JP5038810B2 - Adhesive phosphorescent elastomer molded body - Google Patents

Description

  The present invention relates to an adhesive phosphorescent elastomer molded body having an adhesive surface and an adhesive adjustment surface, and particularly to a molded body molded into a sheet or film.

  In recent years, disaster prevention goods have become indispensable as disaster prevention awareness increases. Among them, stickers and molded articles that contain sticky or adhesive surfaces, including emergency light fixtures and phosphorescent pigments, are used as those that can be night-visioned after a disaster such as an earthquake. These are in several places in complex places such as rooms, as emergency light fixtures require battery replacement, and those that contain phosphorescent pigments can only function as a night vision. It does not perform the function for safety enough. Therefore, by adding a cushioning function to such a night-viewable article, a place where cushioning material has been used so far (for example, window glass caulking, door cushioning, desk / chair corner cushioning, Attaching or attaching to insoles, memo tools, etc.) to make the area visible to night vision will reduce the chance of hitting the body even in the dark. In addition, even if it hits the body, it has a buffering function, so it is effective in preventing injury. On the other hand, if the entire surface is made of adhesive, it will cause problems in use.

  Other applications using an adhesive elastomer capable of night vision include road signs, display boards, and advertisements.

  As a molded article containing a phosphorescent pigment, Patent Document 1 discloses a phosphor in which a phosphorescent pigment is dispersed in a transparent substrate such as a glass plate, a transparent resin plate, or a film. However, Patent Document 1 does not disclose the use of a flexible elastomer as a base material or making at least one surface adhesive. Patent Document 1 describes that it is preferable to suppress phosphorescent pigments having an average particle diameter of 1 to 200 nm and a particle diameter of 400 nm or more in order to maintain visible light transmittance. Has been. However, when the particle diameter is small as in Patent Document 1, the luminance is low and the afterglow time is short.

  Patent Document 2 discloses a buffer material capable of night vision in which a phosphorescent pigment is dispersed in silicone gel or silicone rubber. Patent Document 3 discloses a concavo-convex sheet formed from an elastomer obtained from a liquid rubber raw material containing a phosphorescent pigment. This uneven pattern on the surface of the sheet is for injecting a liquid rubber raw material containing a phosphorescent pigment. However, Patent Documents 2 and 3 do not describe or suggest adjusting the tackiness of a specific surface of the cushioning material, which is the subject of the present invention.

  Patent Document 4 discloses a phosphorescent film obtained by applying a mixture of a phosphorescent pigment and an adhesive such as acrylic hot melt or UV curable rubber to one surface of the translucent film. . Patent Document 4 also discloses that a release agent is attached to the other surface of the translucent film. However, the translucent film used in Patent Document 4 is a resin such as polypropylene, polyester, or polyvinyl chloride, and does not describe the use of a flexible elastomer. Further, in the method of Patent Document 4, the film has no light resistance, and the afterglow time is shortened when an ultraviolet absorber is added to increase the light resistance.

  Patent Documents 5 and 6 disclose a phosphorescent sheet having a multilayer structure including a phosphorescent layer containing a phosphorescent pigment and a transparent or translucent resin layer. The structure of Patent Document 6 also discloses an adhesive layer and release paper provided as necessary. However, in these phosphorescent sheets, a flexible elastomer is not used, and the sheet has a multilayer structure, and the adhesive layer may be peeled off. Moreover, when an ultraviolet absorber is added in order to improve light resistance, the afterglow time becomes short.

Japanese Patent Laid-Open No. 9-95671 JP-A-8-269208 JP-A-8-238702 JP 2001-296804 A Japanese Patent Laid-Open No. 5-100624 JP 2000-290643 A

  An object of the present invention is to provide a flexible elastomer molded article having high impact absorption and efficient luminous storage, while maintaining the integrity and low surface hardness, and an adhesive surface and a surface with adjusted adhesiveness It is providing the phosphorescent flexible elastomer molded object which has this. Another object of the present invention is to provide a luminous luminous flexible elastomer molded article excellent in transparency in addition to the above-described features.

  As a result of repeated research to solve the above problems, the present inventors have provided fine irregularities and / or a thin layer on one surface of a flexible elastomer molded article containing a phosphorescent pigment, It has been found that the above problems can be solved by adjusting the adhesiveness of the surface, and the present invention has been completed.

That is, the present invention is a flexible phosphorescent elastomer molded body formed as a single body and containing a phosphorescent pigment, and has a penetration measured by using a 1/4 cone defined in ASTM D1403 on the adhesive adjustment surface . 200 or less, the surface hardness measured with a JIS K 7312 Type C durometer on the adhesion adjustment surface is 60 or less, and the adhesion strength measured with JIS Z 0237 is 90% or less of the adhesion surface The pressure-sensitive phosphorescent elastomer molded body (1) having a pressure-sensitive adhesive adjustment surface of (1) and / or (2) below adjusted to have a fine unevenness on the surface, and a smooth surface The contact surface area of which is smaller than the adhesive surface;
(2) The surface on which the non-adhesive or low-adhesive thin layer having a thickness of 0.001 to 150 μm and an adhesive strength of 90% or less of the adhesive surface is present on at least a part of the surface. (However, if the thin layer is non-tacky, the thin layer is present on a portion of the surface);
About. Furthermore, the present invention relates to a phosphorescent elastomer molded article having a light transmittance, which contains a specific amount of a phosphorescent pigment having a specific particle diameter.

  According to the present invention, an environment-friendly element molded article, particularly a sheet or film, having an adhesive surface and an adhesive adjustment surface, which has high impact absorption, exhibits phosphorescent properties, and maintains low surface hardness. It can be easily manufactured using raw materials. Moreover, transparency can be provided to the phosphorescent layer by selecting the average particle diameter, the fine particle content, and the amount of the phosphorescent pigment to be used in a specific range.

  In the flexible elastomer molded article of the present invention, the polymer constituting the elastomer is typically polyurethane, polyacrylic or polysiloxane, or a thermoplastic elastomer having a polystyrene block, and the like, and is limited thereto. It is not a thing.

The flexible elastomer molded product of the present invention exhibits excellent shock absorption as a flexible luminous elastomer molded product, and in order to make use of the function as an elastomer, 1/4 is specified in ASTM D1403 in terms of adhesion adjustment. The penetration measured with a cone is 200 or less, and the surface hardness measured with a type C durometer of JIS K 7312 on the adhesion adjusting surface is 60 or less. It is preferable that the penetration is 100 or less and the surface hardness by the type C durometer is 40 or less. The penetration is measured by dropping a conical needle into a flat sample and measuring the depth of penetration. The larger the penetration, the softer the surface. The penetration 200 is the hardness of the surface. Indicates the lower limit. Such a flexible elastomer having a low surface hardness is obtained by forming a crosslinked product having a low crosslinking density by a chemical crosslinking or a secondary crosslinking such as a hydrogen bond or an ionic bond, or a hard segment. An elastic body obtained by the formation of a crystal phase by an elastic gel.

  A polyurethane elastomer can usually be produced from a polyol and an isocyanate compound or a derivative thereof by a urethanization reaction.

  A polyol has a linear or branched molecular skeleton with a number average molecular weight of 300 to 10,000, such as polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene diol, and two ricinoleic acids. Examples thereof include bis (hydroxy fatty acid) esters obtained by combining naturally occurring hydroxyl group-containing fatty acids with diols, and one type may be used or two or more types may be used in combination. Polyether polyols, polyester polyols and mixtures thereof are preferred. In order to suppress the crosslinking density and form a crosslinked body having a low crosslinking density while using a polyol having a relatively low viscosity, a monool may be used in combination.

  The isocyanate compound contains at least two isocyanato groups in the molecule and reacts with a polyol to form a urethane bond, and is an aromatic isocyanate compound such as tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate; cyclohexylene diisocyanate, Either an alicyclic isocyanate compound such as isophorone diisocyanate or dicyclohexylmethane diisocyanate; an aliphatic isocyanate compound such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate may be used alone, or two or more may be used in combination. Good. In addition, oligomers such as biuret bodies, allophanate bodies and isocyanurate bodies of such isocyanate compounds; modified carbodiimides; and prepolymers in which an isocyanate group-containing group is bonded to the end of a polyol can be used. Isocyanate compound is a good elastomer, there is no change over time, and there is no exudation of unreacted substances and oligomers. When using a hydroxyl group of polyol or monool together, the total amount of hydroxyl group of polyol and monool The ratio of the isocyanato group to the diisocyanate, that is, the isocyanate index, is preferably in the range of 0.85 to 1.12, more preferably 0.95 to 1.10.

  In order to promote the reaction between the polyol and the isocyanate compound or derivative thereof, it is effective to use a catalyst as necessary. Examples of the catalyst include N-methylmorpholine, 1-isobutyl-2-methylimidazole, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undecene-7. Examples of amines: carboxylic acid metal salts such as tin octoate and tin naphthenate; organometallic compounds such as dibutyltin dioctate and dibutyltin dilaurate; and metal chelate compounds such as iron acetylacetonate Or two or more of them may be used in combination.

  The polyacrylic elastomer is a general term for elastomers obtained by crosslinking a poly (meth) acrylic acid ester having a functional group at a molecular terminal or a side chain with a crosslinking agent. Examples of (meth) acrylic acid esters include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate; methoxyethyl acrylate and ethoxyethyl acrylate. Examples thereof include alkoxyalkyl acrylates such as these; and methacrylic esters corresponding thereto. The poly (meth) acrylic acid elastomer is synthesized by arbitrarily polymerizing these monomers. For use as a base polymer in the present invention, as a part of the monomer, acrylic acid ester having a hydroxyl group in a side chain such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate; methacrylic acid ester corresponding to them; And / or (meth) acrylic acid such as acrylic acid or methacrylic acid is used to introduce the functional group. Examples of the functional group include a hydroxyl group and a carboxyl group. In order to selectively introduce a functional group at the molecular end, a monomer having no functional group is homopolymerized or copolymerized, and then, in the final stage, a theoretical amount of the monomer containing the functional group is introduced; After group transfer polymerization of a monomer having no functional group and a monomer containing a protective group such as trimethylsiloxy group, a method such as deprotecting the protective group present at the terminal is used. Examples of the crosslinking agent include compounds having an epoxy group, and examples of the catalyst include amines similar to polyurethane elastomers, carboxylic acid metal salts, organometallic compounds, and metal chelate compounds. Furthermore, a polyisocyanate compound, its oligomer or prepolymer can be used as a part or all of the crosslinking agent. A group of polymers having a hydroxyl group as a functional group of a polymer and having a high ratio of the isocyanate-based crosslinking agent in the crosslinking agent is referred to as a polyacryl urethane elastomer. In the present invention, a polyacryl urethane elastomer is also included in the polyacryl elastomer.

  The polyacryl urethane elastomer is a kind of the above polyacryl elastomer and is a poly (meth) having hydroxyl groups at both ends and / or one end as a part of polyol and / or monool of the polyurethane elastomer. By using an acrylate ester, it can be positioned as a (meth) acryl unit introduced into the molecule. Such reactive poly (meth) acrylates include polymethyl acrylate, polyethyl acrylate, isopropyl polyacrylate, butyl polyacrylate; and corresponding polymethacrylates, two or more (meth) Examples thereof include copolymers composed of acrylic units. As the polyol component of the isocyanate prepolymer containing the remaining polyol and / or isocyanato group, polyether polyol, polyester polyol, and the like can be used.

  Polysiloxane elastomer can be obtained by hydrosilylation reaction using platinum group compounds such as chloroplatinic acid and platinum complexes with vinyl group-containing polysiloxane as the base polymer and Si-H bond-containing polysiloxane as the crosslinking agent. it can. At this time, as the vinyl group-containing polysiloxane, either a linear polysiloxane having a vinyl group at both ends alone, or a linear polysiloxane having a vinyl group at one end as necessary is appropriately blended, By controlling the number of vinyl groups per molecule to an average of 0.4 to 2.0, preferably 1.0 to 2.0, crosslinking can be achieved while using a relatively low viscosity vinyl group-containing polysiloxane. A density can be suppressed and a crosslinked body with a low crosslinking density can be formed. The organic group bonded to the silicon atom is a monovalent unsubstituted or substituted hydrocarbon group other than the vinyl group, and is usually easy to synthesize and has a relatively low viscosity in an uncured state and is obtained by curing. Since the obtained elastomer exhibits good properties, a methyl group is common, and improvements such as the use of a phenyl group in part to impart transparency and cold resistance to the elastomer have been made.

  Thermoplastic elastomers having polystyrene blocks have polystyrene blocks as hard segments at both ends, which are soft segments such as polybutadiene blocks, polyisoprene blocks, poly (ethylene butadiene) blocks, poly (ethylene propylene) blocks. The structure is typically a polystyrene-poly (ethylene-butadiene) -polystyrene block copolymer.

Luminescent pigments used in the present invention are zinc sulfide, sulfides such as sulfide (calcium strontium); calcium aluminate, strontium aluminate, aluminate such as aluminate (calcium strontium), Sr ₂ MgSi ₂ A base compound such as a complex oxide such as O ₇ is activated with an activator such as copper, bismuth, rare earth, halogen, and in some cases, it may be further subjected to surface treatment with calcium silicate, It has long afterglow. The phosphorescent pigments may be used alone or in combination of several kinds. Mixing is particularly effective when it is necessary to emit light of a color tone other than the light emission color unique to each phosphorescent pigment.

The volume average particle diameter (D ₅₀ ) of the phosphorescent pigment (hereinafter, simply referred to as “average particle diameter”) is easily available, and does not impair the physical properties of the molded article, and an effective luminance can be obtained. 2 to 1,000 μm is preferable. The brighter the phosphorescent pigment, the brighter brightness is obtained. In order to obtain bright brightness especially with a thin sheet, a region of 10 μm or more and less than 200 μm is more preferable in order to keep the surface smooth. On the other hand, for applications that require high transparency, such as the need to read characters and figures, especially through layers containing phosphorescent pigments, white turbidity due to phosphorescent pigments does not occur, so the inclusion of fine particles with a particle size of 20 μm or less More preferably, the ratio is 30% by volume or less and the average particle size is 30 to 1,000 μm, the fine particle content is 10% by volume or less, and the average particle size is 40 to 1,000 μm. Is particularly preferred. In addition, there are two types of phosphorescent pigments: a crushed amorphous shape and a spherical shape obtained by a method such as plasma treatment. By using a spherical phosphorescent pigment, the transparency of the layer containing the phosphorescent pigment is increased. be able to.

  The compounding amount of the phosphorescent pigment requires that the molded article exhibits sufficient phosphorescent luminance and has a time that can be visually confirmed for 10 minutes or more, whereas if the phosphorescent pigment is blended in a large amount, there is no effect commensurate with it. On the contrary, since the mechanical properties and transparency of the molded article are impaired, the input index per light emitting surface is preferably 0.25 to 60.0, more preferably 0.25 to 20.0, and the afterglow time is emphasized. In that case, 1.0 to 15.0 is more preferable. When emphasizing transparency, the input index per light emitting surface is more preferably 0.25 to 50.0, even more preferably 0.25 to 12.0, and particularly preferably 0.5 to 9.0.

  The elastomer of the present invention is an ultraviolet absorber, a light stabilizer, an antioxidant, a plasticizer, an antifoaming agent, if necessary, within a range that does not adversely affect the afterglow time and transparency that are features of the present invention. You may mix | blend a dehydrating agent. For example, in order to reduce the surface hardness, the thermoplastic elastomer may be blended with 30 to 70% by weight of a hydrocarbon plasticizer compatible with the thermoplastic elastomer. Moreover, in order to improve the adhesiveness of the pressure-sensitive adhesive surface as long as the adhesiveness can be adjusted by the method of the present invention, a component for improving the adhesiveness may be copolymerized or an adhesive may be blended.

  Each of the above-mentioned elastomers other than the thermoplastic elastomer can be obtained by mixing necessary components and curing by reaction. For example, a polyurethane elastomer is mixed with a component other than an isocyanate compound to form a premix, and the isocyanate compound is mixed with a mixing means such as a stirrer, a mixer, and a mixing head, and immediately subjected to molding and curing.

  A polysiloxane elastomer is usually prepared by preparing a premix containing a base polymer and a cross-linking agent and a premix containing a base polymer and a catalyst, mixing them by the same mixing means, molding, and molding at 70 to 120 ° C. The elastomer is formed by heating for 0.5-2 hours. Alternatively, the composition containing all the components and stabilized by blending and stabilizing a reaction inhibitor such as acetylene alcohols such as 3-methyl-1-butyn-3-ol and 1-ethynyl-1-cyclohexanol is sealed. It may be stored in a container at a low temperature, extruded from the container, molded, heated to volatilize the reaction inhibitor, and cured by heating at 120 to 180 ° C. for 1 to 6 hours.

  The thermoplastic elastomer is kneaded with components such as a plasticizer and a tackifier that are blended as necessary, and is molded at a temperature of 150 ° C. or higher by a method such as press molding or extrusion molding. For example, after premixing, extrusion is performed at 200 ° C. by a twin screw extruder.

  The shape of the elastomer molded body of the present invention is not particularly limited, and a sheet or film having a three-dimensional structure such as a rectangular parallelepiped, a cube, a cylinder, or a deformed shape can be obtained when the thickness is ignored. Are also included. A sheet or film that is easily molded and has one surface that has practical adhesiveness as an adhesive substance and the other surface that has adjusted adhesiveness and is widely used in various applications. A sheet having a thickness of 0.5 to 20 mm is more preferable from the viewpoint of balance between characteristics as a light source and mechanical properties, and a sheet having a thickness of 0.5 to 5 mm is particularly preferable because a homogeneous sheet can be easily obtained. In the case of the three-dimensional structure, at least one surface is an adhesive surface, and at least one other surface, for example, a surface parallel to the adhesive surface has adjusted adhesiveness. The adhesive surface has an adhesiveness measured by JIS Z 0237, preferably 0.05 to 15 N / 20 mm, more preferably 1 to 13 N / 20 mm, depending on the purpose.

  Here, having adjusted adhesiveness means that the surface does not exhibit any adhesiveness depending on the purpose, or the adhesive strength measured by the above JIS Z 0237 is 90% of the adhesive strength of the adhesive surface. % Or less, preferably 80% or less, and 0.1% or more, preferably 1% or more. If this ratio exceeds 90%, the effect of adjusting the adhesiveness is not sufficient.

  The elastomer molded body of the present invention has, for example, as described above, (1) the surface of the adhesive adjustment surface has a small unevenness, so that the contact surface area with the target smooth surface is smaller than the adhesive surface. % Or less, preferably 95% or less; and / or (2) non-adhesive or low thickness of 0.001 to 150 μm, preferably 0.5 to 100 μm on the adhesive adjustment surface Depending on whether it has an adhesive thin layer, said adhesive surface and an adhesive adjustment surface are formed. Here, the pressure-sensitive adhesive adjustment surface may be a pressure-sensitive adhesive adjustment surface in which the same surface doubles as the above-described modes (1) and (2).

  Such an elastomer molded body can be molded by any method such as casting, casting, injection molding, transfer molding, extrusion molding, blow molding and the like. For example, an upper surface is formed by casting an elastomer composition of a type that is a fluid elastomer composition in an uncrosslinked state and forms an elastomer molded body by crosslinking into a mold having no upper surface to an arbitrary thickness. An elastomer molded body that becomes a smooth adhesive surface can be produced.

  The surface having the above-mentioned adjusted tackiness can be produced by the following method. By such a method, the surface which has adjusted adhesiveness can be formed, without raising surface hardness compared with the method of sticking a plastic film.

  The first method is to provide fine unevenness on at least one surface so that the surface area of contact with the smooth surface is smaller than that of the adhesive surface, and the surface having adjusted adhesiveness without increasing the surface hardness of the elastomer. Is formed. The irregularities may be regularly or irregularly arranged, and are typically irregular linear lines having an average depth of 0.1 to 1 mm and an average width of 0.02 to 0.2 mm. The recess has a leather-like appearance with 3 to 30 / cm.

  Such irregularities can be formed directly or indirectly by embossing or embossing. Specifically, for example, fine irregularities were formed on the specific surface of the molded flexible elastomer by adjusting the portion of the mold used for molding by providing fine irregularities at a portion corresponding to the specific surface. An adhesive surface can be formed. In the case of a thermoplastic elastomer, fine irregularities can be provided by a stamp heated to a temperature higher than the plasticizing temperature.

  Also, as another method, a release paper or release film provided with fine irregularities is prepared. For example, it is laid on one surface of a mold, and an uncured elastomer is cast or cast on the surface. The surface of the elastomer in contact with the release paper or release film can be provided with fine irregularities to form a surface having adjusted adhesiveness.

  In the second method, a non-adhesive or low-adhesive thin layer having a thickness of 0.001 to 150 μm, preferably 0.05 to 100 μm is provided on at least one surface while maintaining the integrity of the molded product. Thus, a surface having adjusted adhesiveness is formed without increasing the surface hardness of the elastomer. If the thickness of the thin layer is less than 0.001 μm, it is difficult to control the adhesiveness in a controlled manner. If the thickness exceeds 150 μm, there is no increase in the effect. Rather, physical properties other than adhesiveness such as surface hardness The effect of a thin layer appears. Here, the non-adhesive or low-adhesive thin layer refers to a thin layer having an adhesive strength of 90% or less, preferably 80% or less of the adhesive surface.

  Such a thin layer is present on at least a part of the tackiness adjusting surface. That is, the thin layer may completely cover the adhesive adjustment surface, or may partially cover the surface to such an extent that the adhesiveness of the surface is lowered according to the purpose. However, in the case where the thin layer is non-adhesive, the adhesiveness of the adhesive adjustment surface falls within the above-described range, so that the thin layer that covers a part of the adhesive adjustment surface is formed to be controlled.

Specifically, for example, a peelable substance is applied to the adhesive adjustment surface of the molded elastomer by a method such as spraying, impregnation, roll coating, brush coating, etc., diluted with a solvent as necessary. . Such peelable materials include vinylidene fluoride-hexafluoropropylene copolymers, perfluoroalkyl ethers, perfluoroalkyl ether oligomers and polymers, succinic acid bis (perfluoroalkylethyl) esters, tris (perfluoroalkyl) ethylphosphorus. Fluorine compounds such as acid esters; such as polydimethylsiloxane, polymethylphenylsiloxane, polymethyldecylsiloxane, polymethyl (3,3,3-trifluoropropyl) siloxane, for example, a viscosity at 27 ° C. of 10,000 to 3 , 000,000 mm ² / s, non-reactive high viscosity silicone oil or raw silicone rubber; hydrocarbon waxes such as polyethylene wax, paraffin wax, ceresin wax; carnauba wax, Examples include higher fatty acid ester waxes such as montan wax. As another method belonging to the second method, a transparent metal oxide layer such as indium-tin oxide or tin oxide can be formed by vacuum deposition.

  As a diluting solvent, in the case of a fluorine compound, alcohol solvents such as methanol and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; hydrocarbon solvents such as toluene, xylene and petroleum benzine can be used. In the case of silicones and waxes, hydrocarbon solvents such as toluene, xylene and petroleum benzine can be used. In addition, when the elastomer is easily attacked by contact with a solvent, the release material is applied to a mold or release paper so that it can be easily transferred, and processed at a temperature exceeding the volatilization temperature of the solvent for release. A sticky adjustment surface can be formed by forming a thin layer of a functional substance and transferring it to a specific surface of the elastomer to form a thin layer on the elastomer.

  In order to obtain the tackiness adjusting surface, the above two methods can be used in combination. That is, a peelable surface with fine irregularities may be created, and a thin film of a material having releasability may be formed on the surface. As a modification, a thin layer of a releasable substance having fine irregularities may be formed on the elastomer surface directly or by transfer.

  Hereinafter, the present invention will be described in detail by way of examples. In the preparation examples, comparative examples and examples, unless otherwise indicated, parts are parts by weight, and% of the compounding and the like indicates a weight ratio. The present invention is not limited by the examples.

The elastomer molded bodies obtained in Examples and Comparative Examples were evaluated by the following test methods.
(1) Surface hardness A sample having a thickness of 10 mm was prepared, and the surface hardness was measured with a type C durometer according to JIS K7312.
(2) Penetration A sample having a thickness of 50 mm was prepared, and the penetration was measured using a 1/4 cone defined in ASTM D1403.
(3) Adhesiveness A sample having a thickness of 2.0 mm was prepared, and the adhesive strength was measured by peeling it 180 ° according to JIS Z0237. However, about each sample of an Example, it tested about the adhesive adjustment surface and the surface which does not adjust adhesiveness.
(4) Total light transmittance A sample having a thickness of 2.0 mm was measured for the total light transmittance according to JIS K7136.
(5) Afterglow time After irradiating a sample having a thickness of 0.5 to 5.0 mm with a light source having an illuminance of 400 Lux, the time after which the afterglow from the sample was not visible in a dark place was measured. However, comparison of the method for producing the elastomer, the phosphorescent pigment, and the tackiness adjusting surface was performed using a 2.0 mm sample. Measurements were made at 15, 30, 45, and 60 minutes after irradiation, and thereafter at 30 minute intervals.

Polyacrylic elastomer preparation example 1
A pre-mix of a polyacrylic elastomer composition was prepared using the following raw materials.
A-1: Glycerin-polyoxypropylene triol (trifunctional, hydroxyl value: 18.0);
A-2: Polybutyl acrylate having a hydroxyl group at one end (monofunctional, hydroxyl value: 65)
;
C-1: tin octoate;
D-1: Sr ₂ MgSi ₂ O ₇ : Eu, Dy, average particle diameter (D ₅₀ ) 20 μm, irregular shape

  In a mixing tank equipped with a stirrer, 85 parts of A-1 and 15 parts of A-2 were taken and stirred with a stirrer to obtain a polymer mixture. To this, 0.2 part of C-1 and a necessary amount of D-1 were added, and stirring was continued at room temperature until uniform, to prepare premixes 1a to 1h. The addition amount of D-1 is a predetermined amount shown in Table 1 in consideration of the thickness of the formed sheet, and the input amount index according to the following formula, that is, the amount of D-1 per unit area of the sheet: It was determined for each sheet so that However, the thickness of the sample for testing the surface hardness and penetration was the same as that of the 2.0 mm thick sample.

Comparative Example 1
A stainless steel flat mold having an open upper surface was used. A release paper having a layer of a cross-linkable silicone release agent having no migration as a smooth release surface was laid on the bottom surface of the mold with the release surface facing up. Into the premix 1b in the mixing tank, 14 parts of the following B-1 was poured at 20 ° C. with stirring until mixing, and then defoamed with a vacuum pump to prepare a polyacryl urethane composition.
B-1: Prepolymer (NCO: 12.1%) obtained by reacting hexamethylene diisocyanate with polypropylene glycol and having isocyanate groups at both ends;
This was cast into the above mold to a thickness necessary for the above evaluation. This was transferred to a 120 ° C. hot air heating furnace and subjected to crosslinking by urethanization reaction for 10 minutes, and then heated at 70 ° C. for another 12 hours to completely cure the polyacryl urethane elastomer having a smooth and homogeneous composition on both sides. A sheet was obtained. However, the thickness of the sample for measuring the afterglow time was 2.0 mm.

Examples 1-6, A, B
The release surface has a layer of cross-linkable silicone release agent that does not migrate, and the release surface has irregular average irregularities with a depth of 0.3 to 1 mm and a width of 0.03 to 0.1 mm. Using a pre-mix 1a to 1h with a release paper having a leather-like uneven surface (texture) dispersed at 4 lines / cm, and using premixes 1a to 1h, the sample thickness and the input index of D-1 In the same manner as in Comparative Example 1, except that the sheet was changed, one surface was smooth and the other surface (adhesive adjustment surface) had a fine recess transferred from the protrusion on the release surface. A fully cured polyacrylic urethane elastomer sheet was obtained. The surface hardness, afterglow time, and tackiness of the tackiness adjusting surface of each sample were compared. The results are shown in Table 1. In addition, the adhesiveness of the adhesive surface of these sheets showed substantially the same adhesiveness as the corresponding sheet of Comparative Example 1 (see Table 3).

Preparation Example 2
A premix of an acrylic elastomer composition was prepared by changing the average particle size of the phosphorescent pigment. That is, Premixes 2a to 2f were prepared in the same manner as Preparation Example 1 except that the following phosphorescent pigment was used instead of the phosphorescent pigment D-1. The premix prepared using it is shown in parentheses.
D-2: Sr ₂ MgSi ₂ O ₇ : Eu, Dy, average particle diameter (D ₅₀ ) 40 μm, fine particle content 9 volume% or less, particle size 20 μm or less, amorphous (premix 2a)
D-3: Sr ₂ MgSi ₂ O ₇ : Eu, Dy, average particle size 40 μm (D ₅₀ ), content of fine particles having a particle size of 20 μm or less, 9% by volume, spherical shape (premix 2b)
D-4: Sr ₂ MgSi ₂ O ₇ : Eu, Dy, average particle size (D ₅₀ ) 150 μm, content of fine particles having a particle size of 20 μm or less, 4% by volume, indefinite shape (premix 2c to 2f)
The input amount index is a value for a thickness of 2 mm of the molded sample.

Comparative Example 2
A polyacryl urethane composition was prepared in the same manner as in Comparative Example 1 except that the premix 2c was used to obtain a polyacryl urethane elastomer sheet. However, the thickness of the sample for measuring the afterglow time was 2.0 mm.

Examples 7-12
Samples similar to those in Examples were prepared, and the surface hardness, total light transmittance, and afterglow time were compared. That is, Comparative Example 2 except that a release paper having the same leather-like uneven surface as used in Examples 1 to 6, A and B was laid on the bottom surface of the mold and the premixes 2a to 2f were cast. In the same manner as above, a homogeneous and completely cured polyacrylurethaneurethane elastomer sheet is obtained having one surface smooth and the other surface (tackiness adjusting surface) having fine recesses transferred from the protrusions of the release surface. It was. The surface hardness, afterglow time, total light transmittance, and tackiness of the tackiness adjusting surface of each sample were compared. However, a sample having a thickness of 2 mm was used for the afterglow time and the total light transmittance. The results are shown in Table 2. The total light transmittance was also measured for the sheet of Example 2. These results are shown in Table 2. For comparison, in Table 2, data other than the total light transmittance of Example 2 was also recorded. Moreover, the adhesiveness of the adhesive surface of these sheets showed substantially the same adhesiveness as the corresponding Comparative Example 2 sheet (see Table 3).

Examples 13 and 14
Vinylidene fluoride-hexafluoropropylene copolymer is diluted with methyl ethyl ketone to a 5% solution, spray-coated on the bottom of a stainless steel mold similar to Comparative Example 1, air-dried, and then heated to 100 ° C. until methyl ethyl ketone evaporates. By heating, a stainless steel mold having a vinylidene fluoride-hexafluoropropylene copolymer layer as a release layer was produced. In this mold, a mixture of Premix 1b (Example 13) or Premix 2c (Example 14) and B-1 is cast, and thereafter heated under the same heating conditions as in Comparative Example 1, Moving from the peeled surface, a polyacryl urethane elastomer sheet in which a 1 μm thick layer of vinylidene fluoride-hexafluoropropylene copolymer was partially formed on one surface (adhesion adjusting surface) was obtained.

Examples 15 and 16
Similar to Example 13 (Example 15) or Example on the bottom surface of a stainless steel flat box mold having fine irregularities similar to those of the release paper used in Example 1 on the bottom surface and the upper surface being opened. In the same manner as in Example 14 (Example 16), a vinylidene fluoride-hexafluoropropylene copolymer layer was formed. Using this mold, in the same manner as in Example 2, the thickness of one surface is smooth, the other surface (adhesion adjusting surface) is finely uneven, and the vinylidene fluoride-hexafluoropropylene copolymer is thick. Thus, a polyacryl urethane elastomer sheet in which a 1 μm layer was partially formed was obtained.

  The surface hardness, afterglow time, total light transmittance and adhesiveness of the polyacryl urethane elastomer sheets of Examples 13 to 16 and Comparative Examples 1 and 2 were measured. The results are shown in Table 3. However, for each example, Table 3 shows the tackiness of the tackiness adjustment surface. The adhesiveness of the adhesive surface of these polyacrylurethane elastomer sheets showed substantially the same adhesiveness as the corresponding polyacrylurethane elastomer sheets of Comparative Examples 1 and 2.

Polyurethane elastomer preparation example 3
A polyurethane elastomer composition premix was prepared according to the preparation of Premix 1b of Preparation Example 1 except that A-3 below was used instead of A-2.
A-3: n-butanol-polyoxypropylene monool (monofunctional, hydroxyl value: 16.8)
That is, 70 parts of A-1 and 30 parts of A-3 were placed in a mixing tank equipped with a stirrer, and stirred with a stirrer to obtain a polymer mixed solution. To this, 0.2 parts of C-1 and D-1 in an amount that gives an input index of 2.89 when the molded sheet thickness is 2.0 mm are added and stirred at room temperature until uniform. And premix 3 was prepared.

Comparative Example 3
A polyurethane elastomer composition was prepared in the same manner as Comparative Example 1 except that 14.76 parts of the following B-2 was poured into Premix 3.
B-2: Modified carbodiimide of diphenylmethane diisocyanate (NCO: 29.0%)
This was cast and heated in the same manner as in Comparative Example 1 in a mold laid with the same release paper as in Comparative Example 1, to obtain a polyurethane elastomer sheet having a smooth and homogeneous composition on both sides. The sheet used for the measurement of the afterglow time was 2.0 mm in thickness.

Example 17
A homogeneous and completely cured polyurethane having one surface smooth and the other surface (tackiness adjusting surface) having fine irregularities, as in Comparative Example 3, except that the same release paper as in Example 2 was used. An elastomer sheet was obtained.

Example 18
The thickness of the vinylidene fluoride-hexafluoropropylene copolymer was the same as in Example 13 except that a mold having a vinylidene fluoride-hexafluoropropylene copolymer layer as a release layer was used. A polyurethane elastomer sheet in which a layer having a thickness of 1 μm was partially formed on one surface (adhesion adjusting surface) was obtained.

Example 19
One side as in Comparative Example 3, except that a mold having fine irregularities on the bottom surface and having a vinylidene fluoride-hexafluoropropylene copolymer layer as a release layer was used. Was obtained, and the other surface (adhesion adjusting surface) had fine irregularities, and a polyurethane elastomer sheet in which a 1 μm thick layer of vinylidene fluoride-hexafluoropropylene copolymer was partially formed was obtained. .

  The surface hardness and tackiness of the polyurethane elastomer sheets of Examples 17 to 19 and Comparative Example 3 were measured. The results are shown in Table 4. However, about Examples 17-19, Table 3 shows the adhesiveness of an adhesive adjustment surface. The adhesiveness of the adhesive surfaces of the polyurethane elastomer sheets of Examples 17 to 19 was almost the same as that of the polyurethane elastomer sheet of Comparative Example 3.

Preparation Example 4
Instead of D-1 in Preparation Example 3, the following phosphorescent pigment D-5 was used.
D-5: SrAl ₂ O ₄ : Eu, Dy, average particle size (D ₅₀ ) 20 μm, irregular shape That is, 70 parts of A-1 and 30 parts of A-3 are placed in a mixing tank equipped with a stirrer, and stirred. The polymer mixture was obtained by stirring with a machine. To this, 0.2 parts of C-1 and an amount of D-5 that gives an input index of 2.89 when the molded sheet thickness is 2.0 mm are added and stirred at room temperature until uniform. And premix 4 was prepared.

Comparative Example 4
A polyurethane elastomer composition was prepared in the same manner as in Comparative Example 3 except that 14.76 parts of the following B-2 was poured into Premix 4.
B-2: Modified carbodiimide of diphenylmethane diisocyanate (NCO: 29.0%)
This was cast and heated in the same manner as in Comparative Example 1 in a mold laid with the same release paper as in Comparative Example 1, to obtain a polyurethane elastomer sheet having a smooth and homogeneous composition on both sides. The sheet used for the measurement of the afterglow time was 2.0 mm in thickness.

Example 20
A homogeneous and completely cured polyurethane having one surface smooth and the other surface (tackiness adjusting surface) having fine irregularities, except that the same release paper as in Example 2 was used. An elastomer sheet was obtained.

Example 21
The thickness of the vinylidene fluoride-hexafluoropropylene copolymer as in Comparative Example 4 except that a mold having a vinylidene fluoride-hexafluoropropylene copolymer layer as a release layer was used as in Example 13. A polyurethane elastomer sheet in which a layer having a thickness of 1 μm was partially formed on one surface (adhesion adjusting surface) was obtained.

Example 22
One surface as in Comparative Example 4 except that a mold having fine irregularities on the bottom surface and having a vinylidene fluoride-hexafluoropropylene copolymer layer as a release layer was used as in Example 15. Was obtained, and the other surface (adhesion adjusting surface) had fine irregularities, and a polyurethane elastomer sheet in which a 1 μm thick layer of vinylidene fluoride-hexafluoropropylene copolymer was partially formed was obtained. .

  The surface hardness and tackiness of the polyurethane elastomer sheets of Examples 20 to 22 and Comparative Example 4 were measured. The results are shown in Table 5. However, about Examples 20-22, Table 3 shows the adhesiveness of an adhesive adjustment surface. The tackiness of the adhesive surfaces of the polyurethane elastomer sheets of Examples 20 to 22 was almost the same as that of the polyurethane elastomer sheet of Comparative Example 4.

Preparation Example 5
Instead of D-1 in Preparation Example 3, the following phosphorescent pigment D-6 was used.
D-6: ZnS: Cu, Co, average particle diameter (D ₅₀ ) 15 μm, irregular shape That is, 70 parts of A-1 and 30 parts of A-3 are placed in a mixing tank equipped with a stirrer, and stirred by the stirrer. Thus, a polymer mixed solution was obtained. To this, 0.2 parts of C-1 and D-6 in an amount that gives an input index of 2.89 when the molded sheet thickness is 2.0 mm are added and stirred at room temperature until uniform. The premix 5 was prepared.

Comparative Example 5
A polyurethane elastomer composition was prepared in the same manner as in Comparative Example 3 except that 14.76 parts of the following B-2 was poured into Premix 5.
B-2: Modified carbodiimide of diphenylmethane diisocyanate (NCO: 29.0%)
This was cast and heated in the same manner as in Comparative Example 1 in a mold laid with the same release paper as in Comparative Example 1, to obtain a polyurethane elastomer sheet having a smooth and homogeneous composition on both sides. The sheet used for the measurement of the afterglow time was 2.0 mm in thickness.

Example 23
A homogeneous and completely cured polyurethane having one surface smooth and the other surface (tackiness adjusting surface) having fine irregularities, as in Comparative Example 5, except that the same release paper as in Example 2 was used. An elastomer sheet was obtained.

Example 24
The thickness of the vinylidene fluoride-hexafluoropropylene copolymer was the same as in Comparative Example 5 except that a mold having a vinylidene fluoride-hexafluoropropylene copolymer layer as a release layer was used. A polyurethane elastomer sheet in which a layer having a thickness of 1 μm was partially formed on one surface (adhesion adjusting surface) was obtained.

Example 25
One surface as in Comparative Example 5 except that a mold having fine irregularities on the bottom surface and having a vinylidene fluoride-hexafluoropropylene copolymer layer as a release layer was used as in Example 15. Was obtained, and the other surface (adhesion adjusting surface) had fine irregularities, and a polyurethane elastomer sheet in which a 1 μm thick layer of vinylidene fluoride-hexafluoropropylene copolymer was partially formed was obtained. .

  The surface hardness and tackiness of the polyurethane elastomer sheets of Examples 23 to 25 and Comparative Example 5 were measured. The results are shown in Table 6. However, about Examples 23-25, the table | surface shows the adhesiveness of an adhesive adjustment surface. The tackiness of the adhesive surfaces of the polyurethane elastomer sheets of Examples 23 to 25 was almost the same as that of the polyurethane elastomer sheet of Comparative Example 5.

Polysiloxane elastomer preparation example 6
A premix of a polysiloxane elastomer composition was prepared using the following raw materials.
A-4: Polydimethylsiloxane having both ends blocked with dimethylvinylsiloxy units (average polymerization degree 200);
A-5: Polydimethylsiloxane having both ends blocked with dimethylvinylsiloxy units (average polymerization degree 500);
B-3: polydimethylsiloxane blocked at both ends with dimethylhydrogensiloxy units (average degree of polymerization 22);
B-4: Polymethylhydrogensiloxane having both ends blocked with trimethylsiloxy units and comprising 40 mol% of dimethylsiloxane units and 60 mol of methylhydrogensiloxane units (average degree of polymerization 42);
C-2: platinum-tetramethyltetravinylcyclotetrasiloxane complex (platinum atom 2.0%);
D-1: Used for premix 1b.

  That is, 32 parts of A-4 and 17.5 parts of A-5 were charged into a kneader, and 9.8 parts of B-3 and 0.2 part of B-4 were blended therein, and mixed until uniform. Premix 6a was prepared. This was taken out into a container, and the kneader was thoroughly washed with xylene and dried. Then, 32 parts of A-4 and 18.5 parts of A-5 were charged into the kneader, and 0.02 part of C-2 was added thereto. A premix 6b was prepared by adding D-1 in an amount such that the input index was 2.89 and mixing until uniform. This was taken out in a container different from the premix 6a.

Comparative Example 6
Premix 6a and premix 6b were taken in equal amounts, mixed with a stirrer until uniform, and then defoamed with a vacuum pump to prepare a polysiloxane elastomer composition. This was cast into a mold similar to that in Comparative Example 1, and the conditions for curing after casting were set to 70 ° C. for 1 hour. A siloxane elastomer sheet was obtained.

Example 26
Using the same release paper as in Example 2, from the same amount of premix 6a and premix 6b, as in Comparative Example 6, one surface is smooth and the other surface (adhesive adjustment surface) is fine unevenness A homogeneous and fully cured polysiloxane elastomer sheet having a

Example 27
A composition prepared in the same manner as in Comparative Example 6 from Premix 6a and Premix 6b was cast into a mold having a vinylidene fluoride-hexafluoropropylene copolymer layer as a release layer, similar to Example 13. In the same manner as in Comparative Example 6, a polysiloxane elastomer sheet in which a 1 μm-thick vinylidene fluoride-hexafluoropropylene copolymer layer was partially formed on one surface (adhesion adjusting surface) was obtained. It was.

Example 28
One surface as in Comparative Example 6 except that a mold having fine irregularities on the bottom surface and having a vinylidene fluoride-hexafluoropropylene copolymer layer as a release layer was used as in Example 15. Is obtained, the other surface (adhesion adjusting surface) has fine irregularities, and a 1 μm thick layer of vinylidene fluoride-hexafluoropropylene copolymer is partially formed. It was.

  The penetration and tackiness of the polysiloxane elastomer sheets of Examples 26 to 28 and Comparative Example 6 were measured. The results are shown in Table 7. However, for Examples 26 to 28, Table 3 shows the tackiness of the tackiness adjustment surface. The tackiness of the adhesive surfaces of the polysiloxane elastomer sheets of Examples 26 to 28 was almost the same as that of the polysiloxane elastomer sheet of Comparative Example 6.

Styrenic thermoplastic elastomer preparation example 7
A composition containing a styrenic thermoplastic elastomer was prepared using the following raw materials.
A-6: Polystyrene-poly (ethylene butadiene) -polystyrene block copolymer;
E-1: Paraffinic process oil (viscosity at 40 ° C., 20 mm ² / s);
E-2: Hydrogenated terpene resin (softening point 150 ± 5 ° C.);
D-1: Used for premix 1b.
That is, 32.5 parts of A-6, 62.5 parts of E-1 and 5 parts of E-2 were mixed until uniform, then D-1 was added in such an amount that the input index was 2.89. Then, stirring was continued until it became homogeneous to prepare a composition.

Comparative Example 7
The composition was continuously extruded into a sheet at 200 ° C. by a twin screw extruder to obtain a styrene thermoplastic elastomer sheet having a smooth surface.

Example 29
An aluminum pressing die heated to 200 ° C. is pressed against one surface of the thermoplastic elastomer sheet obtained in the same manner as in Comparative Example 7 to provide the same uneven surface (adhesion adjusting surface) as in Example 2. A styrenic thermoplastic elastomer sheet was obtained.

Example 30
On one surface of the thermoplastic elastomer sheet obtained in the same manner as in Comparative Example 7, a vinylidene fluoride-hexafluoropropylene copolymer was spray-coated by diluting to 5% solution with methyl ethyl ketone, and after air drying, methyl ethyl ketone was It heated at 100 degreeC until it volatilized, the 1-micrometer-thick layer of the vinylidene fluoride-hexafluoropropylene copolymer was formed, and the styrene-type thermoplastic elastomer sheet was obtained.

Example 31
A 1 μm-thick vinylidene fluoride-hexafluoropropylene copolymer layer was formed on the uneven surface provided in the same manner as in Example 29 to obtain a styrene-based thermoplastic elastomer sheet. .

  The surface hardness and tackiness of the styrenic thermoplastic elastomer sheets of Examples 29 to 31 and Comparative Example 7 were measured. The results are shown in Table 8. However, about Examples 29-31, Table 6 shows the adhesiveness of an adhesive adjustment surface. The tackiness of the adhesive surfaces of the styrene thermoplastic elastomer sheets of Examples 29 to 31 was almost the same as that of the styrene thermoplastic elastomer sheet of Comparative Example 7.

  In summary, according to the present invention, an elastomer sheet in which one surface is provided with fine irregularities and / or (2) a peelable thin layer is used as an adhesive adjustment surface is provided on one surface. In either case, the surface hardness (or penetration) was not significantly changed as compared with the comparative elastomer sheet not subjected to such treatment, and the tackiness of the tackiness adjusting surface was lowered. The decrease in the tackiness on the tackiness adjustment surface was particularly remarkable when the above methods (1) and (2) were used in combination. With respect to phosphorescence, the afterglow time can be controlled by adjusting the amount of phosphorescent pigment added. In particular, with respect to transparency, it has become possible to obtain a transmittance of 60% or more by increasing the average particle diameter of the phosphorescent pigment and decreasing the content of fine particles. Further, as is clear from the comparison between Example 7 and Example 8, the transparency could be increased by using a phosphorescent pigment having a spherical shape.

  The pressure-sensitive phosphorescent elastomer molded body of the present invention has its luminous properties, flexibility, high shock absorption, and an adhesive surface and an adhesive-adjusted surface, so that it is easy to handle, and signs such as roads It is extremely useful for cushioning materials, disaster prevention products, protective materials used in homes and hospitals, etc.

Claims (6)

Is formed integrally, a flexible phosphorescent elastomer molded body containing phosphorescent pigment, at 200 or less penetration was measured using a 1/4 cone as defined in ASTM D1403 at tack adjustment surface, sticky The adjustment surface has a surface hardness measured with a JIS K 7312 type C durometer of 60 or less, and the adhesion surface and the adhesion strength measured with JIS Z 0237 are adjusted to 90% or less of the adhesion surface. (1) Adhesive phosphorescent elastomer molded body having the adhesive adjustment surface of (1) and / or (2) (1) The adhesive adjustment surface is provided with fine irregularities on the surface, and the contact surface area with the smooth surface is the adhesive surface Smaller surface;
(2) The surface on which the non-adhesive or low-adhesive thin layer having a thickness of 0.001 to 150 μm and an adhesive strength of 90% or less of the adhesive surface is present on at least a part of the surface. (However, if the thin layer is non-tacky, the thin layer is present on a portion of the surface). The phosphorescent elastomer molded product according to claim 1, wherein the phosphorescent pigment has a volume average particle diameter (D ₅₀ ) of 2 to 1,000 µm.   The phosphorescent elastomer molded article according to claim 1 or 2, wherein the amount of the phosphorescent pigment is an input amount index of 0.25 to 60.0 per light source surface. The volume average particle diameter (D ₅₀ ) of the phosphorescent pigment is 30 to 1,000 μm, the content of fine particles having a particle diameter of 20 μm or less is 30% by volume or less, and the amount of the phosphorescent pigment is the input index per light source surface. is from 0.25 to 50.0, according to claim 1 Symbol placement, phosphorescent elastomer molded body having a light transmitting property.   The shape of the phosphorescent pigment is a spherical shape, and the phosphorescent elastomer molded body having light transmittance according to any one of claims 1 to 4.   The phosphorescent elastomer molded article according to any one of claims 1 to 5, wherein the polymer that is a main component of the elastomer is polyurethane, polyacrylic or polysiloxane, or a thermoplastic elastomer having a polystyrene block.