WO2016190019A1 - 再帰性反射性材料 - Google Patents
再帰性反射性材料 Download PDFInfo
- Publication number
- WO2016190019A1 WO2016190019A1 PCT/JP2016/062829 JP2016062829W WO2016190019A1 WO 2016190019 A1 WO2016190019 A1 WO 2016190019A1 JP 2016062829 W JP2016062829 W JP 2016062829W WO 2016190019 A1 WO2016190019 A1 WO 2016190019A1
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- WIPO (PCT)
- Prior art keywords
- layer
- retroreflective material
- transparent
- incident light
- resin layer
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/506—Intermediate layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B41M5/5281—Polyurethanes or polyureas
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/12—Reflex reflectors
- G02B5/126—Reflex reflectors including curved refracting surface
- G02B5/128—Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F13/00—Illuminated signs; Luminous advertising
- G09F13/16—Signs formed of or incorporating reflecting elements or surfaces, e.g. warning signs having triangular or other geometrical shape
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B41M5/5272—Polyesters; Polycarbonates
Definitions
- the present invention relates to a retroreflective material that retroreflects incident light. More specifically, the present invention has excellent washing resistance, and the daytime color visually recognized by inkjet printing and the nighttime color visually recognized by retroreflected light are stably maintained even after repeated washing. It relates to a retroreflective material.
- a retroreflective material that retroreflects incident light has been widely used for display of traffic signs and the like, and for identification of marine equipment, particularly in order to improve visibility at night.
- retroreflective materials are also used in safety clothing, safety vests, sasuki, armbands, life jackets, etc. as safety clothing for police, fire fighting, civil engineering, etc. Widely used.
- apparel such as windbreakers, training wear, T-shirts, sports shoes, swimwear, etc. It is also used for bags, suitcases, etc.
- the retroreflective material is printed with patterns such as letters, symbols, designs, etc.
- the printed pattern is visually recognized during the day, and the retroreflected light is visually recognized when exposed to light at night. In this way, when different visibility is given between daytime and nighttime, it is possible to improve the distinguishability, designability, and the like. Therefore, it is attempted to print a pattern on the retroreflective material.
- Patent Document 1 proposes applying a pattern by dyeing or printing a pattern on a fiber fabric serving as a support for a retroreflective material.
- the method of Patent Document 1 is suitable for applications that are consumed in large quantities or simple patterns, but in applications that are used in small lots and require complex patterns, in terms of cost. Not practical.
- Patent Document 2 a resin coating such as vinyl chloride is applied to the surface of the retroreflective sheet, and a desired pattern is silkscreen printed on the resin-coated surface with the same type of ink as the coating resin.
- a method is disclosed.
- the retroreflective sheet disclosed in Patent Document 2 has a space on the surface of the transparent microsphere (the surface located on the side opposite to the reflective layer), and the space is covered with a transparent plastic film.
- the so-called capsule lens type has a drawback that the resin coating may be easily broken by a physical impact, and further has inferior washing resistance and handling properties.
- the type of resin used for resin coating on which a pattern is printed has not been studied.
- Patent Document 3 discloses a retroreflective article including a core sheet including a retroreflective element and having a display surface, and a topcoat disposed on the display surface, wherein the topcoat is dried. There is disclosed a retroreflective article consisting essentially of at least one water-based acrylic polymer cured by the above-mentioned and wherein the topcoat satisfies a predetermined elastic modulus. Patent Document 3 also discloses that a pattern can be applied to the top coat by laser printing, ink jet printing, or thermal mass transfer printing.
- the texture of the retroreflective material becomes hard, and, for example, there is a drawback that the comfort becomes worse when pasted on clothes. is there. Furthermore, the retroreflective material with a hard texture is inferior in washing resistance, and there is a drawback that the appearance color and reflection performance change when washing is performed.
- Patent Document 4 includes, as a base polymer, a) a urethane acrylic copolymer, b) a blend of a polyurethane polymer and an acrylic polymer having a predetermined molecular weight, c) a blend of at least two polyurethane polymers, and / or a mixture thereof. It is disclosed that an ink receiving layer substantially free of an agent has characteristics that facilitate formation of a non-aqueous inkjet image. Patent Document 4 discloses a retroreflective article having the ink receiving layer. However, when an ink receiving layer using an acrylic resin such as an acrylic polymer or a urethane acrylic copolymer is provided, there is a disadvantage that the texture of the retroreflective material becomes hard and the washing resistance is poor.
- Patent Document 4 also proposes to provide an ink-receiving layer containing a blend of at least two types of polyurethane polymers. In spite of a large variation depending on the type, Patent Document 4 does not sufficiently study the constituent monomer of the polyurethane polymer that improves the washing resistance of the daytime color.
- the object of the present invention is to provide a retroreflective property that has excellent washing resistance and stably maintains the daytime color visually recognized by inkjet printing and the nighttime color visually recognized by retroreflected light even after repeated washing. Is to provide materials.
- the present inventor has conducted intensive studies to solve the above-mentioned problems. As a result, an excellent ink jet receiving layer formed of a polyurethane resin containing a specific structural unit is provided on the outermost surface of the retroreflective material. It has been found that washing resistance can be provided, and the daytime color visually recognized by ink jet printing and the nighttime color visually recognized by retroreflected light can be stably maintained even after repeated washing.
- the fixing resin layer, the transparent microsphere embedded in the fixing resin layer, the reflection layer provided on the surface side of the transparent microsphere opposite to the incident light side, and the incident A retroreflective material comprising an ink jet receiving layer provided on the outermost surface on the light side, wherein the refractive index of the transparent microspheres is set to 1.6 to 2.5, and the ink jet receiving layer is a polycarbonate polyol.
- a polyurethane resin containing 3 to 15 carbon dicarboxylic acid and polyisocyanate as structural units it can be provided with excellent washing resistance. It was found that the color can be maintained stably.
- the present invention has been completed by further studies based on such knowledge.
- Item 1 A fixed resin layer; Transparent microspheres embedded in the fixed resin layer; A reflective layer provided on the surface side of the transparent microsphere opposite to the incident light side; An ink jet receiving layer provided on the outermost surface on the incident light side; With The refractive index of the transparent microsphere is 1.6 to 2.5, A retroreflective material, characterized in that the ink jet receiving layer contains a polyurethane resin containing polycarbonate polyol, a dicarboxylic acid having 3 to 15 carbon atoms, and a polyisocyanate as constituent units.
- Item 2. Item 1.
- the polyurethane resin is a polyurethane resin obtained by reacting a polycarbonate polyol and a dicarboxylic acid having 3 to 15 carbon atoms to synthesize a polycarbonate polyester polyol, and then reacting the polycarbonate polyester polyol with a polyisocyanate.
- the polycarbonate polyol is a polycarbonate polyol obtained by an ester exchange reaction between an aliphatic dihydroxy compound having 2 to 20 carbon atoms and a dialkyl carbonate having 2 to 20 carbon atoms and / or a diaryl carbonate having 6 to 14 carbon atoms.
- the retroreflective material according to any one of 1 to 3. Item 5. Item 5. The retroreflective material according to any one of Items 1 to 4, wherein the polyisocyanate is an aromatic diisocyanate and / or an alicyclic isocyanate having 5 to 18 carbon atoms. Item 6.
- the transparent microsphere is provided on the incident light side from the fixed resin layer, Item 2.
- Item 7. Item 7. The retroreflective material according to Item 6, wherein the incident light side surface of the inkjet receiving layer has a curved shape along the spherical surface of the transparent microsphere.
- Item 8. Item 8. The retroreflective material according to Item 7, wherein the thickness of the inkjet receiving layer is set so as to increase from the apex portion on the incident light side of the transparent microsphere toward the side surface.
- the transparent microsphere portion that is not embedded in the fixing resin layer is embedded in the inkjet receiving layer, and the incident light side surface of the inkjet receiving layer forms a flat surface.
- Retroreflective material Item 10.
- the fixing resin layer is provided on the incident light side from the transparent microsphere, Item 2.
- the reflection layer is provided on the surface side of the transparent microsphere opposite to the incident light side, and the inkjet receiving layer is provided on the incident light side of the fixing resin layer. Retroreflective material.
- the retroreflective material of the present invention has a clear and stable pattern of characters, symbols, designs, etc. printed by ink jet printing by forming an ink jet receiving layer using a specific polyurethane resin on the outermost surface on the incident light side. Can be fixed.
- the retroreflective material of the present invention has excellent washing resistance, and even if washing is repeated, the peeling of the pattern printed on the inkjet receiving layer and the change in appearance color (daytime color) are suppressed. In addition to being able to maintain the pattern stably, it is also possible to suppress a decrease in retroreflective performance due to washing, and to stably maintain the night color visually recognized by the retroreflected light.
- the retroreflective material of the present invention is formed on the surface side of the fixed resin layer 1, the transparent microsphere 2 embedded in the fixed resin layer 1, and the transparent microsphere 2 opposite to the incident light side.
- a reflective layer 3 provided, and an inkjet receiving layer 4 provided on the outermost surface on the incident light side, wherein the refractive index of the transparent microsphere 2 is 1.6 to 2.5, and the inkjet receiving layer 4 is characterized by containing a polyurethane resin containing polycarbonate polyol, a dicarboxylic acid having 3 to 15 carbon atoms, and polyisocyanate as constituent units.
- the retroreflective material of the present invention will be described in detail.
- the retroreflective material of the present invention includes a fixed resin layer 1, a transparent microsphere 2 embedded in the fixed resin layer 1, and a transparent microsphere on the side opposite to the incident light side. 2 is provided with a reflective layer 3 provided on the surface side of 2 and an ink jet receiving layer 4 provided on the outermost surface on the incident light side.
- the fixing resin layer 1, the transparent microspheres 2, and the reflection layer 3 are layers and members for exhibiting retroreflection performance.
- the ink jet receiving layer 4 is a layer for printing patterns such as characters, symbols, designs, and the like by ink jet printing. The ink jet receiving layer 4 also plays a role of imparting excellent washing resistance.
- the specific arrangement of the fixing resin layer 1, the transparent microspheres 2, the reflective layer 3, and the ink jet receiving layer 4 is such that the transparent microspheres 2 are more than the fixing resin layer 1.
- the surface of the transparent microsphere 2 on the side opposite to the incident light side is set depending on whether or not the transparent microsphere 2 is embedded in the fixed resin layer 1.
- the inkjet receiving layer 4 may be provided on the outermost surface on the incident light side.
- the transparent microspheres 2 are arranged on the incident light side of the fixed resin layer 1, as shown in FIGS. 1 and 2, the reflective layer 3 is made of the transparent microspheres 2 and the fixed resin layer. 1 and the ink jet receiving layer 4 may be provided on the incident light side of the transparent microsphere 2.
- the incident light side surface of the inkjet receiving layer 4 may form a curved surface shape along the spherical surface of the transparent microsphere 2 (this mode is referred to as “semi-open”). Sometimes referred to as "type").
- the transparent microsphere 2 portion that is not embedded in the fixed resin layer 1 is embedded in the inkjet receiving layer 4, and incident light of the inkjet receiving layer 3.
- the side surface may be a flat surface (this mode may be referred to as “first closed type”).
- the fixing resin layer 1 is arranged on the incident light side with respect to the transparent microspheres 2, as shown in FIG. 3, the reflective layer 3 is made of the transparent microspheres 2 on the side opposite to the incident light side.
- the ink jet receiving layer 4 may be provided on the incident light side of the fixing resin layer 1 (this mode may be referred to as “second closed type”).
- a transparent resin layer 5 may be provided between the transparent microspheres 2 and the reflective layer 3 as necessary.
- the transparent resin layer 5 it is possible to adjust the reflection luminance and change the color tone of the emitted light.
- the reflective layer 3 is a metal film
- the transparent resin layer 5 also serves to suppress corrosion of the reflective layer 3.
- 4 shows a cross-sectional structure in which a transparent resin layer 5 is provided in a semi-open type retroreflective material
- FIG. 5 shows a cross-sectional structure in which a transparent resin layer 5 is provided in a first closed type retroreflective material
- FIG. 6 shows a cross-sectional structure in which the transparent resin layer 5 is provided in the second closed type retroreflective material.
- a support 6 may be included as a base material for holding the fixing resin layer 1 as necessary.
- a support 6 may be included as a base material for holding the fixing resin layer 1 as necessary.
- the retroreflective material of the present invention is the second closed type
- the surface opposite to the incident light side of the reflective layer 3 in the case where the transparent resin layer 5 is provided, the transparent resin
- An adhesive layer 7 may be included on the surface of the layer 5 on the side opposite to the incident light side, if necessary, in order to impart adhesion to the support.
- a support 6 is included as a base material for holding the shape of the retroreflective material on the surface of the adhesive layer 7 opposite to the incident light side as necessary. It may be.
- transparent microsphere 2 is embedded
- transparent microsphere 2 means that a part of the transparent microsphere 2 is embedded in another layer, and the transparent microsphere 2 is embedded.
- the layer is thicker than the height of the region in which the transparent microspheres 2 are embedded (corresponding to X described later in the case of the fixed resin layer 1), and the surface on the transparent microsphere 2 side is transparent microspheres. 2 indicates that a recess is formed along the shape of 2.
- each layer and member constituting the retroreflective material of the present invention will be described separately for a semi-open type, a first closed type, and a second closed type.
- the resin for forming the fixing resin layer 1 is not particularly limited as long as the transparent microspheres 2 can be embedded and held, and is appropriately set in consideration of the flexibility required for the retroreflective material. That's fine.
- Specific examples of the resin forming the fixing resin layer 1 include, for example, polyolefin resins (polyethylene, polypropylene, etc.), ethylene-vinyl acetate copolymer resins, polyvinyl alcohol, acrylic resins, urethane resins, and ester resins. Etc. Among these, from the viewpoint of imparting excellent flexibility, a urethane resin is preferably used.
- the resin forming the fixing resin layer 1 may be copolymerized with a silane coupling agent, if necessary. Thus, by copolymerizing the silane coupling agent, it becomes possible to provide the fixing resin layer 1 with durability, adhesiveness, and the like.
- the resin forming the fixing resin layer 1 may be cross-linked by a cross-linking agent such as a polyisocyanate cross-linking agent, an epoxy cross-linking agent, or a melamine resin, if necessary. By cross-linking with the cross-linking agent in this way, the fixing resin layer 1 can be provided with heat resistance, washing resistance, and the like.
- the fixing resin layer 1 may contain additives such as dyes, pigments, phosphorescent pigments, inorganic fillers, etc., depending on the use of the retroreflective material and the required functions.
- the thickness of the fixing resin layer 1 is not particularly limited as long as the transparent microspheres can be embedded and held, but for example, 15 to 300 ⁇ m, preferably 20 to 200 ⁇ m can be mentioned.
- the transparent microsphere 2 In the semi-open type retroreflective material, the transparent microsphere 2 is embedded in the fixed resin layer 1 through the reflective layer 3 and transmits the incident light and the outgoing light that is recursively reflected by the reflective layer. Fulfill. In the case where the transparent resin layer 5 is not provided, the transparent microspheres 2 are embedded in a state of being in contact with the reflective layer 3 (see FIG. 1). Further, when the transparent resin layer 5 is provided, the transparent microspheres 2 are embedded in a state of being in contact with the transparent resin layer 5 (see FIG. 4).
- the transparent microsphere 2 having a refractive index of 1.6 to 2.5 is used.
- the transparent microspheres 2 having such a refractive index it is possible to provide an excellent retroreflection performance by focusing on the reflective layer.
- the refractive index of the transparent microsphere 2 is preferably 1.8 to 2.2, and more preferably 1.9 to 2.1.
- the embedding rate of the transparent microspheres 2 on the fixed resin layer 1 side is not particularly limited, and examples thereof include 30 to 70%, preferably 40 to 60%, and more preferably 45 to 55%.
- the embedding rate of the transparent microspheres 2 on the fixed resin layer 1 side is that the transparent microspheres 2 are on the fixed resin layer 1 side with respect to the diameter of the transparent microspheres 2. It is the ratio (%) of the height of the area
- Transparency of microspheres (X / R) x 100 R: Diameter of the transparent microsphere 1 X: The uppermost portion on the incident light side of the reflective layer 3 or the uppermost portion on the incident light side of the transparent resin layer 5 when the transparent resin layer 5 is provided. Length to the bottom of the surface of the transparent microsphere 2 embedded in the layer 1 side
- the embedment rate is a value calculated by measuring each embedment rate for 30 or more transparent microspheres 2 embedded in the retroreflective material, and calculating an average value thereof.
- the average particle size of the transparent microspheres 2 is not particularly limited, but is usually 30 to 200 ⁇ m, preferably 40 to 120 ⁇ m, more preferably 50 to 100 ⁇ m, and particularly preferably 75 to 90 ⁇ m.
- the average particle diameter of the transparent microspheres 2 is obtained by measuring the maximum diameter of the transparent microspheres 2 for 30 of the transparent microspheres 2 with a magnification of 500 times using a microscope. Is a value obtained by calculating.
- the material of the transparent microsphere 2 is not particularly limited as long as it can have the above-described refractive index, and may be any of glass, resin, etc. It is excellent in transparency, chemical resistance, washing resistance, weather resistance and the like, and is suitably used in the present invention.
- the number of transparent microspheres 2 embedded per unit area may be appropriately set according to the retroreflective performance to be provided.
- the number of transparent microspheres 2 is 50 to 500, preferably 100 to 250, and more preferably 150 to 180 per 1 mm 2 of the conductive material.
- the reflective layer 3 is provided between the transparent microsphere 2 and the fixing resin layer 1 and functions to recursively reflect light incident from the transparent microsphere 2.
- the reflective layer 3 is not particularly limited with respect to its constituent materials as long as it can reflect light incident from transparent microspheres, but it is preferably a metal film.
- the metal constituting the metal film include aluminum, titanium, zinc, silica, tin, nickel, silver, and the like.
- aluminum is preferably used from the viewpoint of providing more excellent retroreflection performance.
- the thickness of the reflective layer 3 is not particularly limited, and examples thereof include 100 to 2000 mm, preferably 600 to 1000 mm.
- the ink jet receiving layer 4 In the semi-open type retroreflective material, the ink jet receiving layer 4 is provided on the outermost surface on the incident light side of the retroreflective material and plays a role of providing excellent washing resistance.
- the incident light side surface of the inkjet receiving layer 4 forms a curved surface shape along the spherical surface of the transparent microsphere 2.
- the layer thickness L (90 °) of the ink jet receiving layer 4 is not particularly limited as long as it forms a curved surface along the spherical surface of the transparent microsphere 2.
- the thickness may be appropriately set in the range of 2 to 8 ⁇ m, preferably 2 to 6 ⁇ m, and more preferably 2 to 4 ⁇ m.
- the layer thickness L (90 °) is the layer thickness in the direction of 90 ° from the apex portion on the incident light side of the transparent microsphere 2 with respect to the plane direction.
- the layer thickness of the ink jet receiving layer 4 is preferably set so as to increase from the apex portion on the incident light side of the transparent microsphere 2 toward the side surface. By changing the thickness of the ink jet receiving layer 4 in such a manner, it is possible to further improve the fixing property of ink jet printing. More specifically, the inkjet receiving layer 4 is a surface from the center point of the transparent microsphere 2 to the layer thickness L (90 °) in the direction of 90 ° from the center point of the transparent microsphere 2.
- the ratio of the layer thickness L (45 °) in the 45 ° direction to the direction (layer thickness L (45 °) / layer thickness L (90 °) ) is 1.1 to 5.0, preferably 1.1 to It is desirable to set it to 3.0, more preferably 1.2 to 1.5.
- the layer thickness L of the ink jet receiving layer 4 (90 °) and L (45 °) is specifically a value calculated according to the following equation, the layer thickness L (90 °) in Figure 1 and L The relationship of (45 °) is schematically shown.
- Layer thickness L (90 °) Y (90 °) -X (90 °)
- Layer thickness L (45 °) Y (45 °) -X (45 °) X (90 °) : Distance Y (90 °) from the center point of the transparent microsphere 1 to the interface between the transparent microsphere 1 and the inkjet receiving layer 4 in the direction of 90 ° with respect to the plane direction: Transparency micro Distance X (45 °) from the center point of the sphere 1 to the incident light side surface of the inkjet receiving layer 4 in the direction of 90 ° with respect to the plane direction: 45 ° with respect to the plane direction from the center point of the transparent microsphere 1
- the layer thickness L (90 °) is 2 to 4 ⁇ m, preferably 2, while satisfying the layer thickness L (45 °) / layer thickness L (90 °) .
- Examples thereof include 5 to 4 ⁇ m and a layer thickness L (45 °) of 2.5 to 6 ⁇ m.
- the inkjet receiving layer 4 is formed of a polyurethane resin containing polycarbonate polyol, a dicarboxylic acid having 3 to 15 carbon atoms, and polyisocyanate as constituent units.
- Polycarbonate polyol is a polymer obtained by polycondensation of (a) dihydroxy compound and (b) carbonic acid diester as a raw material monomer by a transesterification reaction, and is a raw material monomer of polycarbonate polyol used as a constituent unit of the polyurethane resin.
- the type is not particularly limited.
- Examples of the (a) dihydroxy compound used as a raw material monomer for polycarbonate polyol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,20-eicosanediol, etc.
- Aliphatic dihydroxy compounds having 2 to 20 carbon atoms linear dihydroxy compounds having 4 to 1000 carbon atoms having an ether group such as diethylene glycol, triethylene glycol, tetraethylene glycol, and polytetramethylene glycol; bishydroxyethyl thioether, etc.
- dihydroxy compounds preferably aliphatic dihydroxy compounds having 2 to 20 carbon atoms, more preferably aliphatic dihydroxy compounds having 4 to 8 carbon atoms, particularly preferably 1,4-butanediol and 1,5-pentanediol. 1,6-hexanediol.
- dihydroxy compounds may be used alone as a raw material monomer for polycarbonate polyol, or may be used in combination of two or more.
- Examples of the (b) carbonic acid diester used as a raw material monomer for the polycarbonate polyol include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate, ethyl isobutyl carbonate, etc.
- dialkyl carbonates examples include alkylene carbonates having 2 to 6 carbon atoms such as pentyl carbonate.
- carbonic acid diesters preferably a dialkyl carbonate having 2 to 20 carbon atoms, a diaryl carbonate having 12 to 16 carbon atoms; more preferably a dialkyl carbonate having 2 to 8 carbon atoms, a diaryl carbonate having 12 to 14 carbon atoms; particularly preferably diethyl carbonate, Diphenyl carbonate is mentioned.
- These carbonic acid diesters may be used alone as a raw material monomer for polycarbonate polyol, or may be used in combination of two or more.
- the molecular weight of the polycarbonate polyol used as the structural unit of the polyurethane resin is not particularly limited, and examples thereof include 500 to 5000, preferably 1000 to 3000.
- the molecular weight of the polycarbonate polyol refers to the number average molecular weight measured by the GPC method using polystyrene as a standard substance.
- polycarbonate polyols may be used alone as a structural unit of the polyurethane resin, or may be used in combination of two or more.
- the dicarboxylic acid used as the structural unit of the polyurethane resin is not particularly limited as long as it has 3 to 15 carbon atoms, but preferably has a carbon number from the viewpoint of further improving the washing resistance.
- Examples thereof include 5 to 13 dicarboxylic acids, more preferably dicarboxylic acids having 8 to 12 carbon atoms.
- dicarboxylic acids include 1,10-decanedicarboxylic acid, 1,9-nonanedicarboxylic acid, and 1,8-octanedicarboxylic acid.
- 1,10-decanedicarboxylic acid is preferable.
- These dicarboxylic acids may be used alone as a structural unit of the polyurethane resin, or may be used in combination of two or more.
- polyisocyanate used as the structural unit of the polyurethane resin is not particularly limited.
- aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane isocyanate, p-phenylene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, C2-C12 aliphatic diisocyanates such as 2,2,4-trimethylhexane diisocyanate and lysine diisocyanate; 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), methylcyclohexane Diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, 1,3-diisocyanatomethyl Chlohexane (hydrogenated XDI), hydrogenated toly
- polyisocyanates preferred are aromatic diisocyanates and alicyclic isocyanates having 5 to 18 carbon atoms; and more preferred are diphenylmethane isocyanate, 4,4′-dicyclohexylmethane diisocyanate, and isophorone diisocyanate.
- polyisocyanates may be used alone as a structural unit of the polyurethane resin, or may be used in combination of two or more.
- the polyurethane resin used for forming the ink-jet receiving layer 4 may contain polycarbonate polyol, dicarboxylic acid having 3 to 15 carbon atoms, and polyisocyanate as structural units, and the ratio thereof is not particularly limited.
- polycarbonate polyol per 100 parts by weight of polycarbonate polyol, 10 to 130 parts by weight, preferably 40 to 120 parts by weight of a dicarboxylic acid having 3 to 15 carbon atoms; 10 to 90 parts by weight, preferably 50 to 90 parts by weight of polyisocyanate.
- 10 to 90 parts by weight preferably 50 to 90 parts by weight of polyisocyanate.
- the polyurethane resin used for forming the inkjet receiving layer 4 may be obtained by simultaneously mixing and polymerizing a dicarboxylic acid having 3 to 15 carbon atoms, a polycarbonate polyol, and a polyisocyanate. From the viewpoint of further improving the properties, a polycarbonate polyol and a dicarboxylic acid having 3 to 15 carbon atoms are polymerized by an ester reaction to synthesize the polycarbonate polyester polyol, and then the polycarbonate polyester polyol and the polyisocyanate are reacted. The resulting polyurethane resin is preferred.
- examples of the polycarbonate polyester polyol include those obtained by reacting 3 to 15 carbon dicarboxylic acid at a ratio of 10 to 130 parts by weight, preferably 40 to 120 parts by weight, per 100 parts by weight of the polycarbonate polyol. .
- the polycarbonate polyester polyol may be polymerized by adding a dihydroxy compound in addition to the polycarbonate polyol and the C 3-15 dicarboxylic acid.
- Specific examples and preferred ones of the dihydroxy compound used for the production of the polycarbonate polyester polyol are the same as those of the dihydroxy compound used as the structural unit of the polycarbonate polyol.
- the ratio of the dihydroxy compound is not particularly limited.
- the compound per 100 parts by weight of the polycarbonate polyol, The compound is 20 to 40 parts by weight, preferably 25 to 35 parts by weight.
- the reaction between the polycarbonate polyester polyol and the polyisocyanate is desirably carried out at a ratio of 20 to 50 parts by weight, preferably 30 to 45 parts by weight of the polyisocyanate per 100 parts by weight of the polycarbonate polyester polyol.
- the polyurethane resin may contain a dihydroxy compound as a constituent unit, if necessary, in addition to the dicarboxylic acid having 3 to 15 carbon atoms, the polycarbonate polyol, and the polyisocyanate.
- a dihydroxy compound as a constituent unit, if necessary, in addition to the dicarboxylic acid having 3 to 15 carbon atoms, the polycarbonate polyol, and the polyisocyanate.
- Specific examples and preferred examples of the dihydroxy compound are the same as those of the dihydroxy compound used as the structural unit of the polycarbonate polyol.
- the ratio is not particularly limited.
- the amount of the dihydroxy compound is 2 to 15 parts by weight, preferably 3 to 10 parts by weight per part.
- the polycarbonate polyester polyol is synthesized after the polycarbonate polyester polyol is synthesized by the method described above. It is preferable to react polyisocyanate with a dihydroxy compound.
- the amount of the dihydroxy compound added to the polycarbonate polyester polyol may be appropriately set according to the ratio of the dihydroxy compound to the polycarbonate polyol described above. For example, 1 to 1 part of the dihydroxy compound per 100 parts by weight of the polycarbonate polyester polyol is used. 8 parts by weight, preferably 2 to 5 parts by weight.
- the structural unit of the polyurethane resin may contain an organic diamine as a chain extender, if necessary.
- the organic diamine contained as the structural unit of the polyurethane resin include alkyl diamines having 2 to 6 carbon atoms such as ethylene diamine, propylene diamine and hexamethylene diamine; alicyclic diamines such as isophorone diamine and dicyclohexyl methane diamine; And hydroxyl group-containing alkyldiamines having 4 to 10 carbon atoms such as hydroxyethylpropyldiamine, hydroxyethylpropylenediamine, dihydroxyethylethylenediamine, dihydroxyethylenediamine, dihydroxyethylpropylenediamine, hydroxypropylethylenediamine, and dihydroxypropylethylenediamine.
- these organic diamines alicyclic diamines are preferable, and isophorone diamine is more preferable. These organic diamines may be used alone or
- the organic diamine is included in the structural unit of the polyurethane resin, the ratio thereof is not particularly limited.
- the organic diamine is 5 to 20 parts by weight, preferably 10 to 15 parts by weight per 100 parts by weight of the polycarbonate polyol. Can be mentioned.
- an organic diamine is contained in the structural unit of the polyurethane resin
- the amount of the organic diamine added to the polycarbonate polyester polyol may be appropriately set according to the ratio of the organic diamine to the polycarbonate polyol described above.
- the organic diamine is 5 to 5 per 100 parts by weight of the polycarbonate polyester polyol. 20 parts by weight, preferably 10 to 15 parts by weight can be mentioned.
- the inkjet receptive layer 4 may contain a polyurethane resin containing, as structural units, a dicarboxylic acid having 3 to 15 carbon atoms, a polycarbonate polyol, and a polyisocyanate. Other resins such as polyurethane resins and silicone resins may be included. Examples of the content of the polyurethane resin in the ink jet receiving layer 4 include 60% by weight or more, preferably 80% by weight or more, and more preferably 90 to 100% by weight.
- the ink jet receiving layer 4 contains additives such as an ultraviolet absorber, an antioxidant, a dye, a pigment, a phosphorescent pigment, and an inorganic filler, depending on the use of the retroreflective material and the required function. It may be.
- the transparent resin layer 5 is a layer provided as necessary between the transparent microspheres 2 and the reflective layer 3 to adjust the reflected luminance or to be emitted.
- the reflective layer 3 is a metal film, it also functions to suppress corrosion.
- the resin that forms the transparent resin layer 5 is not particularly limited as long as it has light transparency, and examples thereof include acrylic resins, polyurethane resins, and polyester resins.
- the resin forming the transparent resin layer 5 may be copolymerized with a silane coupling agent as necessary for the purpose of imparting durability, adhesion, and the like to the transparent resin layer 5.
- the resin that forms the transparent resin layer 5 is a polyisocyanate-based crosslinking agent, an epoxy-based crosslinking agent, or a melamine-based resin as necessary for the purpose of imparting heat resistance, washing resistance, etc. to the transparent resin layer. It may be crosslinked by a crosslinking agent such as
- the transparent resin layer 5 has additives such as an ultraviolet absorber, an antioxidant, a dye, a pigment, a phosphorescent pigment, and an inorganic filler, depending on the use of the retroreflective material and the required function. It may be included.
- the thickness of the transparent resin layer 5 may be appropriately set in consideration of required reflection luminance, color tone, and the like, and is, for example, 0.1 to 30 ⁇ m, preferably 0.1 to 1 ⁇ m.
- the support 5 is a member provided as necessary, and functions as a base material for holding the fixing resin layer 4.
- the support 6 may not be provided in the distribution stage, for example.
- the support body 6 may be directly laminated
- the material constituting the support 6 may be appropriately set based on the use of the retroreflective material, the required strength and flexibility, and the like.
- Specific examples of the material of the support 6 include natural fibers such as pulp; resins such as polyesters such as polyethylene terephthalate and polyethylene naphthalate; metals and the like.
- the shape of the support 6 is not particularly limited, and examples thereof include a sheet shape such as a woven or knitted fabric, a nonwoven fabric, a film, and paper; a thread shape; a string shape.
- it is in the form of a sheet such as a woven or knitted fabric, a nonwoven fabric, a film, or paper.
- First closed type retroreflective material adheresive resin layer 1
- the fixed resin layer 1 functions to embed and hold transparent microspheres as in the case of the semi-open type.
- the type of resin forming the fixing resin layer 1 the type of additive added to the fixing resin layer 1 as necessary, the thickness of the fixing resin layer 1, etc. The same as the case of the semi-open type.
- Transparent microsphere 2 In the first closed type retroreflective material, the transparent microspheres 2 are embedded in the fixing resin layer 1 via the reflective layer 3 as in the case of the semi-open type, and incident light and the reflective layer It fulfills the function of transmitting the retroreflected outgoing light.
- the transparent microspheres 2 are embedded in the arrangement mode, refractive index, embedded ratio on the fixed resin layer 1 side, average particle size, material type, and unit area.
- the number and the like are the same as in the semi-open type.
- the reflective layer 3 is provided between the transparent microsphere 2 and the fixed resin layer 1 and is incident from the transparent microsphere 2 as in the case of the semi-open type. It fulfills the function of retroreflecting the light to be reflected.
- the arrangement mode, the constituent material, the thickness, etc. of the reflective layer 3 are the same as in the semi-open type.
- the ink jet receiving layer 4 In the first closed type retroreflective material, the ink jet receiving layer 4 is provided on the outermost surface on the incident light side of the retroreflective material as in the case of the semi-open type, and has excellent washing resistance. And keeps the daytime and nighttime colors stable even after repeated washing.
- the ink jet receiving layer 4 embeds the transparent microsphere 2 portion that is not embedded in the fixed resin layer 1, and the incident light side surface thereof is a flat surface.
- the ink-jet receiving layer 4 has a layer thickness that covers the top of the incident light side of the transparent microsphere 2 and forms a flat surface on the incident light side surface.
- the layer thickness (L (a) in FIGS. 2 and 5 ) from the apex portion on the incident light side of the transparent microsphere 2 portion to the incident light side surface of the inkjet receiving layer 4 is usually 10 to 40 ⁇ m, preferably Is 10 to 20 ⁇ m, more preferably 12 to 18 ⁇ m.
- L (b) is 70 to 240 ⁇ m, preferably 70 to 160 ⁇ m, more preferably 90 to 140 ⁇ m.
- the type of structural unit of the polyurethane resin forming the inkjet receiving layer 4 the ratio of the structural unit, the method of synthesizing the polyurethane resin, and optionally added to the inkjet receiving layer 4
- the types of additives to be used are the same as in the semi-open type.
- the transparent resin layer 5 is a layer provided as necessary between the transparent microspheres 2 and the reflective layer 3 as in the case of the semi-open type. In addition, it functions to adjust the reflection luminance and change the color tone of the emitted light. Further, when the reflective layer 3 is a metal film, it also functions to suppress corrosion.
- the arrangement mode of the transparent resin layer 5, the type of resin to be formed, the type of additive added as required, the thickness, etc., are the case of the semi-open type It is the same.
- the support 5 is a member provided as necessary, as in the case of the semi-open type, and functions as a base material for holding the fixing resin layer 4. .
- the arrangement and material of the support 6 are the same as in the semi-open type.
- Second closed type retroreflective material adheresive resin layer 1
- the fixing resin layer 1 functions to embed and hold the transparent microspheres and to transmit the incident light to the transparent microspheres 2.
- the resin that forms the fixing resin layer 1 has transparency that allows the incident light to pass through the transparent microspheres 2 and is embedded with the transparent microspheres.
- the same resin as that used for forming the semi-open type fixing resin layer 1 may be used.
- urethane resins are preferable and polyester urethane resins are particularly preferable from the viewpoint of improving washing resistance while further increasing transparency.
- the fixing resin layer 1 is the same as the case of the semi-open type fixing resin layer 1 as long as it has transparency capable of transmitting incident light to the transparent microspheres 2. These various additives may be included.
- the thickness of the fixing resin layer 1 is the same as that of the semi-open type.
- Transparent microsphere 2 In the second closed type retroreflective material, the transparent microspheres 2 are embedded in the fixing resin layer 1 through the reflective layer 3 as in the case of the semi-open type, and incident light and the reflective layer It fulfills the function of transmitting the retroreflected outgoing light.
- the transparent microspheres 2 are disposed on the incident light side surface side of the reflective layer 3 (or the transparent resin layer 5 when the transparent resin layer 5 is provided).
- the embedding rate of the transparent microspheres 2 on the fixed resin layer 1 side is not particularly limited, and examples thereof include 30 to 70%, preferably 40 to 60%, and more preferably 45 to 55%.
- the embedding rate of the transparent microspheres 2 on the fixing resin layer 1 side means that the transparent microspheres 2 correspond to the diameter of the transparent microspheres 2. It is the ratio (%) of the height of the area embedded in the layer 1, and is a value calculated according to the following formula.
- Embedding rate of transparent microspheres 2 (%) (X / R) ⁇ 100 R: Diameter of the transparent microsphere 2
- X Transparent embedded from the bottom of the fixed resin layer 1 (the deepest part of the surface of the fixed resin layer 1 opposite to the incident light side) to the fixed resin layer 1 side To the uppermost part (vertex on the incident light side) of the surface of the microsphere 2
- the refractive index of the transparent microspheres 2 In the second closed type retroreflective material, the refractive index of the transparent microspheres 2, the average particle size, the type of material, the number embedded per unit area, etc. are the same as in the semi-open type. is there.
- the reflective layer 3 is provided on the surface side of the transparent microsphere 2 opposite to the incident light side, and recursively reflects the light incident from the transparent microsphere 2. Fulfills the function.
- the constituent material, thickness, etc. are the same as in the semi-open type.
- the ink jet receiving layer 4 is provided on the incident light side of the fixing resin layer 1 to provide excellent washing resistance, and the daytime color and the nighttime color are maintained even after repeated washing. Plays a role in maintaining stability.
- the ink jet receiving layer 4 is provided on the surface of the fixing resin layer 1 on the incident light side, and the surface of the incident light side is a flat surface.
- the thickness of the ink jet receiving layer 4 is not particularly limited. For example, 10 to 20 ⁇ m, preferably 12 to 18 ⁇ m, and more preferably 12 to 16 ⁇ m.
- the type of structural unit of the polyurethane resin forming the ink jet receiving layer 4 the ratio of the structural unit, the method of synthesizing the polyurethane resin, added to the ink jet receiving layer 4 as necessary
- the types of additives to be used are the same as in the semi-open type.
- the transparent resin layer 5 is a layer provided as necessary between the transparent microspheres 2 and the reflective layer 3 to adjust the reflection luminance or emit light.
- the reflective layer 3 is a metal film, it also functions to suppress corrosion.
- the type of resin forming the transparent resin layer 5 the type of additive added to the transparent resin layer 5 as necessary, the thickness of the transparent resin layer 5, etc. Is the same as in the semi-open type.
- the adhesive layer 7 is provided on the surface of the reflective layer 3 opposite to the incident light side, as needed, in order to provide adhesion to the support. Is a layer.
- the adhesive layer 7 only needs to be formed of an adhesive resin that can provide adhesion to the support.
- an adhesive resin include acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride- Examples thereof include vinyl acetate copolymer resin, styrene-acryl copolymer resin, polyester resin, polyamide resin, and polyolefin resin. These adhesive resins may be used individually by 1 type, and may be used in combination of 2 or more type.
- the support 5 is a member provided as necessary on the surface of the adhesive layer 7 on the side opposite to the incident light side, and the shape of the retroreflective material is It functions as a base material to be held.
- the material of the support 6 is the same as in the semi-open type.
- the retroreflective material of the present invention has characteristics suitable for printing patterns such as characters, symbols and designs by ink jet printing, and can be used as a substrate for ink jet printing. Among these, it is particularly suitable when ink jet printing is performed using an ink in which a pigment is dispersed in a volatile solvent, that is, a so-called solvent ink. Among the solvent inks, those containing a vinyl resin as a binder resin are even more preferable.
- the retroreflective material of the present invention is provided with various patterns by ink jet printing, if necessary, and then safety clothing, apparel, bags, suitcases, shoes, road markings, retroreflective photoelectric sensors, touch panels (for example, , An infrared retroreflection detection type touch panel) and the like.
- the retroreflective material of the present invention is a safety apparel and apparel in view of the fact that it is easy to print patterns such as letters, symbols and designs by ink jet printing and has excellent washing resistance. , Bags, suitcases, shoes, especially safety apparel, apparel applications.
- Method for producing retroreflective material is not particularly limited as long as it can be provided with the above-described configuration, but a preferred example thereof is a semi-open type, The description will be made separately for the first closed type and the second closed type.
- a preferred example of a method for producing a semi-open type retroreflective material is a method including the following steps 1 to 6.
- Step 1 a step of softening the thermoplastic film by heating the release support in which the thermoplastic film is laminated on the base film at a temperature equal to or higher than the softening point of the thermoplastic film
- Step 2 Before, simultaneously with, or after Step 1, the transparent microspheres 2 were sprayed on the thermoplastic film of the release support, and the transparent microspheres 2 were embedded in a softened thermoplastic film at a predetermined ratio.
- Step 3 If necessary, a resin for forming the transparent resin layer 5 is applied to the transparent microsphere 2 side of the release support in which the transparent microspheres 2 are embedded to form the transparent resin layer 5.
- Step 4 A step of laminating the reflective layer 3 on the transparent microsphere 2 side of the release support in which the transparent microsphere 2 is embedded, or on the transparent resin layer 5, Step 5: Applying a resin for forming the fixing resin layer 1 on the reflective layer 3 and laminating the fixing resin layer 1, and Step 6: After peeling the release support, the transparent microsphere 2 side Applying a resin for forming the inkjet receiving layer 4 to the inkjet receiving layer 4 so as to have a curved shape along the spherical surface of the transparent microspheres 3; Process 7: The process which adhere
- the base film of the release support used in Step 1 is not particularly limited as long as the shape can be stably maintained at the softening temperature of the thermoplastic film.
- thermoplastic film of the mold release support body used in the said process 1 the resin film softened at low temperature is preferable, and polyolefin resin films, such as polyethylene and a polypropylene, are mentioned as such a resin film.
- polyolefin resin films such as polyethylene and a polypropylene
- step 2 the transparent microspheres 2 are embedded in the thermoplastic film by gravity sedimentation of the transparent microspheres 2 placed on the softened thermoplastic film. Therefore, in step 2, the degree of softening of the thermoplastic film is determined in consideration of the size, density, density, thickness, etc. of the transparent microspheres 2 in step 1, and the heating temperature and time for softening the thermoplastic film. By appropriately adjusting, the embedding rate of the transparent microspheres 2 on the fixed resin layer 1 side can be controlled.
- the step 3 and the step 4 are performed after the step 2 and after returning the thermoplastic film to a cured state by cooling or cooling.
- the step 3 is performed when the transparent resin layer 5 is provided between the transparent microspheres 2 and the reflective layer 3.
- coating to the transparent microsphere side of resin which forms the transparent resin layer 5 should just be performed by the well-known resin coating method.
- the formation of the reflective layer 3 in the step 4 may be performed by a known metal film forming method such as vapor deposition, sputtering, chemical vapor deposition, or plating. As a method for forming the reflective layer 3, vapor deposition is preferably used.
- step 5 the resin for forming the fixing resin layer 1 may be applied on the reflective layer 3 by a known resin coating method.
- step 6 in order to form the ink jet receiving layer 4, a solution for forming the ink jet receiving layer 4 in which each component constituting the polyurethane resin is dispersed or dissolved is applied to the transparent microspheres 1 side. It may be heated and dried in accordance with
- the type of solvent for dissolving or dispersing each component constituting the polyurethane resin is not particularly limited.
- toluene cyclohexanone, N, N-dimethylformamide (DMF) ), Methyl ethyl ketone (MEK), isopropyl alcohol (IPA) and the like.
- the coating amount of the solution for forming the ink jet receiving layer 4 may be appropriately set so that the ink jet receiving layer 4 has a curved surface shape along the spherical surface of the transparent microsphere 3.
- the conditions for drying the inkjet receiving layer 4 forming solution applied on the transparent microsphere 1 side are the conditions under which each component constituting the polyurethane resin is cured to form the polyurethane resin.
- the temperature may be 100 to 170 ° C. for 2 to 8 minutes, preferably 110 to 160 ° C. for 3 to 5 minutes.
- the inkjet receiving layer 4 in order to increase the thickness of the inkjet receiving layer from the apex portion on the incident light side of the transparent microsphere toward the side surface, for example, formation of the inkjet receiving layer 4 as an inkjet receiving layer is performed.
- the solution is applied so that the solid content concentration is 5.0 to 20.0 mass%, and the layer thickness L (90 °) is a predetermined thickness, and the temperature is 90 to 150 ° C. and the time is 2 to 5 minutes.
- the method of drying is mentioned.
- the step 7 is a step that is performed as necessary before or after the step 6 when the support 5 is provided.
- the bonding method between the fixing resin layer 4 and the support 5 is not particularly limited, and can be performed by, for example, a known laminating method.
- a preferred example of the method for producing the first closed type retroreflective material is the following step 6 in the method for producing the semi-open type retroreflective material. Except for changing to step 6 ′, the manufacturing method is the same as that of the semi-open type retroreflective material.
- the step 6 ′ is the same as the step 6 except that the coating amount of the solution for forming the ink jet receiving layer 4 is changed so that the transparent microsphere 3 is buried and the incident light side surface forms a flat surface. It is.
- a preferred example of a method for producing the second closed type retroreflective material includes a method including the following steps A to H.
- Step A A step of applying a resin for forming the inkjet receiving layer 4 on a release support made of a base film to form the inkjet receiving layer 4
- Step B A step of applying a resin for forming the fixing resin layer 1 on the ink jet receiving layer 4 formed in the step A
- Step C Before, at the same time as or after Step B, the transparent microspheres 2 are sprayed on the ink-jet receiving layer 4 or the resin forming the fixing resin layer 1 so that the transparent microspheres 2 are buried.
- Step D If necessary, a resin for forming the transparent resin layer 5 is applied to the transparent microsphere 2 side of the fixing resin layer 1 in which the transparent microspheres 2 are embedded to form the transparent resin layer 5.
- the process of Step E Step of laminating the reflective layer 3 on the transparent microsphere 2 side of the fixed resin layer 1 in which the transparent microspheres 2 are embedded, or on the transparent resin layer 5;
- Step F If necessary, an adhesive resin for forming the adhesive layer 7 is applied on the reflective layer 3 to form the adhesive layer 7;
- Step G If necessary, the step of bonding the reflective layer 3 or the adhesive layer 7 and the support 6;
- Process H The process of peeling the support body for mold release.
- the base film of the release support used in Step A is not particularly limited as long as it functions as a support, and examples thereof include polyester films such as polyethylene terephthalate and polyethylene naphthalate. .
- a solution for forming the ink jet receiving layer 4 in which each component constituting the polyurethane resin is dispersed or dissolved is applied to the transparent microsphere 1 side. It may be heated and dried in accordance with In the step A, the ink-jet receiving layer 4 forming solution to be used, forming conditions, and the like are the same as in the case of forming the ink-jet receiving layer 4 in the production of the semi-open type retroreflective material.
- step B the resin for forming the fixing resin layer 1 may be applied onto the ink jet receiving layer 4 by a known resin coating method.
- the formation of the fixing resin layer 1 in which the transparent microspheres 2 are buried is performed by burying the transparent microspheres 2 so as to have a predetermined burying ratio before the resin forming the fixing resin layer 1 is solidified. In this state, the resin forming the fixing resin layer 1 is solidified.
- the size and density of the transparent microspheres 2 to be used are taken into account, and then the application density and viscosity of the resin forming the fixing resin layer 1 are adjusted as appropriate to fix the transparent microspheres 2. What is necessary is just to control the embedding rate to the resin layer 1 side.
- the step D is performed when the transparent resin layer 5 is provided between the transparent microspheres 2 and the reflective layer 3.
- coating to the transparent microsphere side of resin which forms the transparent resin layer 5 should just be performed by the well-known resin coating method.
- the formation of the reflective layer 3 in the step E may be performed by a known metal film forming method such as vapor deposition, sputtering, chemical vapor deposition, or plating. As a method for forming the reflective layer 3, vapor deposition is preferably used.
- the adhesive resin for forming the adhesive layer 7 may be applied on the reflective layer 3 by a known resin coating method.
- the step G is a step performed as necessary when the support 5 is provided.
- the method for bonding the reflective layer 3 or the adhesive layer 7 and the support 6 is not particularly limited, and can be performed by, for example, a known laminating method.
- Separation of the release support in the step H may be performed immediately after the step F or G, or may be performed immediately before ink jet printing on the ink jet receiving layer 4.
- inkjet receptive layer forming solution (1) Inkjet receptive layer forming solution A 354 parts by weight of diethyl carbonate and 708 parts by weight of 1,6-hexanediol were reacted at 120 to 200 ° C. for 15 hours, then cooled to 150 ° C., and the pressure was reduced to 30 to 50 mmHg. 786 parts by weight of polycarbonate polyol was obtained. The polyol has a hydroxyl value of about 427. In this polyol, 236 parts by weight of 1,6-hexanediol and 920 parts by weight of 1,10-decanedicarboxylic acid were added, reacted at about 200 to 220 ° C.
- polycarbonate polyester polyol had a molecular weight of about 1647 and a hydroxyl value of about 68. After reacting 150 parts by weight of this polyol, 5 parts by weight of 1,6-hexanediol, 20 parts by weight of isophoronediamine (IPDA) and 60 parts by weight of water-added MDI at about 80 to 120 ° C.
- IPDA isophoronediamine
- isopropanol / toluene (1 1) A polyurethane resin solution having a solid content concentration of 30% and a viscosity of 860 poise was obtained by dissolving in 548 parts by weight of a mixed solvent. Furthermore, 100 parts by weight of the obtained polyurethane resin solution, 90 parts by weight of toluene and 90 parts by weight of isopropanol were mixed, and this was used as an inkjet receiving layer forming solution A.
- This polyol had a molecular weight of about 1513 and a hydroxyl value of 74.
- This polyol 150 parts by weight, 1,4-butanediol 5 parts by weight, isophorone diisocyanate (IPDI) 45 parts by weight, water-added MDI 14.5 parts by weight and IPDA 21.5 parts by weight were reacted, and then dissolved in dimethylformamide.
- a polyurethane resin solution having a solid content concentration of 30% and a viscosity of 660 poise was obtained.
- 100 parts by weight of the obtained polyurethane resin solution, 90 parts by weight of toluene, and 90 parts by weight of isopropanol were mixed, and this was used as an inkjet receiving layer forming solution B.
- Solution C for forming an ink jet receiving layer A polycarbonate polyol was prepared in the same manner as in the case of the inkjet receiving layer forming solution A. Using 1223 parts by weight of the obtained polycarbonate polyol, 767 parts by weight of 1,10-decanedicarboxylic acid and 146 parts by weight of adipic acid, a polycarbonate polyester polyol having a molecular weight of 1979 and a hydroxyl value of 56.6 was obtained in the same manner as in Example 1. It was. After reacting 150 parts by weight of this polyol, 6 parts by weight of 1,6-hexanediol, 53 parts of water-added MDI and 17.2 parts by weight of IPDA at about 80 to 120 ° C.
- a mixed solvent of isopropanol / toluene (1: 1) A polyurethane resin solution having a solid content concentration of 30% and a viscosity of 860 poise was obtained by dissolving in 548 parts by weight. Furthermore, 100 parts by weight of the obtained polyurethane resin solution, 90 parts by weight of toluene and 90 parts by weight of isopropanol were mixed, and this was used as an inkjet receiving layer forming solution C.
- Inkjet receptor layer forming solution D A mixed solution composed of 100 parts by weight of polyurethane (trade name “Chrisbon 3006LV”, manufactured by DIC Corporation), 90 parts by weight of toluene, and 90 parts by weight of IPA was prepared as Solution D for forming an inkjet receiving layer. It has been confirmed that the polyurethane contained in the inkjet receiving layer-forming solution D is not a polyurethane resin containing, as structural units, a polycarbonate polyol, a dicarboxylic acid having 3 to 15 carbon atoms, and a polyisocyanate.
- Inkjet receiving layer forming solution E Prepare a mixed solution consisting of 100 parts by weight of urethane acrylic polymer (trade name “HC10”, manufactured by Chokwang Paint Co Ltd) and 3 parts by weight of a curing agent (trade name “HC10 Hardner”, manufactured by Chokwang Paint Co Ltd), Inkjet receiving layer forming solution E was obtained.
- polyester-cotton taffeta fabric used as the support and the fixing resin layer were bonded by a hot press at 130 ° C., and then the release support was peeled off.
- an intermediate of a retroreflective material in which polyester-cotton taffeta woven fabric (support) / PET (fixed resin layer) / aluminum film (reflective layer) / transparent resin layer / transparent glass sphere is laminated in this order is obtained. It was.
- the embedding rate of the transparent microspheres in the fixed resin layer in the intermediate of the obtained retroreflective material was 50%.
- Example 1 10 mg / cm 2 of the ink-jet receiving layer forming solution A is applied to the transparent glass sphere side of the intermediate of the retroreflective material obtained as described above, and dried at a temperature of 110 ° C. for 3 minutes to receive the ink jet. A layer was formed to produce a retroreflective material (1 m ⁇ 1 m).
- the formed inkjet receiving layer had a layer thickness L (90 °) of 3.66 ⁇ m and a layer thickness L (45 °) / layer thickness L (90 °) of 1.28.
- Example 2 A retroreflective material was produced under the same conditions as in Example 1 except that the inkjet receiving layer forming solution B was used instead of the inkjet receiving layer forming solution A.
- the formed ink jet receiving layer had a layer thickness L (90 °) of 3.00 ⁇ m and a layer thickness L (45 °) / layer thickness L (90 °) of 1.39.
- Example 3 A retroreflective material was produced under the same conditions as in Example 1 except that the inkjet receiving layer forming solution C was used instead of the inkjet receiving layer forming solution A.
- the formed inkjet receiving layer had a layer thickness L (90 °) of 3.17 ⁇ m and a layer thickness L (45 °) / layer thickness L (90 °) of 1.30.
- Comparative Example 1 A retroreflective material was produced under the same conditions as in Example 1 except that the inkjet receiving layer forming solution D was used instead of the inkjet receiving layer forming solution A.
- the formed inkjet receiving layer had a layer thickness L (90 °) of 3.28 ⁇ m and a layer thickness L (45 °) / layer thickness L (90 °) of 1.34.
- Comparative Example 2 A retroreflective material was produced under the same conditions as in Example 1 except that the inkjet receiving layer forming solution E was used instead of the inkjet receiving layer forming solution A.
- the formed inkjet receiving layer had a layer thickness L (90 °) of 3.72 ⁇ m and a layer thickness L (45 °) / layer thickness L (90 °) of 1.34.
- Ink-jet printing solvent for retroreflective material Solvent ink SC22 series (Magenta, cyan, yellow, and black; manufactured by MIMAKI ENGINEERING CO., LTD.) Is used as the ink jet printer. Inkjet printing was performed on the inkjet receptive layer of each retroreflective material obtained above so that the colors shown in Tables 1 and 2 were obtained. Ink-jet printing printed one color on the entire surface per sheet of retroreflective material. The printing conditions of the ink jet printer were set to 48 passes and a drying temperature of 50 ° C.
- washing resistance 4-1 Daytime color (appearance color) visually recognized by inkjet printing Each retroreflective material subjected to inkjet printing was cut into 50 mm ⁇ 250 mm, and the cut retroreflective material was attached to a load cloth (50 mm ⁇ 250 mm) compatible with ISO 6330 using a hot melt adhesive, and ISO 6330- Washing was repeated according to the conditions specified in the 2A method (washing temperature 60 ° C.).
- L *, a *, b * were determined for the retroreflective material before washing, after 10 washings, and after 30 washings. Specifically, first, according to JIS Z 9117 “Retroreflective material”, a D65 light source defined by CIE (International Commission on Illumination) is used to face the sample from an angle of 45 ° with respect to the normal of the sample surface. L *, a *, and b * were obtained by irradiating and receiving reflected light having an angle of 0 ° with the normal of the sample surface using a spectrocolorimeter (SC10T45 manufactured by Suga Test Instruments). The measurement was performed on the center point of the sample.
- CIE International Commission on Illumination
- FIG. 7 shows a chromaticity diagram in which a * and b * of each retroreflective material is plotted before washing, after 10 washings, and after 30 washings.
- a *, b *, L *, and C * (saturation) were obtained from the obtained x, y, and L. Further, the difference between C * before washing and after 10 washings was calculated as ⁇ C * 1, and the difference between C * before washing and after 30 washings was calculated as ⁇ C * 2.
- FIG. 8 shows a chromaticity diagram in which a * and b * of each retroreflective material is plotted before washing, after washing 10 times, and after washing 30 times.
- a retroreflective material in which an inkjet receiving layer was formed using a polyurethane resin containing polycarbonate polyol, a dicarboxylic acid having 3 to 15 carbon atoms, and a polyisocyanate as structural units (Examples 1 to 3)
- the difference in C * (saturation) before and after washing was small, and it was confirmed that the retroreflective performance was stably maintained even after washing.
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Abstract
Description
項1. 固着樹脂層と、
前記固着樹脂層に埋設された透明性微小球と、
入射光側とは反対側の前記透明性微小球の面側に設けられた反射層と、
入射光側の最表面に設けられたインクジェット受容層と、
を備え、
前記透明性微小球の屈折率が1.6~2.5であり、
前記インクジェット受容層が、ポリカーボネートポリオールと、炭素数3~15のジカルボン酸と、ポリイソシアネートとを構成単位として含むポリウレタン樹脂を含有することを特徴とする、再帰性反射性材料。
項2. 前記ポリウレタン樹脂が、ポリカーボネートポリオールと炭素数3~15のジカルボン酸とを反応させてポリカーボネートポリエステルポリオールを合成した後に、当該ポリカーボネートポリエステルポリオールとポリイソシアネートとを反応させて得られるポリウレタン樹脂である、項1に記載の再帰性反射性材料。
項3. 前記ジカルボン酸の炭素数が8~12である、項1又は2に記載の再帰性反射性材料。
項4. 前記ポリカーボネートポリオールが、炭素数2~20の脂肪族ジヒドロキシ化合物と、炭素数2~20のジアルキルカーボネート及び/又は炭素数6~14のジアリールカーボネートとのエステル交換反応により得られるポリカーボネートポリオールである、項1~3のいずれかに記載の再帰性反射性材料。
項5. 前記ポリイソシアネートが、芳香族ジイソシアネート及び/又は炭素数5~18の脂環式イソシアネートである、項1~4のいずれかに記載の再帰性反射性材料。
項6. 前記透明性微小球が、前記固着樹脂層よりも入射光側に設けられ、
前記反射層が、前記透明性微小球と前記固着樹脂層の間に設けられ、且つ
前記インクジェット受容層が、透明性微小球の入射光側に設けられている、項1に記載の再帰性反射性材料。
項7. 前記インクジェット受容層の入射光側表面が、前記透明性微小球の球面に沿った曲面形状を有する、項6に記載の再帰性反射性材料。
項8. 前記インクジェット受容層の層厚が、前記透明性微小球の入射光側の頂点部分から側面に向かうに連れて、厚くなるように設定されている、項7に記載の再帰性反射性材料。
項9. 前記固着樹脂層に埋設されていない前記透明性微小球部分が前記インクジェット受容層の中に埋設されており、前記インクジェット受容層の入射光側表面が平坦面を形成している、項6に記載の再帰性反射性材料。
項10. 前記固着樹脂層が前記透明性微小球よりも入射光側に設けられ、
前記反射層が、入射光側とは反対側の前記透明性微小球の面側に設けられ、且つ
前記インクジェット受容層が、前記固着樹脂層の入射光側に設けられている、項1に記載の再帰性反射性材料。
本発明の再帰性反射性材料は、固着樹脂層1と、固着樹脂層1に埋設された透明性微小球2と、入射光側とは反対側の透明性微小球2の面側に設けられた反射層3と、入射光側の最表面に設けられたインクジェット受容層4とを備える。
以下、本発明の再帰性反射性材料を構成する各層や部材について、セミオープンタイプ、第1クローズドタイプ、及び第2クローズドタイプに分けて説明する。
[固着樹脂層1]
セミオープンタイプの再帰性反射性材料において、固着樹脂層1は、透明性微小球を埋設して保持する機能を果たす。
セミオープンタイプの再帰性反射性材料では、透明性微小球2は、反射層3を介して固着樹脂層1に埋設され、入射光と、前記反射層で回帰反射された出射光を透過させる機能を果たす。透明性樹脂層5を設けない場合は、透明性微小球2は、反射層3に接面した状態で埋設して存在する(図1参照)。また、透明性樹脂層5を設ける場合は、透明性微小球2は、透明性樹脂層5に接面した状態で埋設して存在する(図4参照)。
透明性微小球の埋設率(%)=(X/R)×100
R:透明性微小球1の直径
X:反射層3の入射光側の最上部又は透明性樹脂層5が設けられている場合は透明性樹脂層5の入射光側の最上部から、固着樹脂層1側に埋設している透明性微小球2表面の最下部までの長さ
セミオープンタイプの再帰性反射性材料では、反射層3は、透明性微小球2と前記固着樹脂層1の間に設けられ、透明性微小球2から入射する光を回帰反射させる機能を果たす。
セミオープンタイプの再帰性反射性材料において、インクジェット受容層4は、再帰性反射性材料の入射光側の最表面に設けられ、優れた耐洗濯性を備えさせる役割を果たす。
層厚L(90°)=Y(90°)-X(90°)
層厚L(45°)=Y(45°)-X(45°)
X(90°):透明性微小球1の中心点から面方向に対して90°方向での透明性微小球1とインクジェット受容層4との界面までの距離
Y(90°):透明性微小球1の中心点から面方向に対して90°方向でのインクジェット受容層4の入射光側表面までの距離
X(45°):透明性微小球1の中心点から面方向に対して45°方向での透明性微小球1とインクジェット受容層4との界面までの距離
Y(45°):透明性微小球1の中心点から面方向に対して45°方向でのインクジェット受
容層4の入射光側表面までの距離
更に、前記ポリカーボネートポリエステルポリオールは、ポリカーボネートポリオール及び炭素数3~15ジカルボン酸の他に、ジヒドロキシ化合物が添加されて重合したものであってもよい。ポリカーボネートポリエステルポリオールの製造に使用されるジヒドロキシ化合物の具体例や好ましいもの等については、前記ポリカーボネートポリオールの構成単位として使用されるジヒドロキシ化合物と同様である。前記ポリカーボネートポリエステルポリオールの製造において、ポリカーボネートポリオール及び炭素数3~15ジカルボン酸と共に、ジヒドロキシ化合物を添加する場合、当該ジヒドロキシ化合物の比率については、特に制限されないが、例えば、ポリカーボネートポリオール100重量部当たり、ジヒドロキシ化合物が20~40重量部、好ましくは25~35重量部が挙げられる。
セミオープンタイプの再帰性反射性材料では、透明性樹脂層5は、透明性微小球2と反射層3の間に、必要に応じて設けられる層であり、反射輝度を調整したり、出射される光の色調を変化させたりする機能を果たし、更に反射層3が金属膜の場合には、その腐食を抑制する機能も果たす。
セミオープンタイプの再帰性反射性材料では、支持体5は、必要に応じて設けられる部材であり、固着樹脂層4を保持する基材としての機能を果たす。支持体6は、例えば流通段階では設けられていなくてよい。また、支持体6は、固着樹脂層1に対して直接積層されていてもよいが、接着剤で形成される接着層を介して固着樹脂層1と積層されていてもよい。
[固着樹脂層1]
第1クローズドタイプの再帰性反射性材料では、固着樹脂層1は、セミオープンタイプの場合と同様に、透明性微小球を埋設して保持する機能を果たす。
第1クローズドタイプの再帰性反射性材料では、透明性微小球2は、セミオープンタイプの場合と同様に、反射層3を介して固着樹脂層1に埋設され、入射光と、前記反射層で回帰反射された出射光を透過させる機能を果たす。
第1クローズドタイプの再帰性反射性材料では、反射層3は、セミオープンタイプの場合と同様に、透明性微小球2と前記固着樹脂層1の間に設けられ、透明性微小球2から入射する光を回帰反射させる機能を果たす。
第1クローズドタイプの再帰性反射性材料において、インクジェット受容層4は、セミオープンタイプの場合と同様に、再帰性反射性材料の入射光側の最表面に設けられ、優れた耐洗濯性を備えさせ、洗濯を繰り返しても昼間色と夜間色を安定に維持させる役割を果たす。
第1クローズドタイプの再帰性反射性材料では、透明性樹脂層5は、セミオープンタイプの場合と同様に、透明性微小球2と反射層3の間に、必要に応じて設けられる層であり、反射輝度を調整したり、出射される光の色調を変化させたりする機能を果たし、更に反射層3が金属膜の場合には、その腐食を抑制する機能も果たす。
第1クローズドタイプの再帰性反射性材料では、支持体5は、セミオープンタイプの場合と同様に、必要に応じて設けられる部材であり、固着樹脂層4を保持する基材としての機能を果たす。
[固着樹脂層1]
第2クローズドタイプの再帰性反射性材料では、固着樹脂層1は、透明性微小球を埋設して保持する機能と共に、入射光を透明性微小球2に透過させる機能も果たす。
第2クローズドタイプの再帰性反射性材料では、透明性微小球2は、セミオープンタイプの場合と同様に、反射層3を介して固着樹脂層1に埋設され、入射光と、前記反射層で回帰反射された出射光を透過させる機能を果たす。
透明性微小球2の埋設率(%)=(X/R)×100
R:透明性微小球2の直径
X:固着樹脂層1の最下部(入射光側とは反対側の固着樹脂層1の面の最深部)から、固着樹脂層1側に埋設している透明性微小球2表面の最上部(入射光側の頂点)までの長さ
第2クローズドタイプの再帰性反射性材料では、反射層3は、入射光側とは反対側の透明性微小球2の面側に設けられ、透明性微小球2から入射する光を回帰反射させる機能を果たす。
第2クローズドタイプの再帰性反射性材料において、インクジェット受容層4は、固着樹脂層1の入射光側に設けられ、優れた耐洗濯性を備えさせ、洗濯を繰り返しても昼間色と夜間色を安定に維持させる役割を果たす。
第2クローズドタイプの再帰性反射性材料では、透明性樹脂層5は、透明性微小球2と反射層3の間に、必要に応じて設けられる層であり、反射輝度を調整したり、出射される光の色調を変化させたりする機能を果たし、更に反射層3が金属膜の場合には、その腐食を抑制する機能も果たす。
第2クローズドタイプの再帰性反射性材料において、接着層7は、支持体との接着性を付与するために、必要に応じて、反射層3の入射光側とは反対側の面に設けられる層である。
第2クローズドタイプの再帰性反射性材料では、支持体5は、入射光側とは反対側の接着層7の面に、必要に応じて設けられる部材であり、再帰性反射性材料の形状を保持させる基材としての機能を果たす。
本発明の再帰性反射性材料は、文字、記号、図柄等の模様をインクジェット印刷によってプリントするのに適した特性を備えており、インクジェット印刷の被印刷物として利用できる。中でも、顔料を揮発性の溶剤に分散したインク、所謂ソルベントインクを用いてインクジェット印刷を行う場合に、特に好適である。ソルベントインクの中でも、ビニル系樹脂をバインダー樹脂として含むものがより一層好ましい。
本発明の再帰性反射性材料を製造する方法は、前述する構成を備えさせ得ることを限度として、特に制限されないが、以下、その好適な一例をセミオープンタイプ、第1クローズドタイプ、及び第2クローズドタイプに分けて説明する。
セミオープンタイプの再帰性反射性材料の製造方法の好適な一例として、下記工程1~6を含む方法が挙げられる。
工程1:基材フィルム上に熱可塑性フィルムを積層させた離型用支持体を、当該熱可塑性フィルムの軟化点以上の温度で加熱して当該熱可塑性フィルムを軟化させる工程、
工程2:前記工程1の前、同時又は後に、離型用支持体の熱可塑性フィルムに透明性微小球2を散布し、透明性微小球2が軟化した熱可塑性フィルムに所定の割合で埋没した時点で冷却して前記熱可塑性フィルムを硬化させ、透明性微小球2が埋設した離型用支持体を得る工程、
工程3:透明性微小球2を埋設した離型用支持体の透明性微小球2側に、必要に応じて、透明性樹脂層5を形成する樹脂を塗布し、透明性樹脂層5を形成する工程、
工程4:透明性微小球2を埋設した離型用支持体の透明性微小球2側に、又は透明性樹脂層上5に、反射層3を積層させる工程、
工程5:反射層3上に、固着樹脂層1を形成する樹脂を塗布し、固着樹脂層1を積層させる工程、及び
工程6:離型用支持体を剥離した後に、透明性微小球2側にインクジェット受容層4を形成する樹脂を塗布し、透明性微小球3の球面に沿った曲面形状を有するようにインクジェット受容層4を形成する工程、
工程7:前記工程6の前又は後に、必要に応じて、固着樹脂層1と支持体6を接着させる工程。
第1クローズドタイプの再帰性反射性材料の製造方法の好適な一例は、前記セミオープンタイプの再帰性反射性材料の製造方法における工程6を下記工程6’に変更すること以外は、前記セミオープンタイプの再帰性反射性材料の製造方法と同様である。
工程6’:離型用支持体を剥離した後に、透明性微小球2側にインクジェット受容層4を形成する樹脂を塗布して透明性微小球3を埋没させ、インクジェット受容層4の入射光側表面が平坦面になるようにインクジェット受容層4を形成する工程。
第2クローズドタイプの再帰性反射性材料の製造方法の好適な一例として、下記工程A~Hを含む方法が挙げられる。
工程A:基材フィルムからなる離型用支持体上にインクジェット受容層4を形成する樹脂を塗布し、インクジェット受容層4を形成する工程、
工程B:前記工程Aで形成したインクジェット受理層4上に、固着樹脂層1を形成する樹脂を塗布する工程、
工程C:前記工程Bの前、同時又は後に、前記インクジェット受容層4上又は固着樹脂層1を形成する樹脂上に透明性微小球2を散布し、透明性微小球2が埋没した固着樹脂層1を形成する工程、
工程D:透明性微小球2を埋設した前記固着樹脂層1の透明性微小球2側に、必要に応じて、透明性樹脂層5を形成する樹脂を塗布し、透明性樹脂層5を形成する工程、
工程E:透明性微小球2を埋設した前記固着樹脂層1の透明性微小球2側に、又は透明性樹脂層5上に、反射層3を積層させる工程、
工程F:必要に応じて、反射層3上に、接着層7を形成する接着性樹脂を塗布し、接着層7を形成する工程、
工程G:必要に応じて、反射層3又は接着層7と支持体6を接着させる工程、
工程H:離型用支持体を剥離する工程。
(1)インクジェット受容層形成用溶液A
ジエチルカーボネート354重量部及び1,6-ヘキサンジオール708重量部を120~200℃で15時間反応させ、その後150℃に冷却し、減圧して30~50mmHgとして残留するエタノールを十分に留去し、786重量部のポリカーボネートポリオールを得た。このポリオールの水酸基価は約427である。このポリオール中に1,6-ヘキサンジオール236重量部と1,10-デカンジカルボン酸920重量部を入れ、約200~220℃で8時間反応させ、30~50mmHgで減圧反応を行い、最終的に1750重量部のポリカーボネートポリエステルポリオールを得た。このポリオールの分子量は約1647であり、且つその水酸基価は約68であった。このポリオール150重量部、1,6-ヘキサンジオール5重量部、イソホロンジアミン(IPDA)20重量部、水添加MDI60重量部を約80~120℃で約8時間反応させた後、イソプロパノール/トルエン(1:1)混合溶剤548重量部に溶解し、固形分濃度30%で粘度860ポイズのポリウレタン樹脂溶液を得た。更に、得られたポリウレタン樹脂溶液100重量部、トルエン90重量部及びイソプロパノール90重量部を混合し、これをインクジェット受容層形成用溶液Aとした。
ジフェニルカーボネート1884重量部、1,4-ブタンジオール270重量部及び1,6ヘキサンジオール708重量部を150~210℃で18時間反応を行い、30~50mmHgに減圧し、脱フェノールを充分に行い1134重量部のポリカーボネートポリオールを得た。このポリオール中に460重量部の1,10-デカンジカルボン酸を加え、200~220℃で8時間反応し、30~50mmHgに減圧し、最終的に1500重量部のポリカーボネートポリエステルポリオールを得た。このポリオールの分子量は約1513であり、かつその水酸基価は74であった。このポリオール150重量部、1,4-ブタンジオール5重量部、イソホロンジイソシアネート(IPDI)45重量部、水添加MDI 14.5重量部およびIPDA21.5重量部を反応させて、次いでジメチルホルムアミドに溶解し、固形分濃度30%で粘度が660ポイズのポリウレタン樹脂溶液を得た。更に、得られたポリウレタン樹脂溶液100重量部、トルエン90重量部及びイソプロパノール90重量部を混合し、これをインクジェット受容層形成用溶液Bとした。
インクジェット受容層形成用溶液Aの場合と同様の方法でポリカーボネートポリオールを調製した。得られたポリカーボネートポリオール1223重量部、1,10-デカンジカルボン酸767重量部及びアジピン酸146重量部を使用し、実施例1と同様にして分子量1979、水酸基価56.6のポリカーボネートポリエステルポリオールを得た。このポリオール150重量部、1,6-ヘキサンジオール6重量部、水添加MDI53部及びIPDA17.2重量部を約80~120℃で約8時間反応させた後イソプロパノール/トルエン(1:1)混合溶剤548重量部に溶解し、固形分濃度30%で粘度860ポイズのポリウレタン樹脂溶液を得た。更に、得られたポリウレタン樹脂溶液100重量部、トルエン90重量部及びイソプロパノール90重量部を混合し、これをインクジェット受容層形成用溶液Cとした。
ポリウレタン(商品名「クリスボン3006LV」、DIC株式会社製)100重量部、トルエン90重量部及びIPA90重量部からなる混合液を調製し、インクジェット受容層形成用溶液Dとした。インクジェット受容層形成用溶液Dに含まれるポリウレタンは、リカーボネートポリオールと、炭素数3~15のジカルボン酸と、ポリイソシアネートとを構成単位として含むポリウレタン樹脂ではないことが確認されている。
ウレタンアクリルポリマー(商品名「HC10」、Chokwang Paint Co Ltd社製)100重量部、及び硬化剤(商品名「HC10 Hardner」、Chokwang Paint Co Ltd社製)3重量部からなる混合液を調製し、インクジェット受容層形成用溶液Eとした。
離型用支持体として、厚さ75μmのポリエステルフィルムにラミネートされた厚さ40μmのポリエチレンフィルムを使用し、これを連続的に200℃で2分間加熱して、ポリエチレンフィルムを溶融させた。この状態で、透明性微小球として、平均粒径50μm、屈折率2.25の透明ガラス球を220~300個/mm2となるように略一面に散布し、放冷してポリエチレンフィルムを硬化させた。次いで、離型用支持体上の透明ガラス球側に下記組成の透明性樹脂層形成用溶液を27g/m2塗布し、温度155℃、時間1
.5分の条件で乾燥させ、透明性樹脂層を形成した。
(透明性樹脂層形成用溶液組成)
ポリウレタン樹脂(純分):1.5質量%
トルエン(純度99%以上):49.25質量%
シクロヘキサノン(純度99%以上):49.25質量%
粘度:7秒(25℃、ザーンカップ法No.3)
実施例1
前記で得られた再帰性反射性材料の中間体の透明ガラス球側に、前記インクジェット受容層形成用溶液Aを10mg/cm2塗布し、温度110℃、3分間の条件で乾燥させてインクジェット受容層を形成させ、再帰性反射性材料(1m×1m)を製造した。形成されたインクジェット受容層の層厚L(90°)は3.66μm、層厚L(45°)/層厚L(90°)は1.28であった。
インクジェット受容層形成用溶液Aの代わりに、インクジェット受容層形成用溶液Bを使用したこと以外は、前記実施例1と同条件で再帰性反射性材料を製造した。形成されたインクジェット受容層の層厚L(90°)は3.00μm、層厚L(45°)/層厚L(90°)は1.39であった。
インクジェット受容層形成用溶液Aの代わりに、インクジェット受容層形成用溶液Cを使用したこと以外は、前記実施例1と同条件で再帰性反射性材料を製造した。形成されたインクジェット受容層の層厚L(90°)は3.17μm、層厚L(45°)/層厚L(90°)は1.30であった。
インクジェット受容層形成用溶液Aの代わりに、インクジェット受容層形成用溶液Dを使用したこと以外は、前記実施例1と同条件で再帰性反射性材料を製造した。形成されたインクジェット受容層の層厚L(90°)は3.28μm、層厚L(45°)/層厚L(90°)は1.34であった。
インクジェット受容層形成用溶液Aの代わりに、インクジェット受容層形成用溶液Eを使用したこと以外は、前記実施例1と同条件で再帰性反射性材料を製造した。形成されたインクジェット受容層の層厚L(90°)は3.72μm、層厚L(45°)/層厚L(90°)は1.34であった。
溶剤インクジェットプリンタとして株式会社ミマキエンジニアリング社製商品名CJV30-130を用い、インクとして株式会社ミマキエンジニアリング社製ソルベントインクSC22シリーズ(マゼンタ、シアン、黄、及び黒;ビニル系樹脂をバインダーとして含有)を用いて、表1及び2に記載の各色となるよう、前記で得られた各再帰性反射性材料のインクジェット受容層にインクジェット印刷を行った。インクジェット印刷は、再帰性反射性材料1枚当たり1色を全面に印刷した。なお、前記インクジェットプリンタの印刷条件は、パス数48、乾燥温度50℃に設定した。
4-1.インクジェット印刷によって視認される昼間色(外観色)
インクジェット印刷を行った各再帰性反射性材料を、それぞれ50mm×250mmにカットし、カットした再帰性反射性材料をISO6330対応負荷布(50mm×250mm)にホットメルト接着剤を用いて貼付け、ISO6330-2A法(洗濯温度60℃)に規定される条件に従って洗濯を繰り返した。
前記同条件で、再帰性反射性材料について洗濯を行った。次いで、洗濯前、上記洗濯回数10回後、及び上記洗濯回数30回後の再帰性反射性材料について、再帰反射光の彩度を求めた。具体的には、JIS Z 9117 「再帰性反射材」に準じ、各再帰性反射材を20cm×20cmにカットしたものをサンプルとし、CIE(国際照明委員会)が規定するA光源を用い、観測角0.2°、入射角を30°の角度で測色計(トプコン社製BM-5AS)を用いてx、y、及びL(x、y:色度座標、L:輝度)を求めた。なお、x、y、及びLの測定は、サンプルの中心点について行った。
2 透明性微小球
3 反射層
4 インクジェット受容層
5 透明性樹脂層
6 支持体
7 接着層
Claims (10)
- 固着樹脂層と、
前記固着樹脂層に埋設された透明性微小球と、
入射光側とは反対側の前記透明性微小球の面側に設けられた反射層と、
入射光側の最表面に設けられたインクジェット受容層と、
を備え、
前記透明性微小球の屈折率が1.6~2.5であり、
前記インクジェット受容層が、ポリカーボネートポリオールと、炭素数3~15のジカルボン酸と、ポリイソシアネートとを構成単位として含むポリウレタン樹脂を含有することを特徴とする、再帰性反射性材料。 - 前記ポリウレタン樹脂が、ポリカーボネートポリオールと炭素数3~15のジカルボン酸とを反応させてポリカーボネートポリエステルポリオールを合成した後に、当該ポリカーボネートポリエステルポリオールとポリイソシアネートとを反応させて得られるポリウレタン樹脂である、請求項1に記載の再帰性反射性材料。
- 前記ジカルボン酸の炭素数が8~12である、請求項1又は2に記載の再帰性反射性材料。
- 前記ポリカーボネートポリオールが、炭素数2~20の脂肪族ジヒドロキシ化合物と、炭素数2~20のジアルキルカーボネート及び/又は炭素数6~14のジアリールカーボネートとのエステル交換反応により得られるポリカーボネートポリオールである、請求項1~3のいずれかに記載の再帰性反射性材料。
- 前記ポリイソシアネートが、芳香族ジイソシアネート及び/又は炭素数5~18の脂環式イソシアネートである、請求項1~4のいずれかに記載の再帰性反射性材料。
- 前記透明性微小球が、前記固着樹脂層よりも入射光側に設けられ、
前記反射層が、前記透明性微小球と前記固着樹脂層の間に設けられ、且つ
前記インクジェット受容層が、透明性微小球の入射光側に設けられている、請求項1に記載の再帰性反射性材料。 - 前記インクジェット受容層の入射光側表面が、前記透明性微小球の球面に沿った曲面形状を有する、請求項6に記載の再帰性反射性材料。
- 前記インクジェット受容層の層厚が、前記透明性微小球の入射光側の頂点部分から側面に向かうに連れて、厚くなるように設定されている、請求項7に記載の再帰性反射性材料。
- 前記固着樹脂層に埋設されていない前記透明性微小球部分が前記インクジェット受容層の中に埋設されており、前記インクジェット受容層の入射光側表面が平坦面を形成している、請求項6に記載の再帰性反射性材料。
- 前記固着樹脂層が前記透明性微小球よりも入射光側に設けられ、
前記反射層が、入射光側とは反対側の前記透明性微小球の面側に設けられ、且つ
前記インクジェット受容層が、前記固着樹脂層の入射光側に設けられている、請求項1に記載の再帰性反射性材料。
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JP2004524400A (ja) * | 2001-02-14 | 2004-08-12 | スリーエム イノベイティブ プロパティズ カンパニー | 可塑化ポリ塩化ビニルの代替品 |
JP2003344624A (ja) * | 2002-05-23 | 2003-12-03 | Unitika Sparklite Kk | 再帰性反射体 |
JP2005165302A (ja) * | 2003-11-14 | 2005-06-23 | Kiwa Kagaku Kogyo Kk | セキュリティ用再帰性反射シート及びその製造方法 |
JP2005208083A (ja) * | 2004-01-20 | 2005-08-04 | Unitika Sparklite Kk | 再帰反射材 |
JP2010131817A (ja) * | 2008-12-03 | 2010-06-17 | Ito Kosan Kk | 再帰反射性シート |
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WO2021084968A1 (ja) * | 2019-11-01 | 2021-05-06 | ユニチカスパークライト株式会社 | 再帰性反射性材料 |
JP2021071667A (ja) * | 2019-11-01 | 2021-05-06 | ユニチカスパークライト株式会社 | 再帰性反射性材料 |
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TW201707955A (zh) | 2017-03-01 |
DK3299853T3 (da) | 2020-06-29 |
JP6152133B2 (ja) | 2017-06-21 |
TWI688485B (zh) | 2020-03-21 |
JP2016218311A (ja) | 2016-12-22 |
US10124619B2 (en) | 2018-11-13 |
EP3299853B1 (en) | 2020-05-06 |
EP3299853A1 (en) | 2018-03-28 |
KR102561171B1 (ko) | 2023-07-28 |
US20180154668A1 (en) | 2018-06-07 |
CN107533164A (zh) | 2018-01-02 |
ES2798674T3 (es) | 2020-12-11 |
KR20180010179A (ko) | 2018-01-30 |
CN107533164B (zh) | 2019-11-01 |
EP3299853A4 (en) | 2019-03-20 |
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