forming inert sur ⁇ face layers residual moisture can be removed.
  • the thickness of the inert surface layer is arranged be ⁇ tween 5 - 50 nm.
  • the reactive maleic anhydride is pro ⁇ tected with the inert surface layers.
  • the formed polyethylene film 24 does not ex ⁇ hibit any moisture adsorption. The stable structure in humid air is achieved.
  • the formed adhesive product 8 is used as glue in plywood application 12 to glue veneers together.
  • the adhesive product 8 is heated 20 - 50 ° C over the melting temperature of polyethylene in the heating step 10. Then the re-reconstruction of the surface happens and the active maleic anhydride groups go from inside of the product toward onto the contact ⁇ ing surface of the product.
  • the veneers and the adhe ⁇ sive product are brought into contact in the heating step 10.
  • the adhesive product 8 can be used as a coating material.
  • the adhesive product of the present invention acts very good in the gluing and coating applications.
  • an adhesive product 8 is formed in the form of small particles.
  • the adhesive product comprises an active material layer 25 and a polyolefin layer 26 which form together a core material 21.
  • the polyolefin core layer 26 is surrounded by the active material layer 25. Firstly a fiber is manu- factured, and secondly small particles are formed from the fiber.
  • Example 3
  • an adhesive product 8 is formed in the form of dispersion.
  • the adhesive product comprises an active material layer 25 and a polyolefin layer 26 which form together a core material 21.
  • the polyolefin core layer 26 is surrounded by the active material layer 25. Firstly small particles are manu ⁇ factured, and secondly the small particles are mixed in the liquid medium.
  • the adhesive product according to the present invention is suitable in different embodiments to be used for gluing.
  • the method according to the present invention is suitable in different embodiments to be used for making the most different kinds of adhesive products.
  • the adhesive product according to the pre ⁇ sent invention is suitable in different embodiments to be used in different final products, e.g. adhesive compositions and layered products.

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Abstract

The invention relates to an adhesive product. According to the invention,the adhesive product(8)comprises a core material(21)and an inert surface layer (22)on the core material, and the core material includes at least active material(20)which contains thermoplastic polymer and thermoplastic polymer with anhydride moieties, and the inert surface layer contains thermoplastic polymer, and the inert surface layer has been formed by reconstructing the surface of the core material so that the thin inert surface layer consisting of mainly pure non-polar thermoplastic polymer is formed on the surface of the active material, and a thickness of the thin inert surface layer(22) is below 100 nm on the surface of the core material (21), and the inert surface layer covers at least 30 % of the core material surface. Further, the invention relates to a method for making an adhesive product. Further, the invention relates to use of the adhesive product and a layered product.

Description

AN ADHESIVE PRODUCT, A METHOD FOR MAKING ADHESIVE PRODUCT, AN USE OF ADHESIVE PRODUCT AND A FINAL PRODUCT FIELD OF THE INVENTION
The invention relates to an adhesive product defined in the preamble of claim 1. Further, the in¬ vention relates to a method defined in the preamble of claim 17 for making an adhesive product. Further, the invention relates to use of an adhesive product de¬ fined in the preamble of claim 23. Further, the inven¬ tion relates to a final product defined in the pream¬ ble of claim 26. BACKGROUND OF THE INVENTION
In patent publication WO 2009/103848 it is said that a polyolefin film contains maleated polyole- fin which contains maleic anhydride reactive groups. OBJECTIVE OF THE INVENTION
The objective of the invention is to disclose a new adhesive product and method for making an adhe¬ sive product. Further, another objective of the inven¬ tion is to produce a new type of a final product with good quality.
SUMMARY OF THE INVENTION
The adhesive product according to the present invention is characterized by what is presented in claim 1.
The method for making adhesive product ac¬ cording to the present invention is characterized by what is presented in claim 17. The use of the adhesive product according to the present invention is characterized by what is pre¬ sented in claim 23.
The final product according to the present invention is characterized by what is presented in claim 26.
BRIEF DESCRIPTION OF THE FIGURES The accompanying figures, which are included to provide a further understanding of the invention and constitutes a part of this specification, illus¬ trate some embodiments of the invention and together with the description help to explain the principles of the invention. In the figures:
Fig 1 is a flow chart illustration of a method according to one embodiment of the present inven¬ tion,
Fig 2 is a flow chart illustration of a blow film process,
Fig 3a and 3b show examples of the adhesive product, and
Fig 4 shows a structural picture of a film product .
DETAILED DESCRIPTION OF THE INVENTION
The present invention is based on an adhesive product. According to the present invention the adhe- sive product comprises a core material (21) and an in¬ ert surface layer (22) on the core material, and the core material includes at least active material (20) which contains thermoplastic polymer and thermoplastic polymer with anhydride moieties, and the inert surface layer (22) contains thermoplastic polymer, and the in¬ ert surface layer has been formed by reconstructing the surface of the core material, preferably toward lower surface free energy, so that the thin inert sur¬ face layer consisting of mainly pure non-polar thermoplastic polymer is formed on the surface of the active material, and a thickness of the thin inert surface layer is below 100 nm on the surface of the core mate¬ rial, and the inert surface layer covers at least 30 % of the core material surface. Preferably, the inert sur¬ face is arranged on the active material of the core ma- terial.
Further, the present invention is based on a method for making an adhesive product (8) . According to the present invention thermoplastic polymer (2) and thermoplastic polymer with anhydride moieties (3) are mixed (1), e.g. in an extruder or other device, to form an active material composition (4) , the adhesive prod¬ uct (8) which comprises a core material (21) including at least active material composition (4) and an inert surface layer (22) containing thermoplastic polymer on the core material is formed (7) by reconstructing the surface of the core material by means of heat and with pressure or without pressure and by means of the cooling (9) of the adhesive product (8), so that the thin inert surface layer consisting of mainly pure non-polar thermoplastic polymer is formed on the surface of the active material, and a thickness of the thin inert surface layer is below 100 nm on the surface of the core material, and the inert surface layer is arranged to cover at least 30 % of the core material surface. Preferably, the adhesive product (8) is cooled (9) to provide sufficient time for a surface reconstruction of the core material (21) in order to form inert surface layer (22) on surface of the core material by recon¬ structing the surface of the core material, preferably toward lower surface free energy. Preferably, the adhe¬ sive product (8) is cooled (9) slowly to provide suffi- cient time for a surface reconstruction. In one embodi¬ ment the anhydrides of the active material composition (4) hydrolyzed to acids are activated (5) back to anhy¬ drides during the forming of the adhesive product. For example, in the activation small molecular weight pol¬ ymers, free moieties and impurities are preferably evaporated .
An embodiment of the method of the present invention is shown in figure 1. An embodiment of the film making method is shown in figure 2. Some embodi¬ ments of the adhesive products are shown in figures 3a and 3b and 4.
In the invention the surface of the adhesive product is reconstructed so that long non-modified thermoplastic polymer is arranged on the surface. Dur¬ ing the reconstruction polar anhydride moieties, e.g. anhydride groups, and also acid moieties turn inside in air while non-polar and pure thermoplastic polymer segments point out. Pure non-polar thermoplastic poly- mer molecules forms protective layer on the surface. By means of the reconstruction lower surface free energy is achieved. In one embodiment the reconstruction rate can be raised by increasing temperature or reduc¬ ing molecular weight and crystallinity of adhesive product components. The reconstruction is energy and entropy driven phenomena and hence spontaneous . Reac¬ tive anhydride moieties groups may be protected with thin surface layer of thermoplastic polymer molecules. The thin inert surface layer contains mainly only thermoplastic polymer substantially without the anhy¬ dride moieties, preferably without free anhydride and corresponding acid and their residue. Preferably, when the adhesive product is cooled by air then sufficient time for a surface reconstruction can be achieved. Pref- erably, free and residue substances have been removed from the inert surface. It is important for the adhesive product that it contains the active material with anhy¬ dride moieties which can be activated. Further, it is important for the adhesive product that it contains non- contaminated coupling moieties compatible with desired surface adhered. By means of the active material the ad¬ hesive product can be attached onto desired material surface. The adhesive product of the invention has good wetting and adhesion properties.
In one embodiment of the present invention the core material (21) includes the active material (20) and at least one material without anhydride chem¬ ical groups (23) .
In one embodiment of the present invention the active material (20) and the material (23) without anhydride chemical groups are mixed to form the core material mixture. The uniform core material (21) is formed from the formed core material mixture.
In one embodiment of the present invention the core material (21) comprises at least one first layer (25) formed from the active material (20) and at least one second layer (26) formed from the material (23) without anhydride chemical groups, and the first layer (25) is arranged on the second layer (26) . Pref¬ erably, the inert surface layer (22) is arranged on the active material (20) containing layer.
In one embodiment of the present invention material (23) without anhydride chemical groups is se¬ lected from natural fibres, wood fibres, cellulose, e.g. nanocellulose, polymer, plastic, e.g. thermo- plastic, metal, glass, carbon fiber, ceramics, semi¬ conducting material, photoactive material and similar materials and their combinations.
In one embodiment of the present invention the core material (21) is formed the active material (20) . In one embodiment the core material (21) con¬ tains the active material (20) over 80 % by weight. In one embodiment the core material (21) contains the ac¬ tive material (20) over 90 % by weight.
In one embodiment of the present invention the adhesive product (8) is in the form of beam, board, plate, coil, tube, sheet, film, foam, granu¬ late, particle, pellet, fiber, powder or their combi¬ nations .
Preferably, the inert surface layer (22) is arranged on the outer surface of the adhesive product.
In one embodiment of the present invention the inert surface covers at least 50 % of the core material surface, more preferable at least 60 % of the surface and most preferable at least 80 % of the surface.
In one embodiment the adhesive product (8) is surrounded by the inert surface layer (22) containing thermoplastic polymer.
Preferably, the active material is under the inert surface layer.
In this specification the expression "thermo- plastic polymer" should be understood as any thermo¬ plastic polymer suitable to be used in the present in¬ vention including also its derivatives and modifica¬ tions. Different thermoplastic polymers may have dif¬ ferent properties, e.g. molecular composition, molecu- lar weight and molar mass. In this invention thermo¬ plastic polymer can include at least one polymer com¬ ponent or combination of different polymer components. In one preferred embodiment the thermoplastic polymer is grafted.
In one embodiment the thermoplastic polymer is polyolefin. In one embodiment of the present inven¬ tion polyolefin is selected from a group consisting of polyethylene, polypropylene, other polyolefin and their co-polymers and combinations. In this specifica- tion the expression "polyolefin" should be understood as any polyolefin suitable to be used in the present invention including also its derivatives and modifica¬ tions. Different polyolefin may have different proper¬ ties, e.g. molecular weight and molar mass. In this invention polyolefin can include at least one polyole- fin component or combination of different polyolefin components .
Alternatively, thermoplastic polymer can be other suitable thermoplastic polymer, e.g. EVA (eth¬ ylene vinyl acetate copolymer) or PUR (polyurethane) or the like, or their combination or mixture.
In one embodiment thermoplastic polymer and thermoplastic polymer with anhydride moieties can com¬ prise same polymer, e.g. polyolefin, or polymer composition, e.g. polyolefin composition. In one embodiment thermoplastic polymer and thermoplastic polymer with anhydride moieties contain different polymer, e.g. polyolefin, or comprise different polymer composi¬ tions .
In this specification the expression "inert surface" should be understood as any inert or stable surface of the product.
In one embodiment the active material con¬ tains less than 1.1 % anhydride moieties, free anhy¬ dride and corresponding acid and their residue in re- lation to quantity of thermoplastic polymer in the ac¬ tive material. In one embodiment the product contains less than 1.07 mol-%, preferably less than 0.6 mol-% and more preferably less than 0.3 mol-%, free anhy¬ dride moieties, such as unbounded anhydride and corre- sponding acid, in relation to total amount of anhydride moieties, such as anhydride and corresponding acid .
In a preferred embodiment anhydride moieties act as adhesion promoters.
In the reconstruction the polar and reactive anhydride moieties turn inside in the product (8) and non-polar and pure thermoplastic polymer segments point out. Pure non-polar thermoplastic polymer mole¬ cules form an inert surface layer on the surface of the product. Then the formed inert surface layer pro- tects reactive anhydride moieties groups in the product.
After the re-reconstruction the anhydride moieties point out. Then the anhydride moieties set on the surface of the product (8) in order to make the product reactive.
In a preferable embodiment a migration of the anhydride moieties into the inside of the product hap¬ pens during the reconstruction of the product. In the migration the anhydride moieties go inside in the prod¬ uct .
In a preferable embodiment a re-migration of the anhydride moieties onto the surface of the product happens during the re-reconstruction of the product. In the re-migration the anhydride moieties go from the inside the product toward onto the surface of the product. Preferably the anhydride moieties set on the surface of the product and new anhydride moieties groups go from the inside of the product toward onto the surface.
Preferably, the surface free energy of the material can be determined by means of contact angle measurements .
In one embodiment the inert surface layer has contact angle with distilled water which contact angle is substantially same than the contact angle of said pure non-polar thermoplastic polymer in the surface layer. Preferably, the contact angle is measured to ensure the forming of the inert surface layer.
In one embodiment the contact angle of the inert surface is 0.9 - 1.1 times the contact angle of the pure same thermoplastic polymer, in one embodiment 0.95 - 1.05 times the contact angle of the pure same thermoplastic polymer. Then physical form of the mate¬ rial surface is preferably similar. In contrast to similar polymer material without moieties the contact angle of the polymer is between 90 - 110 %, when meas- ured with distilled water.
Preferably, wettability of the modified ther¬ moplastic polymer product is directly related to the chemical composition of its surface. The wettability is measured by contact angle. In the present invention the contact angle of the adhesive product must be sub¬ stantially in the level of pure thermoplastic polymer when the product is in the stable form. To get good adhesiveness the contact angle of the adhesive product must be low at melted state against polar second mate- rial, e.g. wood based veneer.
In a preferred embodiment the adhesive prod¬ uct is activated, preferably re-activated, by means of re-reconstruction of the surface before the use of the product. Then the inert surface changes from inert to reactive, preferably to adhesive. The adhesive product can be made chemically reactive by re-reconstructing the surface layer so that anhydride moieties are pointing toward surface to be adhered by exposing it to polar matter. Preferably, the adhesive product is stable before the re-activation of the product. In one embodiment the adhesive product is re-activated by heat and polar substrate.
A technical effect of the invention is that a stable adhesive product with non-contaminated active moieties is achieved but the product can be easily re¬ activated by re-heating. An additional technical ef¬ fect is forming adhesive product which is moisture re¬ sistant and heat resistant under normal surrounding conditions. One additional technical effect is that long term stability against moist air is achieved. In one embodiment of the present invention the thickness of the inert surface layer is arranged below 70 nm, preferably 50 nm and more preferably below 30 nm. In one embodiment of the present invention the thickness of the inert surface layer is arranged between 0.1 - 100 nm, in one embodiment between 5 - 100 nm. In one embodi¬ ment the thickness of the inert surface layer is between 5 - 70 nm, in one embodiment between 5 - 50 nm, in one embodiment between 5 - 30 nm and in one embodiment be- tween 10 - 50 nm. It is important for the thickness of the inert surface that the inert surface protects the product and its reactive anhydride moieties groups, and water is not absorbed on the surface of the product. For example water does not go through the inert surface un- der conditions in which relative humidity is less than 65 % and temperature is about 25 °C. Preferably, free surface energy is determined as a function of tempera¬ ture. On the other hand, it is important for the thick¬ ness of the inert surface that the product can be easily re-activated, e.g. by heating quickly. Preferably, the inert surface is hydrophobic.
In one embodiment the product (8) is formed (7) by means of an extrusion process. In one embodiment the product (8) is formed (7) by means of a blown film pro- cess.
In one embodiment, firstly an intermediate product is formed and secondly an adhesive product (8) is formed from the intermediate product. In one embodi¬ ment, an intermediate product in the form of a film (24) is first formed (7) by means of a blown film extrusion process, and the adhesive product (8) is formed from the film (24) . In one embodiment the film is formed by a blown film extrusion and especially by a blown film co- extrusion. In one embodiment the film is formed by means of a cast film extrusion or similar film making extrusion process. The film can be formed any suitable film making process but always the cooling (9) is carried out slowly, for example against non-polar substrate such as air, to ensure inert outer layers on the surface of the film (24) . In one embodiment the blown film production is carried out after an extruder.
Blown film extrusion can be used to make thermoplastic films, tubes or bags. The cross-section of the film can be uniform or multilayered . The film extrusion can be carried out by blowing the film up- ward, downward or horizontal depending on the machine construction used. The thermoplastic polymer material starts in a pellet form, which are successively com¬ pacted and melted in extruder and molten thermoplastic material is then forced, or extruded, through an annu- lar die. The extruder temperature is typically around 190 - 200°C and temperature can be different in dif¬ ferent zones of the extruder heating unit. There can be one or more extruders forcing one or more thermo¬ plastic materials in the die unit and the orifices in the die are arranged such that the different material layers merge together before cooling. This method is called blown film co-extrusion producing multilayered films. The thermoplastic used to make the film can be homogeneous or mixture of different thermoplastic pol- ymers with or without additives. Measured at the annu¬ lar die opening, the temperature of blown film can be as less as about 125 - 135°C or higher. Additionally, higher die temperatures or heated extrusion die lips can be used if needed. Typically production rates are usually in the level of 100 m/min, but can be up to 300 m/min with special machines. Air or other gaseous substance is blown through a hole in the center of the die. The pressure inside the film bubble causes the extruded melt to stretch and expand into a bubble. The gas entering the bubble replaces gas leaving it, so that even and constant pressure is maintained to en- sure uniform thickness of the film. During the pro¬ cess, the bubble is pulled continually forwards from the die and a cooling ring blows air or other gaseous substance onto the film. The film can also be cooled from the inside using internal bubble cooling. This reduces the temperature inside the bubble, while main¬ taining the blown film diameter at the same time. After solidification at the frost line, the film moves into a set of nip rollers which collapse the bubble and flatten it into two flat film layers. Blown film has a less effective cooling process than flat film keeping the film surface at melted state for longer time. Flat film cooling is done by means of chill rolls or water, which have significantly higher spe- cific heat capacities than the air or other gaseous substance used in the blown film cooling process. The film is then pulled by puller rolls onto windup roll¬ ers. Typically the film passes through idler rolls during this process to ensure that there is uniform tension in the film. The film may pass through a treatment zone also. During this zone or stage, the film may be slit to form one or two films, or surface treated with flame, corona or plasma for example.
In one embodiment the adhesive product is a blown-formed product which has been arranged in the form of the film.
In one embodiment an intermediate product in the form of a fiber is first formed by means of a fiber extrusion process, and the adhesive product (8) is formed from the intermediate product.
In one embodiment the product (8) is cooled (9) by air. A technical effect is that then sufficient slow time for a surface reconstruction is achieved. An addi¬ tional technical effect is that the surface stays warm sufficient long time against non-polar substrate. Then a sufficient surface reconstruction is achieved on the surface before the thermoplastic surface reaches glass transition temperature. In one embodiment air is cold or warm. In one embodiment air is dried. In one embodiment air is typical room air.
In one preferred embodiment air is used dur¬ ing the adhesive product making to ensure the coming of the pure thermoplastic polymer onto the surface of the adhesive product (8) and the going of the anhy¬ dride moieties into the inside of the adhesive product (8) . The air used can be dry air or moisture content in the air can be even 80 %. The re-migration of the anhydride moieties towards the surface can happen when the air is completely removed and the adhesive product is pressed against a solid surface, preferably polar surface.
In one embodiment process agents and small mo¬ lecular thermoplastic polymers can be removed during the adhesive product making. Then the chemical bonding in the adhesive product can be improved.
In one embodiment of the present invention the adhesive product or intermediate product is in the form of a film (24) which contains two active material layers including thermoplastic polymer (2) and thermo¬ plastic polymer with anhydride moieties (3) and at least one intermediary thermoplastic polymer layer, e.g. polyolefin layer, and the intermediary thermoplastic polymer layer is arranged between two active material layers and the inert surface layer is ar¬ ranged on the outer surface of the film (24) .
In one embodiment the thickness of the inter¬ mediary thermoplastic polymer layer is between 100 - 300 ym. In one embodiment the thickness of the active material layer is between 30 - 100 ym. Preferably, by means of the thinner active material layer can be achieved more effective process in the film manufac¬ turing, in the adhesive product manufacturing or in the final product manufacturing. Then the manufacturing can be performed at lower temperatures and/or at higher running speed.
In one embodiment of the present invention the inert surface layers containing thermoplastic pol¬ ymer, e.g. polyolefin, are formed on the both surfaces of the film (24) . In alternative embodiment the inert surface layer is formed only on one surface of the film.
In one embodiment of the present invention the adhesive product has been activated (5) before the form¬ ing of the inert surface. Preferably, at the same pro¬ cess stage any free anhydride moieties or pre-compound of the anhydride moieties, e.g. carboxylic acid of the same, is removed or decreased. In one embodiment the ac¬ tivation (5) is carried out at temperatures over about 150 °C. In one embodiment the activation process (5) is started at temperature over 150 °C. The activation pro¬ cess (5) can be accelerated by increasing temperature and/or by catalyst. In a preferred embodiment all water generated during the activation (5) must be evaporated out .
In one embodiment of the present invention thermoplastic polymer (2) and thermoplastic polymer with anhydride moieties (3) are mixed (1) and heated to temperature over 180 °C during the activation (5) .
The thickness of the anhydride moieties con¬ taining layer in the product (8) must be small enough to make stable end products. Thin layer releases internal moisture produced in the activation (5) more easily. The internal moisture ruins the stability. Moisture, as well as hazardous impurities, needs to be removed before and/or during the product manufacturing. In one embodiment the anhydride moieties containing layer includes less than 500 ppm, preferably less than 200 ppm and more preferably 150 ppm, free anhydride and corresponding ac- id. In one embodiment the product includes less than 70 %, preferably less than 50 % and more preferably less than 30 %, water in relation to total amount of the an¬ hydride moieties.
In one embodiment maleic anhydride is used as the anhydride moieties. In one embodiment the anhy¬ dride moieties are activated (5) so that free and/or grafted maleic acid in the active material composition is converted to reactive maleic anhydride during less than 2 minutes, preferably during about 1 minute, at temperature over 180 °C. In one embodiment the anhy¬ dride moieties are activated (5) so that free and/or grafted maleic acid in the active material composition is converted to reactive maleic anhydride during 2 - 4 minutes at temperature over 180 °C. In one embodiment free and/or grafted maleic acid is converted at tempera¬ ture 180 - 190 °C. In one embodiment the active material composition includes maleic anhydride and maleic acid before the converting maleic acid to maleic anhydride. Preferably, the anhydride moieties are activated so that free maleic acid is removed. Preferably, the anhydrides of the active material composition (4) hydrolyzed to ac¬ ids are activated (5) back to anhydrides. Free and re¬ sidual maleic acid and free anhydrides can be removed or decreased during this activation process before and/or after an extrusion, e.g. in a cooling stage, and/or during an extrusion. Preferably, moisture and contaminants are removed. In one embodiment conversion with over about 80 % anhydride and below about 20 % acid is pro¬ vided by the activation. When free maleic acid and male¬ ic anhydride is removed from the product it increases stability of the product. Preferably, the inert surface layer is formed so that there is no free maleic anhy¬ dride on the surface of the product. The free maleic an¬ hydride or corresponding carboxylic acid can be any monomer, oligomer or polymer containing these moieties and able to evaporate or surface segregate below the melting point of the base thermoplastic polymer of the active material .
In this invention any suitable agent, com- pound or composition containing anhydride or derivate of anhydride can be used as anhydride moieties. The anhydride moieties can include one or more than one anhydride moieties component. In one embodiment the anhydride moieties contain functional groups which may be activated into reactive form and which are capable of forming bonding with the second material.
In one embodiment the thermoplastic polymer with anhydride moieties is anhydride grafted thermo¬ plastic polymer or anhydride grafted thermoplastic polyolefin.
In one embodiment thermoplastic polymer has similar or lower molecular weight than molecular weight of the thermoplastic polymer with anhydride moieties .
In one embodiment of the present invention the active material contains less than 10 % by weight, preferably 1 - 4 %, in one embodiment 2 - 7 %, maleic anhydride grafted thermoplastic polymer.
In one embodiment the adhesive product in- eludes suitable additives which can be selected from the group: reinforcement fiber, filler, stabilizer agent, fire retardant agent, coloring agent and other suitable additive and their combinations. In one em¬ bodiment the intermediary layer includes at least one said additive.
In one embodiment of the present invention the adhesive product is capable of forming covalent bonding with the second material, e.g. wood, metal, paper, plastic or other suitable material.
Further, the invention relates to use of the present adhesive product (8) as glue or coating so that the adhesive product (8) is heated (10) at least over the melting point of the thermoplastic polymer in the inert surface for activating the adhesive product and the adhesive product (8) is used in the gluing or the coating. In one embodiment the adhesive product is heated over the melting point of the thermoplastic poly¬ mer in the inert surface. In one embodiment the adhesive product is heated over the melting points of the thermo¬ plastic polymers in the inert surface and in the active material.
In one embodiment of the present invention the adhesive product (8) is used in the manufacturing (12) of a final product (11) in which the final product is coated by the adhesive product.
In one embodiment of the present invention the adhesive product (8) is used in the manufacturing (12) of a final product (11) in which pieces of the final product are glued together by means of the adhesive product ( 8 ) .
In one embodiment of the present invention the adhesive product (8) is used in the manufacturing (12) of a layered product (11) in which layers of the layered product are glued together by means of the adhesive product ( 8 ) .
In one embodiment the adhesive product (8) is used directly as the glue. In one embodiment the glue includes the adhesive product of the present invention which can be treated in a desired way.
Preferably, when the adhesive product (8) of the present invention is pressed against polar second material at elevated temperature, the protective inert surface layer disappears while polar anhydride moie¬ ties groups turn pointing toward interface. Temporari¬ ly anhydride moieties free zone under interface anhy- dride moieties will be fulfilled with bulk anhydride moieties by molecular diffusion. Diffusion/migration is energy and entropy driven and hence spontaneous. After this reactive anhydride moieties are able to make covalent bonds with the second material. Re- reconstruction and diffusion rate are higher at ele- vated temperatures.
Further, the invention relates to a final product (11) formed of two or more layers, such as ve¬ neers, being arranged the one above the other and com¬ bined by means of gluing with glue including said ad- hesive product (8) of the present invention.
In one embodiment, a layered product (11) can be selected from a group consisting of a veneer product, wood board, panel product, plywood, fiber board, film product, composite board, block board, strand board, moulding product or their combinations.
In one embodiment a layered product (11) is formed of two or more veneers being arranged the one above the other and combined by means of glue.
A layer of the layered product can be formed any suitable material. In one embodiment the layer of the layered product is formed wood, metal, paper, glass, plastic, other suitable material or their com¬ binations .
In one embodiment a layered product (11) is formed of two or more wood based veneers being ar¬ ranged the one above the other and combined by means of glue of the present invention.
The method of the present invention offers a possibility to prepare stable adhesive products which are moisture and temperature resistant and are capable of forming covalent bonding with the second material, e.g. with wood, metal, paper, plastic or other suita¬ ble material. The adhesive product is easy to process, and it gives good protection to the final product. Further, the layered product with good dimension sta¬ bility can be achieved. The layered product is post- and re-formable after re-heating, and it has good im¬ pact strength, moisture resistance and fatigue re¬ sistance. The adhesive product and final product, e.g. the layered product, can be formed cost-effectively.
EXAMPLES
In the following, the invention is described in more detail by means of detailed exemplary embodi¬ ment with reference to the accompanying figures.
Example 1
In this example an adhesive product 8 is formed in the form of granulates. The adhesive product comprises an active material layer 25 and a polyolefin layer 26 which form together a core material 21. The polyolefin core layer 26 is surrounded by the active material layer 25. Firstly a film 24 is manufactured, and secondly granulates are formed from the film.
The active material layer 25 is formed from the active material composition 4 containing maleic anhydride grafted polyethylene 3 in polyethylene 2. Pure polyethylene 2 is mixed 1 with maleic anhydride grafted polyethylene 3 at temperature over 180 °C. The residual and hydrolysed maleic acid in the active ma- terial composition 4 is converted to reactive maleic anhydride during 2 - 4 minutes at temperature 180 - 190 °C in the activation step 5. Then maleic acid con¬ tent decreases significantly and reactive maleic anhy¬ dride content increases. The active material composi- tion 4 containing 2 to 10 % by weight maleic anhydride grafted polyethylene 3 in polyethylene 2. Maleic anhy¬ dride grafted polyethylene 3 includes 0.2 to 5 mol-% maleic anhydride. Then total molecular anhydride con¬ centration is 0.004 to 0.25 mol-%.
The film 24 is formed 7 by a blow film co- extrusion which is shown in figure 2. In one example, production rate is about 6 m/min and temperature of the extruder is between 180 - 200 °C in the blown film co-extrusion. Further, in the extrusion the residual and hydrolysed maleic acid in the active material com- position 4 can be converted to reactive maleic anhy¬ dride. The extrusion step in which the anhydride moie¬ ties are activated takes about 1 minute. The length of the film bubble is about 17 m, and the temperature of the film is about 40 °C before nip rollers. Preferably, the activation step 5 is a part of the extrusion step 7.
The thickness of the polyolefin layer 26 is about 200 - 300 ym, and the thickness of the active material layer 25 is about 50 ym. After the film mak¬ ing 7 the film 24 is cooled 9 slowly to provide suffi- cient time for re-crystallization of the polyethylene and surface reconstruction and/or to provide suffi¬ cient time for solidification of the polyethylene and surface reconstruction. In this embodiment, the cool¬ ing is made at a rate of about 1 degree per second. In one embodiment, the cooling happens so that the film cools about 50 degrees per meter from about 200 °C to 100 °C during the first two meters, i.e. about 5 de¬ grees per second. Thin inert surface layers 22 are formed on the both outer surfaces of the film 24, on the surfaces of the active material layers. The inert surface layer is formed by means of reconstruction of the surface. In the reconstruction the polar anhydride groups turn inside the film and non-polar polyethylene segments points out, toward the surface of the film. The inert surface layer contains polyethylene but not reactive maleic anhydride grafted polyethylene. In the film making free anhydride and corresponding acid and their residue are removed. During forming inert sur¬ face layers residual moisture can be removed. The thickness of the inert surface layer is arranged be¬ tween 5 - 50 nm. The reactive maleic anhydride is pro¬ tected with the inert surface layers. The formed polyethylene film 24 does not ex¬ hibit any moisture adsorption. The stable structure in humid air is achieved.
After the film making product granulates 8 are formed from the film 24.
The formed adhesive product 8 is used as glue in plywood application 12 to glue veneers together. In the gluing the adhesive product 8 is heated 20 - 50 °C over the melting temperature of polyethylene in the heating step 10. Then the re-reconstruction of the surface happens and the active maleic anhydride groups go from inside of the product toward onto the contact¬ ing surface of the product. The veneers and the adhe¬ sive product are brought into contact in the heating step 10.
Alternatively, the adhesive product 8 can be used as a coating material.
With low anhydride level in the active mate¬ rial layers there is always excess of substrate groups present in gluing process. This leads to surface anhy¬ dride enrichment by re-reconstruction assisted migra¬ tion on polar groups of the substrate. Higher coverage can be achieved if more time and temperature are used.
It was discovered that the adhesive product of the present invention acts very good in the gluing and coating applications.
Example 2
In this example an adhesive product 8 is formed in the form of small particles. The adhesive product comprises an active material layer 25 and a polyolefin layer 26 which form together a core material 21. The polyolefin core layer 26 is surrounded by the active material layer 25. Firstly a fiber is manu- factured, and secondly small particles are formed from the fiber. Example 3
In this example an adhesive product 8 is formed in the form of dispersion. The adhesive product comprises an active material layer 25 and a polyolefin layer 26 which form together a core material 21. The polyolefin core layer 26 is surrounded by the active material layer 25. Firstly small particles are manu¬ factured, and secondly the small particles are mixed in the liquid medium.
The adhesive product according to the present invention is suitable in different embodiments to be used for gluing. The method according to the present invention is suitable in different embodiments to be used for making the most different kinds of adhesive products. The adhesive product according to the pre¬ sent invention is suitable in different embodiments to be used in different final products, e.g. adhesive compositions and layered products.
The invention is not limited merely to the example referred to above; instead many variations are possible within the scope of the inventive idea de¬ fined by the claims.

Claims

1. An adhesive product, c h a r a c t e r ¬ i z e d in that the adhesive product comprises a core material and an inert surface layer on the core mate¬ rial, and the core material includes at least active material which contains thermoplastic polymer and thermoplastic polymer with anhydride moieties, and the inert surface layer contains thermoplastic polymer, and the inert surface layer has been formed by recon¬ structing the surface of the core material so that the thin inert surface layer consisting of mainly pure non-polar thermoplastic polymer is formed on the sur¬ face of the active material, and a thickness of the thin inert surface layer is below 100 nm on the sur¬ face of the core material, and the inert surface layer covers at least 30 % of the core material surface.
2. The adhesive product according to claim 1, c h a r a c t e r i z e d in that a thickness of the in- ert surface layer is arranged below 50 nm.
3. The adhesive product according to claim 1 or 2, c h a r a c t e r i z e d in that the core material includes the active material and at least one material without anhydride chemical groups.
4. The adhesive product according to claim 3, c h a r a c t e r i z e d in that the active material and the material without anhydride chemical groups are mixed to form the core material mixture.
5. The adhesive product according to claim 3 or 4, c h a r a c t e r i z e d in that the core material comprises at least one first layer formed from the ac¬ tive material and at least one second layer formed from the material without anhydride chemical groups, and the first layer is arranged on the second layer.
6. The adhesive product according to any one of claims 3 to 5, c h a r a c t e r i z e d in that mate- rial without anhydride chemical groups is selected from natural fibres, wood fibres, cellulose, polymer, plastic, metal, glass, carbon fiber, ceramics, semi¬ conducting material, photoactive material and their combinations.
7. The adhesive product according to any one of claims 1 to 6, c h a r a c t e r i z e d in that the core material is formed the active material.
8. The adhesive product according to any one of claims 1 to 7, c h a r a c t e r i z e d in that the adhesive product is in the form of beam, board, plate, coil, tube, sheet, film, foam, granulate, particle, pellet, fiber, powder or their combinations.
9. The adhesive product according to any one of claims 1 to 8, c h a r a c t e r i z e d in that the inert surface covers at least 50 % of the core material surface .
10. The adhesive product according to any one of claims 1 to 9, c h a r a c t e r i z e d in that the adhesive product is surrounded by the inert surface layers containing thermoplastic polymer.
11. The adhesive product according to any one of claims 1 to 10, c h a r a c t e r i z e d in that the anhydride moieties is maleic anhydride.
12. The adhesive product according to any one of claims 1 to 11, c h a r a c t e r i z e d in that thermoplastic polymer is polyolefin.
13. The adhesive product according to claim 12, c h a r a c t e r i z e d in that polyolefin is se- lected from a group consisting of polyethylene, poly¬ propylene, other polyolefin and their co-polymers and combinations .
14. The adhesive product according to any one of claims 1 to 13, c h a r a c t e r i z e d in that the active material contains less than 10 % by weight thermoplastic polymer with anhydride moieties.
15. The adhesive product according to any one of claims 1 to 14, c h a r a c t e r i z e d in that the adhesive product is activated by re-reconstruction of the surface before the use of the adhesive product.
16. The adhesive product according to any one of claims 1 to 15, c h a r a c t e r i z e d in that the anhydride moieties of the adhesive product are capable of forming covalent bonding with the second material.
17. A method for making an adhesive product, c h a r a c t e r i z e d in that thermoplastic polymer
(2) and thermoplastic polymer with anhydride moieties
(3) are mixed (1) to form an active material composition
(4) , the adhesive product (8) which comprises a core material (21) including at least active material com- position (4) and an inert surface layer (22) containing thermoplastic polymer on the core material is formed (7) by reconstructing the surface of the core material by means of heat and by the cooling (9) of the adhesive product (8) so that the thin inert surface layer consisting of mainly pure non-polar thermoplastic polymer is formed on the surface of the active material, and a thickness of the thin inert surface layer is below 100 nm on the surface of the core mate¬ rial, and the inert surface layer is arranged to cover at least 30 % of the core material surface.
18. The method according to claim 17, c h a r a c t e r i z e d in that the adhesive product (8) is formed (7) by means of a blown film extrusion process .
19. The method according to claim 17 or 18, c h a r a c t e r i z e d in that an intermediate product in the form of a film (24) is first formed (7) by means of a blown film extrusion process, and the adhesive product (8) is formed from the intermediate product.
20. The method according to any one of claims
17 to 19, c h a r a c t e r i z e d in that an intermedi¬ ate product in the form of a fiber is first formed by means of a fiber extrusion process, and the adhesive product (8) is formed from the intermediate product.
21. The method according to any one of claims 17 to 20, c h a r a c t e r i z e d in that thermoplastic polymer (2) and thermoplastic polymer with anhydride moieties (3) are mixed to form the active material com¬ position (4) and heated to temperature over 180 °C so that the anhydrides of the active material composition (4) hydrolyzed to acids are activated (5) back to anhy- drides during the forming of the active material compo¬ sition .
22. The method according to any one of claims 17 to 21, c h a r a c t e r i z e d in that maleic anhy¬ dride is used as the anhydride moieties, and the anhy- drides hydrolyzed to acids are activated (5) back to an¬ hydrides so that free and/or grafted maleic acid is con¬ verted to reactive maleic anhydride during less than 2 minutes at temperature over 180 °C.
23. Use of the adhesive product (8) according to any one of claims 1 to 16 as a glue so that the ad¬ hesive product (8) is heated (10) over the melting point of the thermoplastic polymer in the inert sur¬ face for re-activating the adhesive product and the adhesive product is used in the gluing.
24. The use according to claim 23, c h a r a c t e r i z e d in that the adhesive product (8) is used in the manufacturing (12) of a final product (11) in which pieces of the final product are glued togeth¬ er by means of the adhesive product (8) .
25. The use according to claim 23, c h a r a c t e r i z e d in that the adhesive product (8) is used in the manufacturing (12) of a final product (11) in which the final product is coated by the adhesive product .
26. A layered product (11) formed of two or more layers being arranged the one above the other and combined by means of gluing with glue including the adhesive product (8) according to any one of claims 1 - 16.
PCT/FI2012/050237 2012-03-13 2012-03-13 An adhesive product, a method for making adhesive product, an use of adhesive product and a final product WO2013135941A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201290001221.5U CN204824708U (en) 2012-03-13 2012-03-13 Adhesive product and contain stratiform product of this adhesive product
PCT/FI2012/050237 WO2013135941A1 (en) 2012-03-13 2012-03-13 An adhesive product, a method for making adhesive product, an use of adhesive product and a final product
DE212012000254.5U DE212012000254U1 (en) 2012-03-13 2012-03-13 Adhesive product, use of an adhesive product and end product

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/FI2012/050237 WO2013135941A1 (en) 2012-03-13 2012-03-13 An adhesive product, a method for making adhesive product, an use of adhesive product and a final product

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Publication Number Publication Date
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5593759A (en) * 1992-10-20 1997-01-14 Avery Dennison Corporation Pressure-sensitive structural adhesive
US7005176B2 (en) * 2001-12-10 2006-02-28 Teijin Dupont Films Japan Limited Optical adhesive polyester film
US20070014985A1 (en) * 2005-07-14 2007-01-18 Yuan-Huffman Qingwen W Activatable compositions
US20080176012A1 (en) * 2006-09-11 2008-07-24 Mitsunobu Morita Heat-sensitive adhesive agent and heat-sensitive adhesive sheet
US20120052234A1 (en) * 2010-08-30 2012-03-01 Sriram Natarajan Adhesive structure with stiff protrusions on adhesive surface

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2662518T3 (en) 2008-02-18 2018-04-06 Upm Plywood Oy Postconformable plywood product and its manufacturing procedure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5593759A (en) * 1992-10-20 1997-01-14 Avery Dennison Corporation Pressure-sensitive structural adhesive
US7005176B2 (en) * 2001-12-10 2006-02-28 Teijin Dupont Films Japan Limited Optical adhesive polyester film
US20070014985A1 (en) * 2005-07-14 2007-01-18 Yuan-Huffman Qingwen W Activatable compositions
US20080176012A1 (en) * 2006-09-11 2008-07-24 Mitsunobu Morita Heat-sensitive adhesive agent and heat-sensitive adhesive sheet
US20120052234A1 (en) * 2010-08-30 2012-03-01 Sriram Natarajan Adhesive structure with stiff protrusions on adhesive surface

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