• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A retroreflective sheeting utilizing a particular polymer as the bead bond layer is disclosed. The polymeric bead bond comprises urethane and urea linkages, and has a stage prior to thermosetting in which it may be softened by the application of heat and in which it has a relatively nontacky character. Preferably the polymeric bead bond composition is prepared from an isocyanate-functional polymeric compound which has a substantial portion of its isocyanate groups masked with an isocyanate masking agent, and a crosslinking agent which is substantially insoluble in aprotic solvents. The retroreflective sheeting disclosed possesses the unique combination of high reflectance and superior exterior durability.
    公开号:SU1768031A3
    申请号:SU833641402
    申请日:1983-09-01
    公开日:1992-10-07
    发明作者:Клемент Белайл Луис；Рой Борден Томас；Эдвард Грунцингер Мл. Реймонд
    申请人:Миннесота Майнинг Энд Мануфакцуринг Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to multilayer retroreflective materials and to the technology of their manufacture and can be used in the manufacture of reflectors in spotlights and lenses.
    The aim of the invention is to improve the reflectivity, increase the strength and weather resistance of the back-reflecting sheet material.
    According to the invention, non-sticky, in the unvulcanized state, polyurethane or polyurea in the form of a prepolymer with a softening temperature of 40 ° C to 90 ° C in combination with a vulcanizing agent is used as the starting polymer binder.
    Transparent glass microspheres are also used in accordance with the invention.
    A polymeric binder may contain an antioxidant or a stabilizer of ultraviolet rays, as well as additives to increase flowability,
    The retroreflective sheet material of the invention is made of a polylayer of transparent glass microspheres and a polymer layer in which the microspheres are partially embedded, (A) and of a specularly reflecting layer located under the microspheres (B).
    Layer A: is a polymer layer containing urea and / or
    2%
    with

    with
    urethane bonds, thermally cured to an insoluble and infusible state. The B-layer bonding layer is preferably obtained by thermally curing the composition comprising:
    (a) a polymeric compound with isocyanate groups included in it, with a substantial proportion of the free isocyanate groups being blocked by blocking agents that can be removed by heating; and
    (c) a curing agent that causes the formation of cross-links for isocyanate groups, or a catalyst that imparts the ability of cross-linking to other isocyanate groups to isocyanate groups when heated.
    The preferred method for preparing an unvulcanized homogeneous composition that binds balls contains the steps of:
    (a) the preparation of an isocyanate, a functional polymeric compound, which either represents the final isocyanate or contains isocyanate groups in it, in which a substantial part of the isocyanate groups are either blocked, masked, or combined with substituents or agents that can be removed by heating;
    (c) adding a vulcanizing agent that causes the formation of cross-links, preferably a crystalline polyol agent that causes the formation of cross-links, to the masked isocyanate-functional polymer compound, and allowing this mixture to react at an elevated temperature for a period of time sufficient for excretion of no more than about one third of the substituents that can be removed by heating, in order to provide a partial reaction of the agent causing the pattern crosslinking and isocyanate-functional polymer; and
    (c) maintaining the reaction temperature elevated until a homogeneous coating composition is obtained.
    The resulting homogeneous coating composition can be cooled to room temperature and stored, or it can be used immediately as described below.
    An inert to the reaction solvent, for example, benzene, toluene, xylene or similar non-reactive hydrocarbons, may be present in the reaction mixture at a concentration of up to 50 mash. solid matter. The inclusion of a non-reactive solvent is undesirable when a composition with 100% solids is required. If a solvent is used, it should be low boiling enough to evaporate when applied to the surface of a thin film. Preferred solvents include: 2-ethoxy ethyl acetate, 2- (2-ethoxy) ethoxy ethyl acetate, 2-butoxy ethyl - acetate, toluene, xylene, ethyl acetate, butyl acetate, amyl acetate, other similar esters, ketones, chlorinated solvents, nitroaliphatic solvents, dioxane, and the like.
    Layer B is a metallic coating, for example, made of silver, aluminum, etc., of uniform thickness and equal to from 20 to 100 nm.
    A method for producing a back reflective sheet material.
    1. Applying layer B to the temporary substrate by coating, laminating or spraying.
    2. Application of the layer A until vulcanization,
    3. Heating up to 40-90 ° С with subsequent pressing at 100-230 ° С, which provides capillary penetration of the microspheres into the layer A to a depth of 30 to 40% of the value of the diameter of the microspheres.
    5. Molding.
    6. Peeling off the temporary substrate. Example 1. Get two types of reverse-reflective sheet material, one of which used unvulcanized polyurethane coating composition in accordance with this invention, and the other - melamine crosslinked polyester resin (prototype).
    Paper is used as a temporary substrate. The upper layer of the material according to the invention is made on the basis of the composition of the composition, wt.h .:
    Polyurethane obtained in accordance with procedure A (see below) 60.0 Polyurethane obtained in accordance with procedure B (see below) 40.0 Blocked polyisocyanate. obtained according to procedure C (see below) 15.0 Ethylene glycol ether 23.5
    In addition, antioxidants, stabilizers, flow additives and the conventional amount are added to the composition.
    Procedure A.
    The isocyanate 4,4-methylenedicyclohexyl diisocyanate (150 g, 1.14 equivalents) in combination with 86.0 g of 2- (2-ethoxy) ethoxy ethyl acetate and 0.35 g of dibutyldyl-laurataol are introduced into the reaction vessel. Polycaprolactone diol with a total molecular weight of 530 is dissolved in 86.0 g of 2-ethoxyethylacetate. The solution of the polyol is then added to the isocyanate solution under nitrogen atmosphere, with rapid stirring, maintaining the reaction temperature at 40 to 45 ° C. . This temperature is maintained until the free isocyanate (NCO) content reaches 3.5%. Methyl ethyl ketoxime (43.2 g, equivalent to 0.496) is then added to the reaction mixture, maintaining the temperature from 40 to 45 ° C until the isocyanate (NCO) absorption disappears in the infrared spectrum, resulting in 100% blocked isocyanate groups. Then, tris (2-hydroxyethyl) isocyanurate (42.3 g, equivalence 0.485) is added to the reaction mixture in the form of a solid powder to give 0.91 equivalents of active hydrogen atoms per equivalent of the isocyanate group. The temperature is raised to 115 ° C and maintained for 30 minutes. A homogeneous polyurethane coating composition is obtained having a viscosity of 9400 centipoise, containing 66.4% by weight solids and less than 0.1% free isocyanate.
    Procedure B.
    The polyurethane coating composition is prepared according to procedure A, except that the polycaprolactane diol of procedure A is replaced with the same number of equivalents of the polycaprolactane diol of total molecular weight 830.
    Procedure C.
    The isocyanate 4,4-methylenedicyclohexyl diisocyanate (150 g, 1.14 equivalents) mixed with 86.0 g of 2- (2-ethoxy) ethoxyethyl acetate and 0.35 g of dilaurate dibutyl tin are introduced into the reaction vessel. Polycaprolactone diol with a total molecular weight of 530 is dissolved in 86.0 g of 2-ethoxyethylacetate. This polyol solution is then added to the isocyanate solution under nitrogen with rapid stirring, maintaining the reaction temperature at 40 to 45 ° C. This temperature is maintained until a free isocyanate (NCO) content of 3.5% is obtained. Methyl ethyl ketoxime (43.2 g, equivalent to 0.496) is then added to the reaction mixture, maintaining the temperature from 40 to 45 ° C until the absorption of isocyanate (NCO) in the infrared spectrum disappears.
    This top layer composition is thermally vulcanized in an oven at 175 ° C for about 10 minutes to form an upper layer thickness of 0.05 mm.
    Then, the unvulcanized bead-bonding compound was applied onto the vulcanized top layer with a thickness of 0.025 millimeters. For the back reflecting sheet material made according to the present invention, the ball-bonding composition contains the same homogeneous polyurethane coating composition from which the top layer 12 was formed. The ball-bonding composition of the prior art consists of a mixture of free oils of synthetic polyester resin and bottled melamine formaldehyde resin. - The solvent is removed from the polyurethane binder layer by heating to 150 ° C. The stickiness of the sample of this polyurethane binder layer is measured by the method of Sticky Rolling.
    ball, PSTC-6. The ball rolling distance in five separate attempts is from 200 to 600 cm.
    A monolayer of glass balls 13 heated to 100 ° C is applied to the sheet material provided with the layer of bonding balls. The average diameter of the glass beads is 75 ± 7.5 µm, and their surface is treated with an organochromic complex to facilitate the adhesion of the beads to the resin, as well as carbon fluoride to promote an even depth of the beads. The glass beads are deposited onto the bonding bead by pushing the carrier ,
    coated with a bonding bead through a tray filled with glass beads. The layer of balls bound with balls is then heated to 80-90 ° C, with pressure being applied
    by means of a varnishing roll for immersing the balls in a layer that binds the balls to a depth of 30 to 40% of their diameter. The excess balls are removed by a beater that acts on the back side of the carrier.
    after leaving it from the pallet, then vulcanized at 175 ° C for 10 minutes
    Likewise, the solvent is removed by heating the unvulcanized polyether / melamine bonding bead layer to 100 ° C. The stickiness of the sample of this bonding bead layer is also measured by the PSTC-6 sticky rolling method. The ball rolling distance in five separate experiments is from 25 to 75 cm.
    A monolayer of glass beads was applied onto a sticky, unvulcanized polyester / melamine bonding bead by dragging a carrier coated with a bead bonding layer through a tray filled with glass beads. Extra balls are removed by means of a beater acting on the reverse side of the carrier after leaving the pallet. The polyether / melamine resin capillary surrounds the balls so that they are embedded by 30-40% of their diameter in the unvulcanized balls binding layer. Then this bonding bead layer is vulcanized to a non-tacky state by heating to 150 ° C.
    Then, a layer of each sheet is applied to a bead-bonding layer containing a 25% solids resin solution, a polyvinyl butyral resin, and a bottled melamine resin, in a solvent, and vulcanized at 170 ° C for about 10 minutes to form an intermediate layer 15 with a thickness of 0.008 to 0.025 mm. A reflective layer of metallic aluminum, about 100 nm thick, is deposited on the intermediate layer by vapor deposition. Then, the acrylic carrier provided with the copolymer coating is peeled off. An adhesive layer is then applied to the reflective layer by applying a layer of acrylic pressure sensitive adhesive of a thickness of 0.025 mm to the silicon-sticking adhesive layer and laminating the adhesive-coated layer to the reflective layer in order to obtain a finished back-reflective sheet material with embedded lenses.
    The packing density of the balls is determined for each type of sheet material by electron micrographs. The reflectivity at angles of divergence of 0.2 ° and a dip of 5 ° is determined using a telephotometer, model 1.C.2000, from Gamma Scientific Inc.. each type of sheet material are shown in the table.
    Packing sharnikov indicated in the table as a percentage of the theoretically maximum packaging of microspheres with a diameter of 75 ± 7.5 micrometers. The increased concentration of microspheres in the sheet material with the polyurethane balls bonding layer of the present invention is due to the fact that the polyurethane resin is non-stick, which allows glass balls to be displaced before the balls are vulcanized and the glass balls are dredged, allowing more dense packing of balls
    Example 2. Illustrates a reflective material in which the polymer layer is made on the basis of polyurea.
    A carrier consisting of a sticky paper backing coated with a cross-linked acrylic copolymer is coated with an unvulcanized top layer. The latter is a homogeneous polyurethane coating composition prepared according to Example 1.
    This composition is vulcanized in an oven at 175 ° C for 10 minutes to obtain an upper coating with a thickness of 0.05 mm, then an unvulcanized tymilmer-synthetic balls binding composition with a thickness of 0.025 mm is applied to the vulcanized polymer coating. The polyurea ball binding composition is prepared according to the method described below.
    Isocyanate-4,4 methylenedicyclohexyl diisocyanate (150 g, 1.14 equivalents) is mixed with 86.0 g of 2- (2-ethoxy) ethoxyethyl acetate and 0.35 g of dibutyl dicylautaol in the reactor. Polycaprolactone diol, total molecular weight 530, (120.8 g, 0.456 equivalents) is dissolved in 86.0 g of 2-ethoxy-ethyl acetate. A polyol solution is then added to the isocyanate solution with vigorous stirring and under nitrogen atmosphere, keeping the reaction temperature within the range of 40 to 45 ° C approximately. This temperature is maintained until the content of free isocyanate groups (NCO) is 4.2%. Then, 59.5 g (0.684 equivalents) of methyl ethyl ketoxime is added to the reaction mixture, keeping the temperature within the range of 40-45 ° C until the absorption of isocyanate (NCO) disappears from the IR spectrum, resulting in 100% blocked isocyanate groups. To this solution, 71.8 g (0.684 equivalents) of 4,4-bis- (aminocyclohexyl) methane was added to the coating solution (as a result, 1.0 equivalent of active hydrogen atoms per equivalent of the isocyanate group are obtained) immediately before being applied in order to obtain uncured a polyurea ball-binding composition.
    The solution is removed from the polyurea layer binding the beads by heating it to 150 ° C. The stickiness of a sample of this polyurethane ball-binding layer is measured using the PSTC-6 ball adhesive stick method. The rolling distances of the balls in five separate experiments are 200 cm, 320 cm, 400 cm, 490 cm and 600 cm, respectively. A monolayer of glass sheets 13 is applied onto the sheet material,
    a polyurea-carrying layer that binds balls by spraying balls onto a layer in the form of a cascade. The bead-bonding layer is then thermally vulcanized by heating to 175 ° C for 10 minutes, as described in Example 1. The reflective sheeting is completed in the manner described in Example 1. It is established (as in Example 1) that the packing density of the balls is 96%. from the theoretical maximum. The reflection values of the sheet material are 250-300 candela / m2, according to the measurement method specified in Example 1.
    Example 3 illustrates a polymer ball-binding layer having a softening range from 40 to 50 ° C.
    Example 3. A carrier containing a sticky paper backing coated with a cross-linked acrylic copolymer is coated with a layer according to Example 1.
    Then, the uncured, ball-bonding composition is coated over the vulcanized surface coating with a thickness of 0.025 mm. A balling composition is prepared according to the method described below.
    The polyurethane coating composition is prepared according to method A of example 1, except that the polycaprolactone diol of method A is replaced with the same number of equivalents of polycaprolactone diol (378 g, 0.605 equivalent) of a total molecular weight of 1250. The resulting composition has 0, 91 equivalents of active hydrogen atoms per equivalent of isocyanate group.
    The solvent is removed from the polyurethane binder layer by heating to 150 ° C. The stickiness of the sample of this polyurethane binder layer is measured using the PSTC-6 Adhesive Rolling Method. The rolling distances of the balls in five separate experiments are about 200-600 cm.
    A monolayer glass bead 13, heated to 100 ° C, is applied to the sheet material, the layer bearing the balls, according to Example 1. The ball layer, described below, is heated to 40-50 ° C by applying pressure through a packing roller. embedding the balls 13 into a layer bonding the balls 14 to 30-40% of their diameter. Excess balls are removed with a beater, as described in example 1, the layer binding the balls is immediately vulcanized by heating to 175 ° C for 10 minutes. The preparation of reflective sheet material is completed in the manner described in Example 1. The balls are packed and the reflectivity of the sheet material is measured according to the method described in Example 1. The packing density of the balls is about 80% of the theoretical maximum, and the reflection value is in the range of 220-250 candela. / m2. Example 4 illustrates a polymer ball-binding layer with a softening temperature of 60-70 ° C.
    Example 4. A carrier consisting of
    a sticky paper substrate coated with a cross-linked acrylic copolymer is coated with an unvulcanized surface coating 12. The surface coating is a homogeneous
    polyurethane coating composition obtained according to example 1.
    This surface composition is vulcanized in an oven at 175 ° C for 10 minutes, obtaining a surface coating with a thickness of
    0.05 mm.
    Then, the unvulcanized bead-binding composition with a thickness of 0.025 mm was applied to the vulcanized surface coating. Binding balls
    the composition contains a homogeneous polyurethane coating composition prepared according to method B of example 1, except that methyl ethyl ketoxime is added at a concentration of 29.1 (0.34
    equivalent). This results in a composition having about 70% of the blocked isocyanate groups.
    The solvent is removed from the polyurethane ball-binding layer by
    heating to 150 ° C. The stickiness of a sample of this polyurethane ball binder layer is measured using the Ball Adhesive Rolling Method, PSTC-6. Ball spacing in five separate experiments
    is about 200-600 cm. A monolayer of glass beads heated to 100 ° C is applied to the sheet material carrying the ball binding layer in accordance with Example 1. The ball coated layer is then
    heat up to about 60-70 ° C, pressurized by means of a packing roller in order to seal the balls 13 into the layer of binding 14 to 30-40% of their diameter. The excess beads are removed with a beater, according to Example 1. Then, the layer of the bonding beads is immediately vulcanized at 175 ° C for approximately 10 minutes. Receiving reflective sheet material is completed in the manner described in
    Example 1. The packing of the balls and the reflection value of the sheet material are measured as described in Example 1. The packing density of the balls is about 80% of the theoretical maximum, and the reflection value is in the range of 220-250 kanades / m2.
    Example 5 illustrates a polymer bead bonding layer with a vulcanization temperature of 100 ° C.
    Example 5. A carrier consisting of a sticky paper substrate coated with a cross-linked acrylic copolymer is coated with an unvulcanized surface coating 12. The surface coating is a homogeneous polyurethane coating composition prepared according to Example 1.
    This surface composition is cured in an oven at 175 ° C for about 10 minutes to obtain a surface coating 12 of 0.05 mm thickness. Then, the uncured, ball-bonding composition is applied to the vulcanized surface coating 0.025 mm thick. The balling composition consists of a homogeneous polyurethane coating composition prepared according to the method described below.
    Method G.
    150 g (1.14 equivalents) of isocyanate-4,41-methylenedicyclohexyl diisocyanate are mixed in a reactor with 86,0 g of 2- (2-ethoxy) - ethoxyethyl acetate and 0.35 g of dibutyl dilaurathauralva. A polycaprolactone diol of total molecular weight 530, available under the trade name Niax R polyol PCP-0200 (supplier: Union Carbide) in an amount of 169.0 g (0.605 equivalent) is dissolved in 86.0 g of 2-ethoxyethyl acetate. The polyol solution is then added to the isocyanate solution under a nitrogen atmosphere with vigorous stirring, maintaining the temperature at about 40-45 ° C. This temperature is maintained until the content of free isocyanate groups (NCO) is 3.5%. 74.5 g (0.496 equivalents) of tert.-butyl acetoacetate, then added to the reaction mixture, keeping the temperature within the range of 40-45 ° C until the absorption of the isocyanate (NCO) disappears in the IR spectrum, resulting in a 100% yield blocked isocyanate groups. Then, 93.1 g (1.07 equivalents) of tris (2-hydroxyethyl) -isocyanurate is added to the reaction mixture in the form of a solid powder to obtain 2.0 equivalents of active hydrogen atoms per equivalent of the isocyanate group. The temperature is raised to 90 ° C and maintained at this value for 30 minutes. A homogeneous polyurethane coating composition is obtained with a viscosity of 12,000 centipauses, the solids content is 68.0 wt. % and the content of free isocyanate groups less than 0.1%
    The solvent is removed from the polyurethane bonding bead layer by heating to 150 ° C. The stickiness of the sample of this polyurethane ball tie
    The layer is measured using the PSTC-6 Sticky Rolling Method. The rolling distances of the balls in five separate experiments are about 200-600 cm.
    Monolayer glass beads 13, heated
    0 to 100 ° C, applied to the sheet material, carrying the layer binding the balls, in accordance with the method described in Example 1. The layer binding the layers is then immediately vulcanized using
    5 oven temperatures up to 100 ° C for about 10 min. Preparation of the back-reflective layer is completed in accordance with Example 1. The packing density of the balls and the reflection value of the sheet.
    Material 0 is measured as described in Example 1. The packing density of the balls is about 80% of the theoretical maximum, and the reflection value is in the range of 220-250 candela / m,
    5 Example 6 illustrates a polymer,
    bonding balls, a layer with a vulcanization temperature of 230 ° C.
    Example 6. A carrier consisting of a paper peel-off substrate coated with
    0 cross-linked with acrylic polymer, coated with uncured surface coating. The surface coating is a homogeneous polyurethane coating composition.
    5 obtained, according to example 1.
    This surface composition is vulcanized using a furnace temperature of about 175 ° C for about 10 minutes to obtain a surface coating of thickness
    0 0.05 mm.
    The uncured, bead-bonding composition of a thickness of 0.025 mm is then applied to the vulcanized surface coating 12. Binding balls
    5 the composition is a homogeneous polyurethane coating composition prepared according to method 3 described below.
    150 g (1.14 equivalents) of isocyanat-4.40 methylenedicyclohexyl-diisocyanag is mixed with 86.0 g of 2- (2-ethoxy) e-yuxi-ethyl acetate and 0.35 g of dibutyltin dilaurate in the reactor. The polycaprolactane diol of total molecular weight 530 (available
    5 in the trade name Niax R polyoi PCP-0200, supplied by Union Carbide) in an amount of 169.0 g (0.605 equivalent) is dissolved in 86.0 g of 2-ethoxyethyl acetate. A polyol solution is then added with vigorous stirring to the isocyanate solution under a nitrogen atmosphere, keeping the reaction temperature within the range of about 40-45 ° C. This temperature is maintained until the content of free isocyanate groups (NCO) is reached in the amount of 3.5%. Then, 57.0 g of E-caprolactam is added to the reaction mixture, keeping the temperature within the range of 100-115 ° C until the isocyanate (NCO) absorption spectrum disappears in the IR spectrum, resulting in 100% blocked isocyanate groups. Then, 37.2 g (0.428 equivalents) of tris (2-hydroxyethyl) isocyanurate is added to the reaction mixture in the form of a solid powder to obtain 0.8 equivalent of active hydrogen atoms per equivalent of the isocyanate group. The temperature is raised to 135 ° C and maintained at this value for 30 minutes. A homogeneous polyurethane coating composition is obtained with a viscosity of 18,500 centipauses, a solids content of 72.3% by weight and a content of free isocyanate groups of less than 0.1%.
    The solvent is removed from the polyurethane layer binding the balls by heating it to 150 ° C. The stickiness of the sample of this bonding bead, polyurethane layer is measured by the PSTC-6 bead rolling method. The rolling distance of the balls in five separate experiments is about 200-600 cm,
    A monolayer of glass beads 13 heated to 100 ° C is applied to the sheet material carrying the layer binding the balls according to the method described in Example 1. The layer connecting the balls is immediately vulcanized using the temperature up to 230 ° C. 10 min. The preparation of the back-reflective sheet material is completed in the manner described in Example 1. The packing density of the balls and the reflection value are measured as indicated in Example 1. The density
    from, 2
    权利要求:
    Claims (2)
    [1]
    1. A reflective sheet material made of a monolayer of transparent glass microspheres, a polymer layer in which the microspheres are partially embedded, and of a specularly reflective layer located under the microspheres, characterized in that, in order to improve the reflectivity, the strength and weatherability are inversely reflecting sheet material, the polymer layer is made of a non-sticky in the unvulcanized state polyurethane or polyurea with a softening temperature of 40-90 ° C, and the concentration of transparent glass microspheres in the sheet material is 80-96% of the estimated quantity.
    [2]
    2. A method for producing a back-reflecting sheet material by applying a composition to form a polymer layer on a temporary substrate, applying a monolayer of transparent glass microspheres, pre-pressing and curing by heating, followed by applying a specularly reflective layer, characterized in that To increase the strength and weather resistance of a back-reflecting sheet material, a mixture of polyurethane or polyurea formulations is used as a composition, in which 70-100% isocyanate groups are blocked, with a vulcanizing agent containing an active hydrogen atom, at a ratio that provides 0.8-2.0 equivalents of active hydrogen atom to 1 equivalent of isocyanate groups, the mixture is heated to 40-90 ° C, and the vulcanization after prepressing is carried out at 100-230 ° C.
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    同族专利:
    公开号 | 公开日
    EP0102818B1|1990-11-22|
    DE3382007D1|1991-01-03|
    JPH0417787B2|1992-03-26|
    EP0102818A2|1984-03-14|
    IN161933B|1988-02-27|
    EP0102818A3|1985-08-28|
    AT58602T|1990-12-15|
    AU565656B2|1987-09-24|
    CA1244306A|1988-11-08|
    AU1861583A|1984-03-08|
    MX172454B|1993-12-16|
    BR8304778A|1984-04-10|
    JPS5971848A|1984-04-23|
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    申请号 | 申请日 | 专利标题
    US41457482A| true| 1982-09-02|1982-09-02|
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