JP2008539097A - Self-adhesive laminate - Google Patents

Abstract

The decorative laminate includes an adhesive layer coated laminate substrate. The adhesive layer is a layer of a solventless acrylic polymer-containing adhesive material that is physically cured. The adhesive layer has self-adhesiveness at room temperature. The adhesive-coated laminate substrate has a peel force of at least 0.2 N / mm ² after being applied to the carrier. Also provided are methods for producing an adhesive-coated laminate substrate, its use as a coating material, and a composite of the adhesive-coated laminate substrate and a carrier material.

Description

Cross-reference of related applications The subject matter of this application is provisional application 60 / 652,257, filed February 11, 2005, and international patent application number EP 2004/009001, filed August 12, 2004. Related to the issue. Similarly, the international patent application number EP 2004/009001 claims priority based on the German patent application 2003 103 7351 filed on 14 August 2003. The entire publications of these related patent applications are hereby incorporated into the present specification and become a part of this specification, including but not limited to the portions that will become particularly apparent below.

The present invention relates to a decorative laminate substrate coated with a self-adhesive layer of an adhesive material comprising an acrylic polymer. Furthermore, this invention relates to the manufacturing method of the said laminated body.

  Laminated sheets (or “laminate substrates”) are commonly used for decorative applications in many areas of everyday life. They are used in the personal and commercial fields, for example for indoor structures and furniture coverings for windows, stairs and floor linings or covers.

  Laminated sheets are often made from cellulose sheets impregnated with a curable synthetic resin and pressed while heating under high pressure. One or more sheets on one or two sheet sides indicate a decorative color or decoration. The laminate sheet (known as high pressure laminate or HPL) is commercially available, for example, under the trade name RESOPAL ™ by Resopal GmbH (Wilsonart International Company).

  Laminated sheets can be applied with a water based adhesive to a carrier substrate such as chipboard, fireboard or plywood used for wall, floor or lining finishes or other purposes. Depending on the type of adhesive, various conditions must be accurately maintained to obtain a coating of high quality and stability. In accordance with known application methods, it is common to bond the laminated sheet and carrier immediately after application of the adhesive or after a short waiting time. The bonding is carried out according to the method described above under a pressing pressure of 2-5 bar and at a temperature of up to 120 ° C.

  Furthermore, the application of the adhesive is typically uniformly distributed on the laminated sheet and / or carrier surface in order to avoid warping. This is especially true in the case of adhesive systems containing water, where the application amount should be kept as low as possible.

  By applying the adhesive non-uniformly and holding the pressing pressure, pressing temperature and / or pressing time inaccurately, unsatisfactory results may be obtained during bonding. Thus, for example, excessively high temperatures can cause warpage and material damage. On the other hand, adhesion is often insufficient due to low temperature or low pressure. Depending on the adhesive system, the press pressure and temperature must be maintained for several minutes up to several hours. If necessary, one must wait overnight to reach final cure.

  Working with solvent-containing contact adhesives requires adhesion to comply with protection and disaster prevention regulations. Furthermore, the use of solvent-containing contact adhesives is generally classified as problematic from the perspective of health and environmental policy. By using a water-based dispersion adhesive (such as casein glue), the carrier surface partially swells, which frequently occurs when, for example, particleboard is used as the carrier material. As a result, a slightly corrugated or non-uniform plane is obtained. Furthermore, drying of the water or solvent containing contact adhesive may require several hours.

Reactive adhesives, such as epoxide, polyester or polyurethane adhesives, are also health concerns and require accurate knowledge and retention of processing conditions.
Previous adhesives and methods of bonding are typically high in equipment costs, for example, due to uniform and high press pressure and to maintain temperature. Depending on the adhesive, it may take several hours for curing, eg, sufficient adhesion to be obtained.

  Due to the circumstances described above, the use and satisfactory processing of laminated sheets is often relatively difficult, especially in the field of individuals or in the field of technicians. There is a need for decorative laminated panels that are improved, efficient, safe and inexpensive.

It is a general object of the present invention to provide an improved adhesive-coated laminate substrate, particularly for use as a decorative or protective laminate cover for materials such as wood, metal or inorganic boards.
A further particular object of the present invention is to overcome one or more of the problems described above. It takes into account and adapts the needs of individual users for simple processing or application in addition to the needs of the commercial field.

Another object of the present invention is to provide a decorative adhesive-coated laminate substrate that adheres quickly and firmly to the surface of a carrier substrate without having to accept long latencies.
A laminate that adheres quickly and firmly to the carrier can be obtained without the need to accurately hold and use high pressures or temperatures during application.

Another object of the present invention is to simplify or eliminate the handling and application of adhesives on a carrier. In particular, the difficulty of applying the adhesive uniformly to the carrier is avoided by applying the adhesive uniformly instead of the laminated substrate.
Furthermore, it is an object of the present invention to provide a decorative laminated substrate that can be bonded without using water or solvent, and is as objectivity as possible from the viewpoint of health and safety. .

Finally, it is an object of the present invention to provide a decorative laminate substrate that provides a uniform plane after being applied to a carrier.
The general objects of the present invention can be achieved at least in part through an improved decorative laminate substrate coated with an adhesive layer. The adhesive layer can include a layer of a solventless acrylic polymer-containing adhesive material that is physically cured. The adhesive layer has self-adhesive properties at room temperature.

  The present invention relates to a laminate comprising a laminated base material, a non-pressure sensitive adhesive layer applied to the laminated base material, and a self-adhesive layer applied to the non-pressure sensitive adhesive layer. Further included. The pressureless adhesive layer serves as a barrier layer (eg, a “primer”) to prevent the self-adhesive layer from penetrating and to provide a primed surface to the laminated substrate. . The self-adhesive layer includes a layer of a physically curable, solvent-free adhesive material that includes an acrylic polymer. The self-adhesive layer is self-adhesive at room temperature, meaning that it does not require heating for activation, and can be contacted with or without pressure or with light manual pressure It can be activated manually.

The present invention also includes a method for producing the laminate of the present invention.
Further provided is a composite material of a carrier and an adhesive-coated laminate substrate, and the use of an adhesive-coated laminate substrate for coating the carrier.

A decorative laminate having an adhesive layer, wherein the adhesive layer is a solvent-free adhesive layer that is physically cured and has self-adhesive properties at room temperature The laminate sheet has a peeling-off force of at least 0.2 N / mm ² after being applied to the carrier at room temperature. It is possible to produce a usable laminate that adheres quickly and firmly to the carrier in a manner that is not easily predictable, without having to accept long waiting times.

  Furthermore, the following advantages are achieved by the present invention. Applying the adhesive coated laminated substrate to the carrier can be accomplished without the use of high pressures and temperatures. Immediate adhesion to the carrier is generally sufficient, with just a short press pressure on the adhesive-coated laminate substrate, eg, by hand. Furthermore, the adhesive-coated laminated base material adheres firmly to the carrier. Therefore, for example, the peeling force of the adhesive-coated laminated base material from the carrier is very high. Furthermore, high peel resistance and high static shear strength are achieved.

  In addition, when a temperature load is applied to the composite of the adhesive-coated laminated base material and the carrier for a longer time, the adhesive remains stable, and the decorative adhesive-coated laminated base material has Obviously, it does not peel from the carrier. Adhesive properties such as peel force, shear strength, and peel resistance are also inherently retained with temperature loading. The above-mentioned features have already been achieved with a low application amount of adhesive or layer thickness so that it can be used in a material saving manner. Another advantage should be found that the end user himself does not need to undertake the application of the adhesive. The reverse laminate substrate can be prepared in advance with adhesive and processed quickly. That is, it can be applied to the carrier regardless of the processing conditions of the adhesive (such as uniform application) that must be observed.

  According to the invention, a laminated substrate that has already been applied with an adhesive can be stored for a relatively long time. As is typical of previous adhesive systems, it is not necessary to apply the laminated substrate to the carrier immediately after applying the adhesive. The adhesive-coated laminate substrate of the present invention provides a particularly uniform and flat surface after application to a carrier. Furthermore, according to the present invention, the bonding of the plates can be carried out using solvents and dispersants that are particularly advantageous with regard to environmental and health aspects. Finally, the adhesive used in accordance with the present invention contains only a low volatility plasticizer with relatively low evaporation.

  The advantages described above provide a relatively simple and easily attachable adhesive-coated laminate substrate for individual users and technicians without mechanical equipment. The above processing can be undertaken directly on site without the machinery or special equipment that must be used for the processing. Due to the possibility of concise and rapid application, the adhesive-coated laminate substrate according to the present invention is also particularly suitable for home users to cover or upgrade furniture, door surfaces, walls and the like.

  Other objects and advantages will become apparent to those skilled in the art from the following detailed description, taken together with the appended claims.

  The present invention provides a decorative laminate substrate having a self-adhesive layer applied either directly or indirectly to one side of the laminate substrate. In one embodiment of the invention, the self-adhesive layer comprises a solventless acrylic polymer-containing adhesive material that is physically applied at room temperature. The adhesive-coated laminate substrate of the present invention provides improved bond strength or adhesion, heat and moisture resistance, and sufficient shear or creep resistance when bonded to a carrier. The adhesive-coated laminate substrate is relatively easily applied by the end user as compared to typical known adhesive systems.

  According to the present invention, “laminated substrate” includes, for example, materials such as glass fiber fabric, paper, wood, textile, plastic film, paper-based laminate, laminated fabric, laminated wood, etc. Deposit (so-called, laminated) paper or fabric strips or glass fiber mats and coat or dip them with synthetic resins such as epoxies, melamine resins, thermoplastics, phenoplasts, urea-formaldehyde resins, And it is manufactured using pressure and heating. They are referred to by those skilled in the art as “laminates” and in various applications (eg, printed circuits), in aircraft, automobiles, marine components, weatherproof covers, sports equipment (eg, skiers) and decorative applications, It is used in various embodiments, for example, plates, round rods, tubes, long and shaped products.

  In one embodiment of the present invention, it has proven particularly advantageous to use a high pressure laminate (HPL) as the laminate substrate. The HPL has a layer of fiber strip (preferably paper) impregnated with a curable resin, and optionally one or more decorative layers, where the decorative layer includes Is provided with a decorative color and / or pattern and is preferably impregnated with a resin for the main component of melamine. The strips are bonded together under heating and pressure above about 5 mPa. According to the present invention, a continuously produced laminated material (CPL) can also be used as a laminated substrate.

  As will be appreciated by those skilled in the art, the following teaching provided herein, various and alternative types, shapes, and configurations of laminated substrates are used for use in the laminates of the present invention. be able to. Alternatives and details regarding the above materials can be found in, for example, current art literature, eg, “Ullmann's Encyclopedia of Industrial Chemistry” 4th Edition, Vol. 15, p. 326 and standards DIN EN 438, Part 1 to Part 6, ISO 4586-1, and ISO 4586-2 (incorporated herein by reference, respectively).

In one embodiment of the present invention, the laminated base material is preferably a decorative high-pressure laminated material produced by the following method. In the method, the fiber strip is impregnated with at least a curable resin and then pressed by simultaneously using heat (a temperature in the range of about 120 ° C. to about 150 ° C. is advantageous) at a pressure of at least 7 mPa, The resin is first flowed and then cured. It is desirable to obtain a uniformly closed material having a high density (advantageously about 1.35 g / cm ³ ) and the desired surface properties. Within the scope of this method, a discontinuous multi-stage press is used.

  In another embodiment of the present invention, a laminated substrate wherein the fiber strip is impregnated with a thermosetting resin and then continuously pressed on a double band press at high temperatures (preferably in the range of about 140 to about 200 ° C.). Proved to be particularly advantageous. The above method is particularly useful in the production of continuous production laminates (CPL).

  In another embodiment of the invention, a plastic laminate, in particular a polyester laminate made from a paper strip impregnated with at least one polyester resin, is used as the laminate substrate. Thereby, one or both sides of the laminate advantageously have decorative paper impregnated with a polyester resin.

  The thickness of the laminated substrate of the present invention can in principle be freely selected according to the field of application, and the thickness is generally in the range of 0.2 mm to 20 mm or 0.3 to 15 mm. . More desirably, the thickness can also be in the range of 0.5 mm to 3.0 mm or in the range of 0.6 to 2.5 mm. In one embodiment, a thickness of 0.6 to 1.6 mm is particularly desirable and a thickness of 0.6 to 1.2 mm is even more desirable.

  In one of the particularly preferred embodiments of the present invention, a self-adhesive layer is formed on at least one surface of the laminated base material using a solvent-free adhesive material that is physically cured. As used herein, “solventless” refers to an applied adhesive layer that does not contain organic liquid and water that act as a solvent or dispersant. In one embodiment, the self-adhesive layer is at least partially in the form of an acrylic polymer or copolymer containing adhesive material.

  In one particularly preferred embodiment of the present invention, the adhesive includes vinyl acetate-ethylene and acrylic terpolymers. Examples of such terpolymers are available from Air Products and Chemicals, Inc., Allentown, Pa. And is commercially available under the trademark FLEXBOND153. Other FLEXBOND adhesives such as FLEXBOND AF75 and FLEXBOND EAF60 are useful in forming the laminates of the present invention.

  In one embodiment of the invention, the self-adhesive layer includes at least one elastomer, at least one less volatile plasticizer, and at least one hydrocarbon-based resin. One or more additional components of the adhesive layer include natural rubber, polyisobutylene rubber, ethylene-propylene rubber (EPR), styrene-butadiene rubber, ethylene-propylene-diene-terpolymer rubber (EPDM), butyl rubber, ethylene- It can be an elastomer component selected from vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylate copolymers, ethylene- (meth) acrylic acid- (meth) acrylate terpolymers, and acrylate rubbers. The elastomer may also be a block copolymer as described below. One or more of the above elastomeric components can be mixed with an acrylic polymer, i.e. a polymer containing acrylic and / or acrylate groups, such as the vinyl acetate-ethylene-acrylic terpolymer described above.

  In one preferred embodiment of the present invention, the additional elastomer is about 300,000-3,500,000 g / mol, desirably about 400,000-1,500,000 g / mol, and more desirably about 800,000 g. A high molecular weight polyisobutylene rubber having a number average molecular weight of / mol (according to GPC). The polyisobutylene rubber can be copolymerized with one or more comonomers selected from styrene, ring-substituted styrene, divinylbenzene, isoprene, indene, 1,3-butadiene, and cyclopentadiene. The fraction of isobutene in the polyisobutylene rubber is desirably about 90%.

  In one embodiment of the invention, the total weight of the elastomer fraction is from about 10 to about 70 wt%, and preferably from about 30 to about 60 wt%, based on the dry weight of the adhesive. In this amount, the acrylic polymer (eg, vinyl acetate-ethylene-acrylic terpolymer) constitutes at least about 10% by weight of the adhesive and depends on whether other elastomers are also present, Up to about 70% by weight can be constituted. The balance of the adhesive composition includes about 15-40% by weight of the plasticizer, about 15-30% by weight of the hydrocarbon-based resin, and about 0.01-2% by weight of an antioxidant. .

  The plasticizer can be a low molecular weight polyisobutylene having a molecular weight of about 800 to about 5000 g / mol. The weight fraction of the low molecular weight polyisobutylene can be about 18 to about 25 wt%, based on the total weight of the adhesive.

  According to one embodiment of the present invention, isobutylene polymers that can be used in the adhesive are from Bayer AG, BAYER BUTYL (isobutylene and isoprene copolymer) and POLYSAR BUTYL XL (isobutylene, isoprene and divinylbenzene copolymer). Can be obtained under the trade name of

  According to one embodiment of the present invention, the end block of at least two vinyl-aromatic monomers (block A) and at least one intermediate block (block B) (contains a conjugated diene or ethylene-butylene copolymer or A block copolymer having an ethylene-propylene copolymer) can be used as the elastomer. Although the said form is based also on a manufacturing method, it can be a linear form, a graft form, or a star form.

  Typical block copolymers having the simplest structure have the structure, polystyrene-polybutadiene-polystyrene (SBS) or polystyrene-polyisoprene-polystyrene (SIS), or polystyrene-polyethylene / polybutylene-polystyrene. Typical radical or star polymers include those where the B block has three or four branches (radicals) or more branches (stars).

  The end block A of the copolymer is formed from one or more vinyl-aromatic monomers, which are styrene, ring alkylated styrenes such as α-methylstyrene and vinyl toluene, and polycyclic vinyl- Advantageously, it is selected from aromatic compounds such as vinyl naphthalene. Styrene and α-methylstyrene are preferred. Styrene is particularly preferred. The block made up as end block A can also be present one or several times in the middle of the polymer chain in addition to those at the end.

  If the intermediate block of the block copolymer comprises a conjugated diene, the intermediate block can be a homopolymer of a conjugated diene, a copolymer of several conjugated dienes, or a conjugated diene and a vinyl-aromatic compound (as long as the conjugated diene dominates For example, it can be a copolymer derived from styrene or α-methylstyrene. The conjugated diene is preferably selected from compounds having 4 to 8 carbon atoms, such as butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and piperylene, with butadiene and isoprene being preferred.

  When block B contains a conjugated diene, the block B may be partially or fully hydrogenated. Furthermore, the A block may also be partially or fully hydrogenated.

  The average molecular weight of the A block is about 5000-125,000 g / mol, and preferably about 6000-60,000 g / mol (weight average according to GPC). The average molecular weight of the B block is about 10,000 to 300,000 g / mol, and preferably about 30,000 to 150,000 g / mol (weight average according to GPC). The total weight of the block copolymer is desirably from about 25,000 to about 350,000 g / mol, more desirably from about 35,000 to 300,000 g / mol (weight average according to GPC). Advantageously, the fraction of A block is about 5-65 wt%, and more desirably about 35-50 wt%, relative to the block copolymer. Another advantageous range is about 5-30 wt%.

Details of the preparation of the block copolymers described above are described, for example, in EP 0537115 and US 3,239,478; 3,427,269; 3,700. No. 3,633; No. 3,753,936; and No. 3,932,327 (see the entirety of each publication and incorporated herein). .
The polymers described above can be used individually or in combination with each other.

  When used as an additional thermoplastic elastomer, the weight fraction of the block copolymer is desirably about 5-50 wt%, and more desirably about 10-40 wt%, based on the total weight of the adhesive. A more desirable range for the weight fraction of the block copolymer is about 12-25 wt%, and more desirably about 15-20 wt%. In some applications, another advantageous range is about 30-40 wt%.

  Non-exemplary block copolymers that can be used within one embodiment of the present invention are KRATON G1650, G1651, G1652, G1657, G4309 (various block length linear styrene-ethylene / butylene-ethylene block copolymers). , KRATON RP-6906, KRATON DX1122, and KRATON D1118X. These polymers can be obtained from KRATON Polymers, LLC.

In one advantageous embodiment, the adhesive is a synthetic plastic that has low volatility (evaporation loss or migration) at high temperatures (greater than about 120 ° C.) to provide particularly long-term tackiness. Contains agents.
Desirably, the plasticizer contained in the adhesive is a synthetic plasticizer having a high boiling point and a less volatile vapor pressure, and only exhibits slight evaporation from the adhesive.

  The plasticizer is advantageously selected from mineral oils, paraffin oils, olefin oligomers, and polymers having a low molecular weight. As the oligomer, for example, polypropylene, polybutene (for example, the above-mentioned low molecular weight polyisobutylene), hydrogenated polyisoprene, hydrogenated butadiene and the like can be used, and the molecular weight is about 350 to about 10,000 g / mol. Is advantageous.

The plasticizer weight fraction is desirably about 0-40 wt%, and more desirably about 15-40 wt%, or about 15-30 wt%, based on the total weight of the adhesive.
Furthermore, in order to obtain strong tackiness, a hydrocarbon-based resin can be added to the adhesive as desired. The tackiness (tack) allows for strong tackiness with low press pressure during assembly.

The group of hydrocarbon resins (tackifier) included in the adhesive includes natural and modified resins such as rubber resin, wood resin, tallow oil resin, and distillate resin. ), And rosin, hydrogenated resins, dimerized resins, and polymerized resins.
Similarly, glycerol and pentaerythritol esters of natural and modified resins (eg, those described above) can be used.

  Other resins that can be used as adhesives in the adhesive are polyterpene resins, hydrogenated polyterpene resins, copolymers and terpolymers of natural terpenes, such as styrene / terpene, α-methylstyrene / terpene, and vinyltoluene / Terpenes. For example, a phenol-modified terpene resin obtainable by condensation of terpene and phenol can also be used. Finally, petroleum based aliphatic, alicyclic, aromatic and aliphatic / aromatic resins can be used as the hydrocarbon resin. Other resins which can be used according to the invention and are known to the expert are mentioned in the document EP 0 537 715 (incorporated herein by reference in their entirety). ).

  The hydrocarbon resin may have a weight fraction of about 0 to 80 wt%, more preferably about 10 to 50 wt%, and even more preferably about 15 to 30 wt%, based on the total weight of the adhesive. it can.

  In one embodiment of the present invention, the self-adhesive layer and / or adhesive material is optionally provided with common stabilizers, antioxidants, and other auxiliaries known and available to those skilled in the art. , Fillers, and / or additives. Antioxidants can be advantageously selected from hindered phenols and multifunctional phenols such as sulfur and phosphorus containing phenols. An overview of the above stabilizers and additives is given in the documents of US Pat. No. 6,143,818 and EP-A-0537115 (see the entirety of each publication, hereby Incorporated). The weight fraction of the stabilizer is desirably about 0.1 to 2 wt%, and preferably about 0.1 to 1 wt%, based on the total weight of the adhesive.

  The self-adhesive laminates of the present invention desirably have high tack, strong immediate adhesion (viscosity), high cohesive strength, and good shear or creep resistance. As a result of the latter feature, the applied adhesive layer or applied laminate can be mechanically loaded. In one embodiment of the invention, the applied adhesive also advantageously has water resistance, weak acid resistance and alkali resistance. Using adhesives that do not contain water or other solvents or dispersants means that they do not cause swelling of the material along with the absorbent carrier substrate due to the liquid. In one embodiment of the invention, the adhesive used does not swell.

In one embodiment of the present invention, the adhesives described above are used, which are about 100% solids, a density of about 1 g / cm ³ (20 ° C.), about 15,000-65, 160 ° C. Viscosity of 000 mPas, processing temperature of 150-190 ° C., softening point of about 90-135 ° C. (DIN 52011), static shear resistance of about 5-15 kg at room temperature (based on DIN EN 1943), about 35-65 N / 25 mm And a shear strength loss temperature of from about 60 ° C. to about 105 ° C., and more preferably from about 65 ° C. to about 97 ° C. (see below for measurement method).

  In a particularly preferred embodiment of the present invention, the adhesive layer applied to the laminate sheet is covered with a release layer (preferably made of siliconized paper or film) for protection. In this state, the sheet can be stored for a long period of time, preferably up to 12 months, without losing its adhesive properties or undergoing a visible reduction.

The applied or added-on level of the adhesive described above to the laminated substrate is generally about 80 to about 300 g / m ² , desirably about 140 to about 240 g / m ² , and further Desirably about 150 to about 200 g / m ² . In one embodiment of the present invention, the adhesive layer is added in an amount of about 75 to about 150 g / m ² .

  The layer thickness of the self-adhesive layer of the laminated substrate is generally from about 0.05 to about 0.50 mm, or from about 0.08 to about 0.30 mm, more preferably from about 0.14 to about 0.00. 24 mm, and especially about 0.15 to about 0.20 mm. In one embodiment of the present invention, the self-adhesive layer has a thickness of about 0.175 mm. If both a self-adhesive layer and a pressure-sensitive adhesive layer are used, each layer can have a thickness of about 0.125 mm. The adhesive layer can be applied using a roller coater or other suitable coating equipment.

  Each adhesive layer is desirably applied as a water-based emulsion to the release layer or the laminated substrate, but the adhesive layer can be applied using an organic solvent-based emulsion or a hot melt. Although it is desirable to apply the adhesive layer first to the release paper and then to dry, the adhesive layer can also be applied first to the laminated substrate. When the adhesive emulsion is applied, the adhesive is dried, for example, at 100 ° C. for 5 minutes to form the applied solventless adhesive layer.

  According to the present invention, the pressing time when applying the adhesive-coated laminated substrate is less than 5 seconds. Advantageously, a press time of 1 to 3 seconds is sufficient to provide adhesion to the carrier with the following mechanical properties.

  According to one embodiment of the present invention, the pressing pressure required to apply the adhesive-coated laminated substrate to the carrier surface is a maximum of 2 bar. Desirably, the required pressing pressure is about 0.2-1 bar, and more preferably about 0.3-0.6 bar. In general, light pressure and manual work are sufficient to achieve complete adhesion. If the surface is large, uniform pressure using a roller is advantageous.

  With respect to one embodiment of the present invention, the application of the adhesive-coated laminated substrate is preferably performed in a temperature range of about 5 ° C to about 35 ° C. It is advantageous to apply the adhesive-coated laminate substrate on a carrier at room temperature.

In one embodiment of the present invention, the peel force required to peel from the carrier the adhesive-coated laminate substrate applied on the carrier is at least about 0.2 N / mm ² . Desirably, the peel force is from about 0.2 to about 2 N / mm ² , and more preferably from about 0.5 to about 1.5 N / mm ² , and even more preferably from about 0.8 to about 1.2 N. / Mm ² . These values of the peel force are achieved when the adhesive-coated laminate substrate is applied at room temperature using the press pressure described above, or by light manual pressure, or using a roller. Is desirable. The peel force is measured according to the method described in European standard EN311 (referenced in its entirety and incorporated herein).

  Alternatively, the peel force increases as the press pressure increases beyond the range of values described above. However, this is not a requirement of the present invention and can be achieved as desired if desired.

  Similarly, the peeling force of the adhesive-coated laminated base material from the carrier can be strengthened by heating for a short time before or before joining the laminated base material and the adhesive layer to the carrier. This criterion is not a requirement and is simply desired. Further, if the surface of the laminated base material to which the adhesive is applied is roughened using a normal grinding agent before the adhesive is applied, the peeling force may be affected. it can.

  Finally, it may be advantageous to pre-treat the surface of the laminate to which the adhesive is applied with a normal adhesive adhesive primer (ie, a preliminary paint or primer that provides adhesion) ( Not a requirement). Common adhesive primers include, for example, ethylene-acrylamide copolymers, high molecular weight isocyanates, and reactive silicon-organic compounds.

  With respect to one embodiment of the present invention, the adhesive coated laminated substrate is not observed to delaminate the laminated substrate from the carrier material (particularly particle board) up to a temperature load of up to 80 ° C. for at least 2 hours. It is characterized by that. In particular, with the composite of the laminate according to the invention and the carrier, no delamination is observed after a temperature load of about 50 ° C. to about 70 ° C. for at least 2 hours. The adhesive-coated laminate substrate is tested at room temperature by introducing the sample laminate substrate applied on the carrier into a furnace filled with ambient air. This means that the air inside the furnace has the same temperature and moisture content as the ambient air. At the beginning of the test, a temperature of about 20-23 ° C. and a relative humidity of 60-65% are exemplary conditions. Subsequently, the furnace is closed and heated to 80 ° C. and maintained at this temperature for at least 2 hours.

  The adhesive-coated laminated substrate of the present invention can be applied to various carriers, and the type of carrier is not particularly limited. Preferred carrier materials are melamine coated particle board, laminated film coated carrier plate, chipboard, medium density fiber plate, hard fiber plate, plywood board, veneer sheet, solid wood, honeycomb, Foams, metal plates, thin plates, inorganic carriers, natural and synthetic rocks, tiles and gypsum boards.

  The present invention further contemplates and includes a composite material comprising one of the carriers described above and an adhesive-coated laminate substrate adhered onto the carrier. Apply the laminated substrate to both liquid absorbent (absorbent) carriers, such as uncoated particleboard and uncoated wood, and non-liquid absorbent (nonabsorbable) carriers, such as coated wood, coated particleboard, etc. It can be advantageous to do so.

  One composite of an embodiment of the present invention is characterized by a uniform and flat surface on the surface of the applied laminated substrate. Accordingly, the maximum height difference on the surface of the decorative layer is about 0.05 to 0.5 mm, and more preferably about 0.05 to 0.2 mm. The uniformity can be easily measured by visual inspection, for example, a practice in which a light source (eg, a neon tube) reflects undistortedly on the surface of a laminated substrate applied to the carrier.

  According to one embodiment of the present invention, the adhesive coated laminated substrate applied to the carrier is generally compared to the laminated substrate applied to the carrier using conventional methods / adhesives: It has a more uniform and flat surface.

  Particularly advantageously, this feature appears on its own when the adhesive-coated laminate substrate is applied to an absorbent or liquid absorbent carrier. In this case, the laminated substrate forms a more uniform and flat surface than a sheet applied using a solvent or dispersant-containing adhesive.

  In another aspect, the present invention under consideration relates to the use of the adhesive-coated laminate substrate described above to coat a carrier material (preferably selected from the carrier materials described above). The carrier used can be both liquid absorbing (absorbent) and non-liquid absorbing.

  Similarly, the present invention provides the carrier material and adhesive-coated laminate substrate for indoor or outdoor structures, for example, to cover walls, linings and doors, and to manufacture and cover furniture and furniture parts. It is related to using it.

  Due to the aforementioned adhesive properties of the adhesive-coated laminate substrate on the carrier material (especially particle board) and the peel resistance with temperature load, the composite is also temporarily heated to a high temperature. Suitable for the production of parts of furniture to be used, for example, work plates in the kitchen.

The present invention also provides a method for producing a decorative laminated substrate having a self-adhesive layer. In one embodiment of the present invention, the adhesive material is applied to the laminated substrate at a temperature of 150-190 ° C. (advantageously, the decorative surface or the reverse side opposite the decorative layer) followed by cooling. It is characterized by making it.
Advantageously, it is desirable to apply the adhesive to a continuously proceeding laminate using a stationary roller or nozzle. The application speed of the adhesive to the laminate is desirably about 1 to 30 m / min.

The adhesive on the laminate substrate, about 80 to about 300 g / m ^2, preferably from about 140 to about 240 g / m ^2, and more desirably applied in an amount of from about 150 to about 200 g / m ^2.
The applied adhesive is advantageously covered with a release layer (advantageously made from siliconized paper or siliconized film).

  In another embodiment of the invention, the laminated substrate has two different adhesive layers applied to the laminated substrate. A pressureless adhesive layer is first applied to one side of the laminated substrate, and a self-adhesive layer is applied to the pressureless adhesive layer and thereby indirectly applied to the laminated substrate. . The self-adhesive layer includes a layer of a solventless acrylic polymer-containing adhesive material that is physically cured. The self-adhesive layer desirably has self-adhesive properties at room temperature. It is desirable that a release layer, such as a release paper or release film, be applied to the self-adhesive layer and maintain adhesion or tack until used.

  The self-adhesive layer preferably includes a vinyl acetate-ethylene and acrylic terpolymer. The pressure-sensitive adhesive layer includes an adhesive material having a glass transition temperature of about 20 ° C. or higher. The pressure-sensitive adhesive layer desirably acts as a barrier layer or primer that separates the self-adhesive layer from the laminated substrate. It is desirable that the barrier provided by the pressure-sensitive adhesive excludes or reduces the penetration of the self-adhesive into the laminated substrate. In one embodiment of the present invention, the pressure-sensitive adhesive layer is, for example, polyvinyl acetate. The pressureless adhesive layer may also be an acrylic primer as described below.

In one embodiment of the invention, the pressure-sensitive adhesive layer also has an loading of about 10 to about 30 g / m ² and the self-adhesive layer is about 75 to about 100 g / m ^2. The addition amount of Desirably, the pressure-sensitive adhesive is applied to the laminated substrate and subsequently the self-adhesive layer is at least partially cured or dried prior to application to the applied pressure-sensitive adhesive. . The pressure-sensitive adhesive layer desirably improves heat resistance and extends the shelf life of the laminate prior to end use or application to a carrier. Both the self-adhesive layer and the pressure-sensitive adhesive layer can be applied as, for example, a water-based emulsion, a solvent-based emulsion, or a hot melt.

  The adhesive-coated laminated base material can be prepared by the following method. First, the release layer is coated with a solvent-free acrylic polymer-containing adhesive layer that is physically cured. This is accomplished by first coating the release layer with an aqueous or other solvent-based acrylic adhesive, preferably containing about 35-75% by weight, or about 45-65% by weight adhesive solids. Can be achieved. The water or other solvent is then removed by evaporation at about 30-150 ° C, preferably about 75-120 ° C, for 1-15 minutes, or about 3-8 minutes, sufficient to dry. . The adhesive layer has a dry thickness of about 50-500 μm, or about 80-300 μm, and can have a wet thickness of about twice the thickness.

  Suitable release layers are available from Wausau Paper Co., Rhinelander, Wisconsin. Silicone coated paper, Type 402-6010, available from Various other plastic-coated papers and plastic films can also be used as the release layer. The adhesive layer can be thermoplastic or thermosetting, and is preferably thermoplastic. Suitable adhesive polymers include, but are not limited to, the acrylic polymers, copolymers and terpolymers described above.

  Second, the adhesive can be applied to the surface of the laminated substrate by placing the adhesive-coated release layer (having an adhesive surface facing the laminated substrate) on the laminated substrate. If the laminate substrate is a cellulosic high pressure laminate or another laminate having a relatively smooth surface, the surface is sanded or roughened before application of the adhesive. It may not be desirable to increase. Solventless adhesives are relatively viscous or solid and will not readily penetrate valleys and depressions present on rough surfaces. When the surface of the laminated substrate is relatively smooth, the adhesive can establish contact over the entire surface and obtain good adhesion.

  Alternatively, both sand and undercoating can be performed on the surface of the laminated substrate before application of the adhesive. Sanding creates a rough surface with valleys and depressions that are filled by a coating with a suitable primer. Suitable primers include readily drying solvent-based primers that have a polymer component that is compatible with the adhesive to be applied. For example, the acrylic primer is dried to form an acrylic smooth surface having an excellent affinity for the acrylic adhesive layer. One suitable polyolefin-based primer contains about 50% by weight solids and is sold by Lord Chemlok under the trade name 459X. The primer coating has a dry thickness of about 10-50 μm, or about 15-40 μm, and can have a wet thickness of about twice the thickness. Once the primer is dried, the adhesive can be applied to the undercoat surface of the laminated substrate.

Third, pressure is applied to the release layer to press the adhesive onto the surface of the laminated substrate. A suitable pressure is about 3 to 70 N / cm ² , preferably about 10 to 50 N / cm ² . Once the adhesive is pressed onto the laminated substrate, the release layer can be peeled off manually to expose the adhesive. For example, the release layer can be peeled manually, and the adhesive layer can be used to adhere the laminated substrate to a wall, floor, counter, or other surface.

  FIG. 1 illustrates an exemplary process 10 useful for coating the adhesive layer onto the laminated substrate. The adhesive layer 12 bonded to the release layer 14 is unwound from the roll 16. The above-described layers are bonded to the laminated substrate 18 within the nip defined by the nip rolls 20 and 22 and the adhesive layer 12 faces the surface 17 of the laminated substrate 18. Typically, the laminated substrate 18 is positioned so that the surface 17 is on its back surface (ie, the surface used to bond the adhesive-coated laminated substrate 28 to a wall, floor or object).

  FIG. 2 schematically illustrates another process 11 that is similar to the process 10 except for the presence of a heater. Before the adhesive layer 12 is applied to the surface 17 of the laminated substrate 18 and pressed, the adhesive layer 12 is applied to an external infrared heater 24 and / or an internal heater (not shown) in the roll 20. Can be used and heated. Alternatively or additionally, the laminated substrate 18 can be heated using an infrared heater 26 prior to application of the adhesive layer 12. In any case, the heating is sufficiently high to soften the adhesive layer 12 and provide a good adhesive layer to the laminated substrate 18, about 30-120 ° C., preferably 50- The temperature can be 80 ° C. The release layer 14 can be peeled away and the adhesive-coated laminate substrate 28 can be further bonded to the object.

  Examples of embodiments of the present invention are described below, but in no way limit the concept of the present invention.

1. All data for the production of adhesive-coated laminated substrates refers to weight.
An adhesive based on 25% SIS, 15% SBS, and 60% hydrocarbon-based resin (with 10% polybutene content) from a supply container heated to 180 ° C. has a width of 60 cm And it introduce | transduced into the roller heated at 180 degreeC. The thermoplastic liquefied adhesive is applied to the HPL sheet carried by the roller and traveling with the roller at 15 m / min (the gap between the roller and the HPL sheet is 3 mm) and the adhesive is 180 g / m Applied in ² quantities. For protection, siliconized paper was applied to the still warm adhesive layer. Subsequently, the HPL sheet coated with the adhesive was cooled.

2. Application of adhesive-coated laminated substrate to carrier material The adhesive-coated laminated substrate was applied to a carrier at room temperature. First, the position of the laminate on which the adhesive layer was covered with the siliconized release paper was adjusted on the carrier. Subsequently, the release paper is partially peeled off at the end portion (preferably a thin end portion), and the adhesive-coated laminated substrate having the exposed adhesive layer is pressed onto the carrier at the end portion. did. Next, under the adhesive-coated laminated base material, the release paper was extracted stepwise, and the laminated base material was manually pressed onto the carrier. Advantageously, the adhesive coated laminated substrate can be uniformly pressed onto the carrier substrate using a hard rubber roller. The next processing of the end can be done using a normal doctor, file and grinder.

3. Mechanical properties of composite materials
Peel Resistance According to the present invention, measured values for the peel resistance of the self-adhesive HPL for various substrates are shown below.
The peel resistance was measured according to EN311. Pressing the adhesive-coated laminated substrate onto the carrier was done by a light press by hand or using a roller.

  All the above measured values are based on a roughened HPL sheet. In the case of a smooth HPL surface, applying the adhesive in a dry state from the release layer to the HPL surface results in a somewhat higher peel resistance than the roughened surface, or wets the adhesive. Thus, when applied to the HPL surface, it can result in somewhat lower peel resistance.

Measurement of Tempering of Sheet Strength Loss A laminated substrate having an adhesive layer according to one embodiment of the present invention was cut to a size of 25 mm width and 70 mm length. The specimen was applied to the carrier in such a manner that there was a partial overlap of the 25 mm longitudinal bond area. A weight of 500 g was added to the lower end of the free test piece. Subsequently, the test set was placed in a furnace preheated to 40 ° C. and placed there at 40 ° C. for 30 minutes. Next, the heating furnace was heated at a rate of 0.37 ° C./min until the test piece was pulled away from the carrier.

Using the adhesive-coated laminated sheet according to the present invention, the shear resistance loss temperature (60 ° C. to 105 ° C.) was evaluated.
following;
1) FLEXBOND 153 for forming a self-adhesive layer;
2) FLEXBOND 153 for forming a self-adhesive layer and polyvinyl acetate for forming a pressure-sensitive adhesive layer:
Were used to prepare additional laminate samples (12.7 cm × 20.3 cm).
The laminate sample was applied to a chipboard and / or melamine carrier and tested. The adhesive layer was applied at about 5 mils (127 μm) and dried at 100 ° C. for 5 minutes.

The sample demonstrated heat resistance when applied to a carrier by maintaining adhesion and laminate bondability above 80 ° C. The sample was placed in a 60 ° C. oven and the temperature was raised to 10 ° C. every 2 hours until delamination was observed.
Each of the above samples further demonstrated a desirable long shelf life by maintaining laminate integrity at 75 ° C. for over 1.5 months.

The sample demonstrated moisture resistance by maintaining laminate bonding at a temperature of 65 ° C. and 95% humidity for over 14 days.
The samples further demonstrated desirable shear strength by having peel forces greater than 0.2 N / m ² (eg, about 0.26 and 0.35 N / mm ² , respectively). The peel resistance was measured according to EN311. The pressing of the substrate was performed by lightly pressing manually or using a roller.

  The invention disclosed herein by way of example can be suitably implemented with the exclusion of any element, portion, stage, or component not specifically disclosed herein.

  In the foregoing detailed description, the invention has been described with reference to certain preferred embodiments thereof, and numerous details have been set forth for the purpose of specific description, but the invention is not limited to additional embodiments. It will be apparent to those skilled in the art that certain details described herein can be varied significantly without departing from the basic nature of the invention.

FIG. 1 schematically illustrates a method for preparing the adhesive-coated laminated base material of the present invention. FIG. 2 schematically illustrates another method for preparing the adhesive-coated substrate of the present invention.

Claims (41)

A laminated substrate; and an adhesive layer covering the surface of the substrate;
An adhesive-coated laminate substrate comprising:
The adhesive layer comprises a physically curable, solventless adhesive material comprising an acrylic polymer;
The adhesive layer is self-adhesive at room temperature. The adhesive-coated laminated substrate of claim 1, wherein after being applied to a carrier substrate, the laminated substrate has a peel force of at least about 0.2 N / mm ² at room temperature. The adhesive-coated laminate substrate according to claim 1, wherein the laminate substrate has a peel force of about 0.5 to about 1.5 N / mm ² after being applied to a carrier substrate.   The adhesive-coated laminate substrate according to claim 1, wherein the release of the laminate substrate from the carrier does not appear to a temperature load of at least about 80 ° C for at least about 2 hours. The adhesive layer has the amount of from about 10 to about 300 g / m ^2, the adhesive-coated laminate substrate of claim 1. The adhesive layer has the amount of about 75 to about 100 g / m ^2, the adhesive-coated laminate substrate of claim 1.   The adhesive-coated laminate substrate according to claim 1, wherein the adhesive layer further comprises at least one of an additional thermoplastic elastomer, a block copolymer, a hydrocarbon-based resin, and a plasticizer.   The adhesive-coated laminate substrate according to claim 1, wherein the acrylic polymer comprises a terpolymer of vinyl acetate-ethylene and acrylic.   The adhesive-coated laminate substrate according to claim 1, wherein the laminate substrate comprises a high-pressure laminate (HPL) or a continuous production laminate (CPL).   The adhesive-coated laminate substrate according to claim 1, further comprising a release layer, wherein the adhesive layer is disposed between the laminate substrate and the release layer.   The adhesive-coated laminated substrate according to claim 10, wherein the release layer comprises a silicon-treated release paper or release film.   The adhesive-coated laminated substrate according to claim 1, further comprising a pressure-sensitive adhesive layer.   The adhesive-coated laminated substrate according to claim 12, wherein the pressure-sensitive adhesive layer is disposed between the laminated substrate and the self-adhesive layer.   The adhesive-coated laminate substrate according to claim 13, wherein the pressureless adhesive layer comprises a second adhesive material having a glass transition temperature of about 20 ° C. or higher. The non pressure sensitive adhesive layer has the amount of from about 10 to about 30 g / m ^2, the adhesive-coated laminate substrate according to claim 14.   The adhesive-coated laminated substrate according to claim 1, wherein the adhesive layer is applied to the substrate by a roller coater.   A composite material comprising the adhesive-coated laminate substrate of claim 1 applied to a carrier.   18. The composite material of claim 17, wherein the carrier is selected from the group consisting of uncoated particle board, uncoated wood material, metal, ceramic, glass, coated wood material, coated particle board, and combinations thereof. The method for producing an adhesive-coated laminated substrate according to claim 1, comprising the following steps:
Heating the adhesive material to a temperature of about 150C to about 190C;
Applying the adhesive material to the laminated substrate; and cooling the adhesive material to form an adhesive layer.   The method of claim 19, wherein the adhesive material is applied using a roller coater. Laminated substrate;
A laminate comprising: a non-pressure sensitive adhesive layer applied to the laminated substrate; and a self-adhesive layer applied to the non-pressure sensitive adhesive layer,
The self-adhesive layer comprises a solvent-free adhesive material that is physically cured;
The self-adhesive layer has self-adhesion at room temperature.   The laminate of claim 21, further comprising a release layer disposed on the self-adhesive layer.   The laminate of claim 21, wherein the pressureless adhesive layer comprises an adhesive material having a glass transition temperature of about 20 ° C. or higher. The non pressure sensitive adhesive layer comprises the amount of about 10 to about 30 g / m ^2, and the self-adhesive layer comprises an amount of from about 75 to about 100 g / m ^2, according to claim 21 Laminate.   The laminate of claim 21, wherein the self-adhesive layer comprises an adhesive material comprising an acrylic polymer.   The laminate of claim 21, wherein the self-adhesive layer comprises a vinyl acetate-ethylene and acrylic terpolymer.   27. A laminate according to claim 26, wherein the pressure-sensitive adhesive layer comprises polyvinyl acetate. A method of coating a laminated substrate with an adhesive comprising the steps of:
Providing a release layer coated with a layer of a physically curable, solventless adhesive comprising an acrylic polymer;
Applying the adhesive to the surface of the laminated substrate by placing a release layer coated with the adhesive on the laminated substrate; and applying pressure to the release layer to apply the adhesive Pressing on the surface of the laminated substrate:
The release layer can be peeled manually to expose the adhesive on the laminated substrate.   30. The method of claim 28, wherein the laminated substrate comprises a high pressure laminate of cellulose strip.   30. The method of claim 28, wherein the adhesive is applied to the surface of the laminated substrate without first sanding the surface of the laminated substrate. Further comprising the step of undercoating the surface of the laminated substrate to form an undercoating surface;
30. The method of claim 28, wherein the adhesive is applied to the primer surface.   32. The method of claim 31, further comprising sanding the surface of the laminated substrate prior to priming the surface of the laminated substrate.   29. The method of claim 28, wherein the pressure is applied by passing the adhesive coated release layer and the laminated substrate between a pair of nip rolls.   30. The method of claim 28, wherein the release layer comprises silicone coated paper.   29. The physically cured, solventless adhesive layer is provided by applying an aqueous acrylic adhesive to the release layer and drying the adhesive on the release layer. The method described in 1.   30. The method of claim 28, wherein the physically cured, solventless adhesive layer has a thickness of about 50 to about 500 [mu] m.   30. The method of claim 28, wherein the physically cured, solventless adhesive layer has a thickness of about 100 to about 300 [mu] m.   30. The method of claim 28, further comprising heating at least one of the adhesive and the laminated substrate prior to applying the pressure to the release layer.   32. The method of claim 31, wherein the primer surface comprises an acrylic primer.   40. The method of claim 39, wherein the primer has a dry thickness of about 10 to about 50 [mu] m.   39. The method of claim 38, wherein the heating comprises heating at least one of the adhesive and the laminated substrate to a temperature of about 30 to about 120C.

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